WO2011111847A1 - 樹脂組成物 - Google Patents
樹脂組成物 Download PDFInfo
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- WO2011111847A1 WO2011111847A1 PCT/JP2011/055862 JP2011055862W WO2011111847A1 WO 2011111847 A1 WO2011111847 A1 WO 2011111847A1 JP 2011055862 W JP2011055862 W JP 2011055862W WO 2011111847 A1 WO2011111847 A1 WO 2011111847A1
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- 0 CC(C)(c1ccc(*)cc1)c(cc1)ccc1O/C1=*/CC/C(/Oc2ccc(C(C)(C)c(cc3)ccc3N=C=O)cc2)=N\C(\Oc2ccc(C(C)(C)c3ccc(*)cc3)cc2)=N1 Chemical compound CC(C)(c1ccc(*)cc1)c(cc1)ccc1O/C1=*/CC/C(/Oc2ccc(C(C)(C)c(cc3)ccc3N=C=O)cc2)=N\C(\Oc2ccc(C(C)(C)c3ccc(*)cc3)cc2)=N1 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
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- 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
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- 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
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
- C09J161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09J161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09J161/14—Modified phenol-aldehyde condensates
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- 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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
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- 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
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- 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
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/107—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by filling grooves in the support with conductive material
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- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
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- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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- 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
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/54—Inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/72—Fillers; Inorganic pigments; Reinforcing additives
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- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0209—Inorganic, non-metallic particles
Definitions
- the present invention relates to a resin composition containing a specific phenol resin. Furthermore, it is related with the adhesive film, prepreg, and circuit board using the same. Moreover, it is related with the fine wiring groove
- Patent Document 1 discloses a resin composition containing a solvent-soluble polyimide. It is described that the insulating layer formed by this composition achieves balanced resin physical properties such as surface roughness, peel strength, elastic modulus, breaking strength, breaking elongation and the like. However, the performance was not satisfactory, and nothing was described about MIT folding resistance.
- Patent Document 2 describes MIT folding resistance using a polyimide film, but does not describe any low linear thermal expansion coefficient.
- Patent Document 3 describes a resin composition using an imide skeleton resin, but does not describe any MIT folding resistance.
- the problem to be solved by the present invention is a resin composition that is excellent in laminating properties when used in an adhesive film, has a low linear thermal expansion coefficient of an insulating layer obtained by curing the resin composition, and has excellent flexibility. Is to provide.
- the present inventors have completed the present invention with a resin composition containing a specific phenol resin. That is, the present invention includes the following contents.
- a resin composition comprising (A) an imide skeleton-containing bifunctional phenol resin.
- the content of the (A) imide skeleton-containing bifunctional phenol resin is 0.1 to 30% by mass with respect to 100% by mass of the nonvolatile content in the resin composition.
- the resin composition as described.
- a prepreg characterized in that the resin composition according to any one of [1] to [6] is impregnated in a sheet-like fiber substrate made of fibers.
- a circuit board wherein an insulating layer is formed of a cured product of the resin composition according to any one of [1] to [6].
- a method for forming a fine wiring groove in an insulating layer wherein the resin composition contains an inorganic filler having an average particle size of 0.02 to 5 ⁇ m.
- [16] The method for manufacturing a trench type circuit board according to [15], further including a desmear process.
- [17] The method for producing a trench circuit board according to any one of [15] to [16], further comprising a plating step.
- [18] The method for producing a trench type circuit board according to any one of [15] to [17], further comprising a step of removing the copper layer.
- the resin composition containing a resin having an imide skeleton-containing bifunctional phenol resin of the present invention has excellent laminating properties when used in an adhesive film, and the linear thermal expansion coefficient of an insulating layer obtained by curing the resin composition Therefore, it has become possible to provide a resin composition having a low flexibility and excellent flexibility.
- FIG. 6 is a diagram showing a wiring shape of Example 3.
- 10 is a diagram showing a wiring shape of Comparative Example 4.
- FIG. 6 is a diagram showing a wiring shape of Example 3.
- the present invention is a resin composition containing (A) an imide skeleton-containing bifunctional phenol resin.
- the (A) imide skeleton-containing bifunctional phenol resin used in the present invention is not particularly limited as long as it has two phenolic hydroxyl groups and an imide skeleton in one molecule.
- the insulating layer after curing of the resin composition has an appropriate crosslinking density, and folding resistance and laminating performance are exhibited simultaneously.
- the following general formula (1) and the following general formula (4) are preferable
- the following general formula (2) and the following general formula (5) are more preferable
- the following general formula (3) and the following general formula (6) are further included.
- the following general formula (7) is even more preferable.
- R 3 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R 3 may be the same or different from each other.
- Two R3 bonded to adjacent carbon atoms may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms, and R4, R5, and R6 are each independently a hydrogen atom. , A phenyl group, or a hydrocarbon group having 1 to 10 carbon atoms.
- R7 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R7 may be the same as or different from each other. And two R7 bonded to adjacent carbon atoms may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms.
- R 3 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R 3 may be the same or different from each other.
- Two R3 bonded to adjacent carbon atoms may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms, and R4, R5, and R6 are each independently a hydrogen atom.
- a phenyl group, or a hydrocarbon group having 1 to 10 carbon atoms, and two R4, R5, and R6 may be the same as or different from each other.
- R5 and R6 bonded to the carbon atom may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms
- Y is a single bond, -SO2-, -O-, -CO-. , -C (CF3) 2-, -S-, or divalent carbonization having 1 to 20 carbon atoms Is a group selected from the original.
- R7 is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen element, and a plurality of R7 may be the same as or different from each other. And two R7 bonded to adjacent carbon atoms may be bonded to each other to form a cyclic group containing an aromatic ring having 4 to 20 carbon atoms, Y is a single bond, -SO2-, -O-, It is a group selected from —CO—, —C (CF 3) 2 —, —S—, or a divalent hydrocarbon group having 1 to 20 carbon atoms.
- Y is a group selected from a single bond, —SO 2 —, —O—, —CO—, —C (CF 3) 2 —, —S—, or a divalent hydrocarbon group having 1 to 20 carbon atoms. .
- the content of the component (A) in the resin composition is not particularly limited, but the upper limit of the content of the component (A) in the resin composition is an adhesive film. From the viewpoint of improving the laminating property of the resin composition, it is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, and more preferably 10% by mass or less, with respect to 100% by mass of the nonvolatile content in the resin composition. Is even more preferred. From the viewpoint of lowering the linear thermal expansion coefficient of the insulating layer obtained from the resin composition, the lower limit of the content of the component (A) in the resin composition is based on 100% by mass of the nonvolatile content in the resin composition. It is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 1.5% by mass or more, still more preferably 3% by mass or more, and particularly preferably 5% by mass or more.
- the weight average molecular weight of the component (A) is not particularly limited, but the upper limit of the weight average molecular weight of the component (A) is from the viewpoint of improving the laminating property of the adhesive film. 1500 or less is preferable, 1000 or less is more preferable, and 750 or less is still more preferable.
- the lower limit of the weight average molecular weight of the component (A) is preferably 200 or more, more preferably 300 or more, and still more preferably 400 or more, from the viewpoint of preventing crystallization in the resin composition varnish.
- the weight average molecular weight in the present invention is measured by a gel permeation chromatography (GPC) method (polystyrene conversion).
- the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L is measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.
- the number of folding endurances of the cured product of the resin composition containing the component (A) of the present invention can be grasped by the measuring method described in ⁇ Measurement and evaluation of MIT folding endurance> described later.
- the upper limit of the folding endurance of the cured product of the resin composition of the present invention is preferably 250 times, more preferably 300 times, still more preferably 350 times, still more preferably 400 times, even more preferably 500 times, and 800 times. Is particularly preferred, 1000 being especially preferred, and 10,000 being even more preferred.
- the lower limit of the folding endurance of the cured product of the resin composition of the present invention is preferably 50 times, more preferably 100 times, still more preferably 150 times, still more preferably 170 times, particularly preferably 190 times, and 210 times. Is particularly preferred.
- the linear thermal expansion coefficient of the cured product of the resin composition containing the component (A) of the present invention is determined by the evaluation method described in ⁇ Measurement and Evaluation of Glass Transition Temperature (Tg) and Linear Thermal Expansion Coefficient> below. be able to.
- the upper limit of the linear thermal expansion coefficient of the cured product of the resin composition of the present invention is preferably 40 ppm, more preferably 39 ppm, and still more preferably 38 ppm.
- the lower limit value of the linear thermal expansion coefficient of the cured product of the resin composition of the present invention is preferably 36 ppm, more preferably 35 ppm, still more preferably 34 ppm, still more preferably 33 ppm, particularly preferably 30 ppm, particularly preferably 15 ppm. Is particularly preferred.
- the resin composition of the present invention may contain an inorganic filler in order to further reduce the coefficient of thermal expansion of the insulating layer obtained from the resin composition.
- the inorganic filler is not particularly limited, but silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Examples thereof include barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among them, silica is preferable.
- amorphous silica, fused silica, crystalline silica, synthetic silica, pulverized silica, hollow silica, and spherical silica are preferable, and fused silica and spherical silica are more preferable. These may be used alone or in combination of two or more.
- the average particle size of the inorganic filler is not particularly limited. From the viewpoint of improving the flexibility of the insulating layer obtained from the resin composition, it is possible to form fine wiring on the insulating layer, and by laser. From the viewpoint of improving workability, it is preferably 5 ⁇ m or less, more preferably 2.5 ⁇ m or less, still more preferably 1 ⁇ m or less, still more preferably 0.7 ⁇ m or less, even more preferably 0.5 ⁇ m or less, and even more preferably 0.45 ⁇ m or less. Particularly preferred.
- the average particle size of the inorganic filler becomes too small, when the resin composition is a resin varnish, the viscosity of the resin varnish increases and the handling property is prevented from being lowered, and the dispersibility is improved.
- the average particle size is preferably 0.02 ⁇ m or more, more preferably 0.05 ⁇ m or more, further preferably 0.1 ⁇ m or more, and further preferably 0.2 ⁇ m or more. Even more preferred.
- the average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory.
- the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter.
- a laser diffraction type particle size distribution measuring device LA-500 manufactured by Horiba Ltd. can be used.
- the upper limit of the amount of inorganic filler added is 100% by mass. 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, still more preferably 55% by mass or less, and particularly preferably 50% by mass or less.
- the lower limit of the addition amount of the inorganic filler is preferably 5% by mass or more, preferably 10% by mass when the nonvolatile content in the resin composition is 100% by mass from the viewpoint of reducing the thermal expansion coefficient of the insulating layer. % Or more is more preferable, 20% by mass or more is more preferable, 30% by mass or more is further more preferable, and 35% by mass or more is particularly preferable.
- Inorganic fillers include silane coupling agents, acrylate silane coupling agents, sulfide silane coupling agents, vinyl silane coupling agents, mercaptosilane coupling agents, styryl silane coupling agents, and isocyanate silane cups. Moisture resistance and dispersibility are improved by surface treatment with surface treatment agents such as ring agents, organosilazane compounds, epoxy silane coupling agents, aminosilane coupling agents, ureido silane coupling agents, titanate coupling agents. Those are preferred. These may be used alone or in combination of two or more.
- the resin composition of the present invention can contain an epoxy resin in order to improve the heat resistance, insulation reliability, flexibility, and adhesion to the metal film of the insulating layer obtained from the resin composition.
- the epoxy resin is not particularly limited, but bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S type epoxy resin, fat Cyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, epoxy resin having butadiene structure, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin , Diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalene diol, glycidyl etherified product of phenol, and diglycidyl ether of alcohol Halides,
- epoxy resins are bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, butadiene from the viewpoint of heat resistance, insulation reliability, flexibility, and adhesion to a metal film.
- An epoxy resin having a structure is preferred.
- liquid bisphenol A type epoxy resin (“Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.), naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D” manufactured by Dainippon Ink and Chemicals, Inc.), Naphthalene type tetrafunctional epoxy resin (“HP4700” manufactured by Dainippon Ink and Chemicals, Inc.), naphthol type epoxy resin (“ESN-475V” manufactured by Tohto Kasei Co., Ltd.), epoxy resin having a butadiene structure (Daicel Chemical Industries ( "PB-3600” manufactured by Co., Ltd.), epoxy resins having a biphenyl structure ("NC3000H", “NC3000L” manufactured by Nippon Kayaku Co., Ltd., "YX4000” manufactured by Japan Epoxy Resin Co., Ltd.), and the like.
- Epicoat 828EL manufactured by Japan Epoxy Resin Co., Ltd.
- naphthalene type bifunctional epoxy resin (“HP4032
- the content of the component (C) in the resin composition is not particularly limited, but the upper limit of the content of the component (C) in the resin composition is acceptable for the film. From the viewpoint of preventing the decrease in flexibility, the content is preferably 60% by mass, more preferably 50% by mass, and still more preferably 40% by mass with respect to 100% by mass of the nonvolatile content in the resin composition.
- the lower limit of the content of the component (C) in the resin composition is 100% by mass of non-volatile content in the resin composition from the viewpoint of improving the glass transition temperature of the insulating layer and decreasing the coefficient of linear thermal expansion. 5 mass% is preferable, 10 mass% is more preferable, 15 mass% is still more preferable.
- the resin composition of the present invention may contain the component (D) in order to improve the heat resistance of the insulating layer obtained from the resin composition, improve the insulation reliability, and lower the dielectric loss tangent. it can.
- the component (D) is not particularly limited as long as it has a function of curing the epoxy resin. Specifically, the phenolic curing agent, the naphthol curing agent, the active ester curing agent, and the benzoxazine curing agent. And cyanate ester-based curing agents. These may be used alone or in combination of two or more.
- the content of the component (D) in the resin composition is not particularly limited, but the upper limit of the content of the component (D) in the resin composition is acceptable for the film. From the viewpoint of preventing the decrease in flexibility, the content is preferably 50% by mass, more preferably 45% by mass, and still more preferably 40% by mass with respect to 100% by mass of the nonvolatile content in the resin composition.
- the lower limit of the content of the component (D) in the resin composition is preferably 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition from the viewpoint of improving the glass transition temperature of the insulating layer. 10 mass% is more preferable and 15 mass% is still more preferable.
- the ratio of the number of epoxy groups in the epoxy resin (C) in the resin composition of the present invention to the total number of active hydrogen groups in the components (A) and (D) is from (1: 0.2) to (1: 2). ), Preferably (1: 0.3) to (1: 1.5), more preferably (1: 0.4) to (1: 1). If the equivalent ratio is out of the above range, the mechanical strength and water resistance of the cured product tend to decrease.
- the resin composition of the present invention can improve heat resistance and insulation reliability by containing a phenolic curing agent and a naphtholic curing agent.
- curing agent from a heat resistant and water-resistant viewpoint, the phenol type hardening
- the resin composition of this invention can reduce a dielectric loss tangent by containing an active ester type hardening
- the active ester curing agent used in the present invention has an ester group with high reaction activity such as a phenol ester compound, a thiophenol ester compound, an N-hydroxyamine ester compound, an esterified compound of a heterocyclic hydroxy compound, and an epoxy. It has a resin curing action.
- curing agent the compound which has 2 or more active ester groups in 1 molecule is preferable, and it is obtained from the compound which has polyhydric carboxylic acid, and the aromatic compound which has a phenolic hydroxyl group.
- An aromatic compound having two or more active ester groups in the molecule is more preferable, and an aromatic compound obtained from a compound having at least two or more carboxylic acids in one molecule and an aromatic compound having a phenolic hydroxyl group And an aromatic compound having two or more active ester groups in the molecule of the aromatic compound is more preferable. Further, it may be linear or multi-branched. In addition, if the compound having at least two carboxylic acids in one molecule is a compound containing an aliphatic chain, the compatibility with the epoxy resin can be increased, and if the compound has an aromatic ring, the heat resistance is increased. Can be high.
- an active ester curing agent obtained from a carboxylic acid compound and a phenol compound or a naphthol compound is preferable.
- the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
- succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid and terephthalic acid are preferred from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferred.
- phenol compound or naphthol compound examples include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenol phthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, and o-cresol.
- dihydroxybenzophenone trihydroxybenzophenone
- tetrahydroxybenzophenone Dicyclopentadienyl diphenol and phenol novolak are more preferable, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadienyl diphenol and phenol novolak are still more preferable, dicyclopentadienyl diphenol and phenol.
- Novolac is particularly preferred, and dicyclopentadienyl diphenol is particularly preferred. It may be used in combination of two or more.
- curing agent Although there is no restriction
- an active ester curing agent described in JP-A-2004-277460 can be used, and a commercially available one can also be used.
- active ester curing agents include those containing a dicyclopentadienyl diphenol structure, acetylated phenol novolacs, benzoylated phenol novolacs, etc. Among them, dicyclopentadienyl diphenol structures are preferred. The inclusion is more preferable.
- EXB9460S-65T manufactured by DIC Corporation, active group equivalent of about 223
- DC808 manufactured by Japan Epoxy Resin Co., Ltd., active group equivalent of about 149
- YLH1026 manufactured by Japan Epoxy Resin Co., Ltd., active
- Group equivalent of about 200 YLH1030 (Japan Epoxy Resin Co., Ltd., active group equivalent of about 201)
- YLH1048 Japan Epoxy Resin Co., Ltd., active group equivalent of about 245), and the like. It is preferable from the viewpoint of storage stability and the thermal expansion coefficient of the cured product.
- the resin composition of the present invention can increase the glass transition temperature of the insulating layer by containing a benzoxazine-based curing agent.
- curing agent Specifically, HFB2006M (Showa High Polymer Co., Ltd.), Pd, Fa (made by Shikoku Kasei Kogyo Co., Ltd.), etc. are mentioned. It is done.
- the resin composition of this invention can reduce a dielectric loss tangent by containing a cyanate ester type hardening
- the cyanate ester-based curing agent is not particularly limited, and is a novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester resin, dicyclopentadiene type cyanate ester resin, bisphenol type (bisphenol A type, bisphenol F type). , Bisphenol S type, etc.) cyanate ester resins, and prepolymers in which these are partially triazines. These may be used alone or in combination of two or more.
- the weight average molecular weight of the cyanate ester curing agent is not particularly limited, but is preferably 500 to 4500, and more preferably 600 to 3000.
- cyanate ester curing agent examples include, for example, bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4′-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3, Bifunctional cyanate resins such as 5-dimethylphenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) ether , Phenol novolac Examples thereof include polyfunctional cyanate resins derived from cresol novolac, dicyclopentadiene structure-containing phenol resins, prep
- cyanate ester resin As a commercially available cyanate ester resin, a phenol novolac type polyfunctional cyanate ester resin represented by the following formula (8) (manufactured by Lonza Japan Co., Ltd., PT30, cyanate equivalent 124), represented by the following formula (9): A prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified to form a trimer (Lonza Japan Co., Ltd., BA230, cyanate equivalent 232), containing a dicyclopentadiene structure represented by the following formula (10) Examples include cyanate ester resins (Lonza Japan Co., Ltd., DT-4000, DT-7000).
- n represents an arbitrary number (preferably 0 to 20) as an average value.
- n a number of 0 to 5 as an average value.
- the resin composition of the present invention can contain (E) a curing accelerator from the viewpoint of efficiently curing the resin composition.
- the curing accelerator is not particularly limited, and examples thereof include a metal curing accelerator, an imidazole curing accelerator, an amine curing accelerator, an organic phosphine compound, and an organic phosphonium salt compound.
- the metal curing accelerator examples include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin.
- organometallic complex examples include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate.
- Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate.
- organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.
- cobalt (II) acetylacetonate cobalt (III) acetylacetonate, zinc (II) acetylacetonate, zinc naphthenate, iron (III) Acetylacetonate is preferable, and cobalt (II) acetylacetonate and zinc naphthenate are particularly preferable. These may be used alone or in combination of two or more.
- the metal curing accelerator In order to efficiently cure the epoxy resin and the cyanate ester curing agent, it is preferable to use a metal curing accelerator.
- the addition amount of the metal-based curing accelerator is preferably such that the metal content based on the metal-based curing accelerator is 25 to 500 ppm, preferably 40 to 200 ppm when the nonvolatile content in the resin composition is 100% by mass. Is more preferable. If it is less than 25 ppm, it tends to be difficult to form a conductor layer having excellent adhesion to the surface of the low-roughness insulating layer, and if it exceeds 500 ppm, the storage stability and insulation of the resin composition tend to decrease. It becomes.
- imidazole curing accelerators examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2- Ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1- Cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2- Fe Louis imidazolium trimellitate, 2,4-d
- amine curing accelerators examples include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5 , 4, 0) -undecene (hereinafter abbreviated as DBU) and the like.
- trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5 , 4, 0) -undecene (hereinafter abbreviated as DBU) and the like.
- organic phosphine compounds and organic phosphonium salt compounds examples include TPP, TPP-K, TPP-S, TPTP-S, TBP-DA, TPP-SCN, and TPTP-SCN (trade name of Hokuko Chemical Co., Ltd.). .
- the content of curing accelerators other than metal-based curing accelerators such as imidazole-based curing accelerators, amine-based curing accelerators, organic phosphine compounds, and organic phosphonium salt compounds is such that the nonvolatile content in the resin composition is 100% by mass.
- the range is preferably 0.05 to 3% by mass, and more preferably 0.07 to 2% by mass. If it is less than 0.05% by mass, the adhesion strength with the underlying conductor layer tends to decrease, and if it exceeds 3% by mass, the dielectric loss tangent of the cured product tends to increase.
- the content is metal-based curing accelerator.
- other curing accelerators imidazole curing accelerators, amine curing accelerators, organic phosphine compounds, organic phosphonium salt compounds, etc.
- the resin composition of the present invention can contain (F) a thermoplastic resin from the viewpoint of improving the mechanical strength of the cured product and the film forming ability when used in the form of an adhesive film.
- thermoplastic resins include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone. Examples thereof include a resin and a polyester resin. Of these, polyvinyl acetal resin and phenoxy resin are preferable. These may be used alone or in combination of two or more.
- the thermoplastic resin preferably has a glass transition temperature of 80 ° C. or higher.
- the “glass transition temperature” here is determined according to the method described in JIS K 7197. When the glass transition temperature is higher than the decomposition temperature and the glass transition temperature is not actually observed, the decomposition temperature can be regarded as the glass transition temperature in the present invention.
- the decomposition temperature is defined as a temperature at which the mass reduction rate is 5% when measured according to the method described in JIS K 7120.
- the weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 150,000, still more preferably in the range of 15,000 to 100,000. The range is even more preferable. If it is smaller than this range, the effect of improving the film forming ability and mechanical strength tends to be insufficient. If it is larger than this range, the compatibility with the cyanate ester resin and the epoxy resin is lowered, and the surface of the insulating layer is roughened. Later roughness tends to increase.
- the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion).
- the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L is measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.
- phenoxy resin examples include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, Examples thereof include those having one or more skeletons selected from a trimethylcyclohexane skeleton. Two or more phenoxy resins may be mixed and used.
- the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
- Examples of commercially available products include 1256 and 4250 (bisphenol A skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin, and YX6954 (containing bisphenolacetophenone skeleton) manufactured by Japan Epoxy Resin. Phenoxy resin), FX280, FX293 manufactured by Toto Kasei Co., Ltd., YL7553, YL6954, YL6794, YL7213, YL7290, YL7482 manufactured by Japan Epoxy Resins Co., Ltd., and the like.
- polyvinyl acetal resin examples include those manufactured by Denki Kagaku Kogyo Co., Ltd., electrified butyral 4000-2, 5000-A, 6000-C, 6000-EP, Sekisui Chemical Co., Ltd., ESREC BH series, BX series, and KS. Series, BL series, BM series, etc. are mentioned.
- polyimide resin examples include polyimide “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd.
- linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadienes, diisocyanate compounds and tetrabasic acid anhydrides (described in JP-A-2006-37083), polysiloxane skeleton-containing polyimides (JP-A-2002-2002). And modified polyimides such as those described in JP-A No. 12667 and JP-A No. 2000-319386.
- specific examples of the polyamide-imide resin include polyamide-imide “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd.
- modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.
- polyethersulfone resin include polyethersulfone “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
- polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solven Advanced Polymers Co., Ltd.
- the content of the thermoplastic resin (F) in the resin composition is not particularly limited, but is preferably 0.5 to 20% by mass with respect to 100% by mass of the nonvolatile content in the resin composition, More preferably, it is 1 to 10% by mass.
- the blending ratio of the thermoplastic resin is less than 0.5% by mass, since the viscosity of the resin composition is low, it becomes difficult to form a uniform resin composition layer. The viscosity of the resin composition becomes too high, and it tends to be difficult to embed it in the wiring pattern on the substrate.
- the resin composition of the present invention can contain (G) rubber particles from the viewpoint of increasing the mechanical strength of the cured product and improving the stress relaxation effect.
- the rubber particles are not dissolved in an organic solvent when preparing the resin composition, are not compatible with components in the resin composition such as an epoxy resin, and exist in a dispersed state in the varnish of the resin composition. Those that do are preferred.
- Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles. Examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles.
- the core-shell type rubber particles are rubber particles having a core layer and a shell layer.
- the outer shell layer is a glassy polymer and the inner core layer is a rubbery polymer.
- Examples include a three-layer structure in which the shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer.
- the glassy polymer layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber).
- Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N, (Ganz Kasei Co., Ltd.
- NBR acrylonitrile butadiene rubber
- SBR styrene butadiene rubber
- acrylic rubber particles include Methbrene W300A (average particle size 0.1 ⁇ m), W450A (average particle size 0.5 ⁇ m) (manufactured by Mitsubishi Rayon Co., Ltd.). These may be used alone or in combination of two or more.
- the average particle size of the (G) rubber particles to be blended is preferably in the range of 0.005 to 1 ⁇ m, more preferably in the range of 0.2 to 0.6 ⁇ m.
- the average particle diameter of the rubber particles in the present invention can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in a suitable organic solvent by ultrasonic waves, etc., and the particle size distribution of the rubber particles is created on a mass basis using FPRA-1000 (manufactured by Otsuka Electronics Co., Ltd.). Can be measured by setting the average particle size.
- the content in the case of blending rubber particles is preferably in the range of 1 to 10% by mass and preferably in the range of 2 to 5% by mass with respect to 100% by mass of the nonvolatile content in the resin composition. Is more preferable.
- the resin composition of this invention can further contain (H) a flame retardant from a viewpoint of a flame retardance improvement.
- (H) flame retardants include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides.
- organic phosphorus flame retardants include phenanthrene-type phosphorus compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd., and Ajinomoto Co., Inc.
- Phosphoric acid ester compounds such as OP930 manufactured by Daihachi Chemical Co., Ltd., FX289 compounds manufactured by Tohto Kasei Co., Ltd.
- phosphorus-containing epoxy resins such as FX305, phosphorus such as ERF001 manufactured by Toh
- organic nitrogen-containing phosphorus compounds include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Seisakusho Co., Ltd. Examples thereof include phosphazene compounds.
- metal hydroxide magnesium hydroxide such as UD65, UD650, UD653 manufactured by Ube Materials Co., Ltd., B-30, B-325, B-315, B-308 manufactured by Sakai Kogyo Co., Ltd.
- aluminum hydroxide such as B-303 and UFH-20. These may be used alone or in combination of two or more.
- the resin composition of the present invention contains a thermosetting resin other than an epoxy resin such as a maleimide compound, a bisallyl nadiimide compound, a vinyl benzyl resin, and a vinyl benzyl ether resin within the range where the effects of the present invention are exhibited. Can do. These may be used alone or in combination of two or more.
- BMI1000, BMI2000, BMI3000, BMI4000, BMI5100 (manufactured by Daiwa Kasei Kogyo Co., Ltd.), BMI, BMI-70, BMI-80 (manufactured by KEI Kasei Co., Ltd.), ANILIX-MI (Mitsui Chemical Fine) BANI-M, BANI-X (manufactured by Maruzen Petrochemical Co., Ltd.) as a vinyl benzyl resin, V5000 (manufactured by Showa Polymer Co., Ltd.), vinyl benzyl ether resin V1000X, V1100X (manufactured by Showa Polymer Co., Ltd.).
- the resin composition of the present invention can optionally contain various resin additives other than those described above as long as the effects of the present invention are exhibited.
- the resin additive include organic fillers such as silicon powder, nylon powder and fluorine powder, thickeners such as olben and benton, silicone-based, fluorine-based and polymer-based antifoaming agents or leveling agents, and silane coupling.
- Agents, adhesion imparting agents such as triazole compounds, thiazole compounds, triazine compounds and porphyrin compounds, and colorants such as phthalocyanine / blue, phthalocyanine / green, iodin / green, disazo yellow and carbon black.
- the use of the resin composition of the present invention is not particularly limited, but it is characterized by achieving laminability, flexibility, and low linear thermal expansion coefficient by using the resin composition of the present invention, such as an adhesive film and a prepreg. Sheet-like laminated materials, circuit boards, solder resists, underfill materials, die bonding materials, semiconductor sealing materials, hole-filling resins, component-filling resins, and the like, and can be used in a wide range of applications that require resin compositions. Especially, it can use suitably in order to form an insulating layer in manufacture of a multilayer printed wiring board.
- the resin composition of the present invention can be applied to a circuit board in a varnish state to form an insulating layer, but in general, it is preferably used in the form of a sheet-like laminated material such as an adhesive film or a prepreg. .
- the softening point of the resin composition is preferably 40 to 150 ° C. from the viewpoint of the laminating property of the sheet-like laminated material.
- the adhesive film of the present invention is prepared by a method known to those skilled in the art, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, and applying the resin varnish to a support using a die coater or the like. It can be produced by drying the organic solvent by heating or blowing hot air to form the resin composition layer.
- organic solvent examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol.
- aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These may be used alone or in combination of two or more.
- Drying conditions are not particularly limited, but the content of the organic solvent in the resin composition layer is preferably 10% by mass or less, and more preferably 5% by mass or less. As drying conditions, suitable drying conditions can be appropriately set by simple experiments. Although it depends on the amount of organic solvent in the varnish, it is preferable to dry the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for about 3 to 10 minutes.
- the thickness of the resin composition layer formed in the adhesive film is preferably 10 to 100 ⁇ m from the viewpoint of increasing the number of folding resistances when the MIT folding resistance test of the cured resin composition is performed, 90 ⁇ m is more preferable, 20 to 80 ⁇ m is further preferable, 25 to 70 ⁇ m is still more preferable, 30 to 65 ⁇ m is even more preferable, 35 to 60 ⁇ m is particularly preferable, and 40 to 55 ⁇ m is particularly preferable.
- the support in the present invention examples include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, plastic films such as polycarbonate and polyimide. Can be mentioned.
- PET polyethylene terephthalate
- PET polyesters
- PET polyethylene naphthalate
- plastic films such as polycarbonate and polyimide.
- PET is particularly preferable.
- a metal foil such as a copper foil or an aluminum foil can be used as the support, and an adhesive film with a metal foil can be obtained.
- the support may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
- the release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.
- the thickness of the support is not particularly limited, but is preferably 10 to 150 ⁇ m,
- the support in the present invention is peeled after being laminated on an inner layer circuit board or the like, or after forming an insulating layer by heat curing. If the support is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing step can be prevented, and the surface smoothness of the insulating layer after curing can be improved. In the case of peeling after curing, it is preferable that the support is subjected to a release treatment in advance. In addition, it is preferable to form the resin composition layer formed on a support body so that the area of a layer may become smaller than the area of a support body.
- a plastic film similar to the support can be further laminated as a protective film on the surface of the resin composition layer on which the support is not in close contact.
- the protective film may be subjected to a release treatment in addition to the mat treatment and the corona treatment.
- the release treatment may be performed with a release agent such as a silicone resin release agent, an alkyd resin release agent, or a fluororesin release agent.
- the thickness of the protective film is not particularly limited, but is preferably 1 to 40 ⁇ m.
- a multilayer printed wiring board using adhesive film can be manufactured using the adhesive film manufactured as described above. An example of the method will be described next.
- the resin composition layer is protected with a protective film, the resin composition layer is peeled off and then laminated on one or both sides of the inner circuit board so that the resin composition layer is in direct contact with the inner circuit board.
- a method of laminating the inner layer circuit board under reduced pressure by a vacuum laminating method is preferably used.
- the laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the inner layer circuit board may be heated (preheated) as necessary before lamination.
- the inner layer circuit board in the present invention is mainly formed by a patterned conductor layer on one side or both sides of a substrate such as a glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate or the like. Say something.
- a substrate such as a glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate or the like.
- a substrate such as a glass epoxy, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate or the like.
- the lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., and the pressure bonding pressure is preferably 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2 ). Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.
- Vacuum lamination can be performed using a commercially available vacuum laminator.
- a commercially available vacuum laminator for example, vacuum applicator manufactured by Nichigo Morton Co., Ltd., vacuum pressurizing laminator manufactured by Meiki Seisakusho Co., Ltd., roll dry coater manufactured by Hitachi Industries, Ltd., Hitachi AIC Co., Ltd. ) Made vacuum laminator and the like.
- the lamination process which heats and pressurizes under reduced pressure can also be performed using a general vacuum hot press machine.
- a general vacuum hot press machine For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side.
- the degree of vacuum is preferably 1 ⁇ 10 ⁇ 2 MPa or less, and more preferably 1 ⁇ 10 ⁇ 3 MPa or less.
- heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the bleeding of the resin.
- the first stage press is performed at a temperature of 70 to 150 ° C. and the pressure is in a range of 1 to 15 kgf / cm 2
- the second stage press is performed at a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm 2 Is preferred.
- the time for each stage is preferably 30 to 120 minutes.
- Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.
- the heat curing conditions are selected from 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, and more preferably 160 ° C. to 200 ° C. for 30 to 120 minutes.
- drilling can be performed by a known method such as drilling, laser, or plasma, or by combining these methods as necessary. Of these, drilling with a laser such as a carbon dioxide laser or a YAG laser is preferred.
- the roughening treatment in the present invention is preferably performed by a wet roughening method using an oxidizing agent.
- the oxidizing agent include permanganate (potassium permanganate, sodium permanganate, etc.), dichromate, ozone, hydrogen peroxide / sulfuric acid, nitric acid and the like.
- alkaline permanganate solution (potassium permanganate, aqueous sodium hydroxide solution of sodium permanganate, etc.), which is an oxidizer widely used for roughening insulating layers in the production of multilayer printed wiring boards by the built-up method It is preferable to perform roughening using.
- a conductor layer is formed on the surface of the resin composition layer on which uneven anchors are formed by the roughening treatment by a method combining electroless plating and electrolytic plating.
- a plating resist having a pattern opposite to that of the conductor layer can be formed, and the conductor layer can be formed only by electroless plating.
- the peel strength of the conductor layer can be further improved and stabilized by annealing at 150 to 200 ° C. for 20 to 90 minutes.
- a method of patterning the conductor layer to form a circuit for example, a subtractive method or a semi-additive method known to those skilled in the art can be used.
- the prepreg of the present invention can be produced by impregnating the resin composition of the present invention into a sheet-like fiber base material by a hot melt method or a solvent method, followed by heating and semi-curing. That is, it can be set as the prepreg which will be in the state which the resin composition of this invention impregnated the sheet-like fiber base material.
- the sheet-like fiber base material it is preferable to use those made of fibers that are commonly used as prepreg fibers such as glass cloth and aramid fibers.
- the solvent method is a method in which a sheet-like fiber base material is immersed in a resin varnish obtained by dissolving a resin in an organic solvent, the resin varnish is impregnated into the sheet-like fiber base material, and then dried.
- a multilayer printed wiring board using prepreg can be produced using the prepreg produced as described above. An example of the method will be described next.
- One or several prepregs of the present invention are stacked on the inner circuit board, sandwiched by a metal plate through a release film, and press laminated under pressure and heating conditions.
- the pressurizing and heating conditions are preferably a pressure of 5 to 40 kgf / cm 2 (49 ⁇ 10 4 to 392 ⁇ 10 4 N / m 2 ) and a temperature of 120 to 200 ° C. for 20 to 100 minutes.
- the prepreg can be laminated on a circuit board by a vacuum laminating method and then cured by heating. Thereafter, in the same manner as described above, the surface of the cured prepreg is roughened, and then a conductor layer is formed by plating to produce a multilayer printed wiring board.
- a semiconductor device can be manufactured by using the multilayer printed wiring board of the present invention.
- a semiconductor device is manufactured by bonding a semiconductor element to the connection electrode portion on the multilayer printed wiring board.
- the mounting method of the semiconductor element is not particularly limited, and examples thereof include wire bonding mounting, flip chip mounting, mounting with an anisotropic conductive film (ACF), mounting with a non-conductive film (NCF), and the like.
- a fine wiring groove can be formed in the insulating layer by including a specific inorganic filler in the resin composition.
- a manufacturing method by a built-up method in which insulating layers and conductor layers are alternately stacked on a core substrate is known.
- a curable resin composition is laminated on an inner layer circuit board with an adhesive film, and the curable resin composition is cured to form an insulating layer.
- vias for interlayer connection are formed using a laser, desmear on the via bottom and the insulating layer are roughened with an oxidizing agent such as an alkaline potassium permanganate solution, and electroless plating is performed on the rough surface by a semi-additive method.
- a plating seed layer is formed, and then a conductor layer is formed by electrolytic plating.
- an unnecessary plating seed layer is removed by etching to form a circuit.
- the desmear at the bottom of the via and the insulating layer are roughened with an oxidizing agent such as an alkaline potassium permanganate solution, electroless plating and electroplating are performed on the rough surface, and finally the unnecessary copper layer on the surface layer is removed.
- an oxidizing agent such as an alkaline potassium permanganate solution
- electroless plating and electroplating are performed on the rough surface
- the unnecessary copper layer on the surface layer is removed.
- a dry method such as plasma can be used for desmear.
- the corner resin of the formed groove is removed, and a preferable rectangle cannot be maintained, and the wiring formed thereafter does not become the assumed fine wiring. There was a problem.
- a metal film with a metal film layer formed on the support layer or a metal with a metal film layer formed on the support layer and a curable resin composition layer formed on the metal film layer.
- the support layer is a film or sheet having a self-supporting property, and a metal foil, a plastic film, or the like can be used, and a plastic film is particularly preferably used.
- the metal foil include aluminum foil and copper foil.
- a metal foil made of a metal different from the metal film layer to be formed is employed.
- the plastic film include polyethylene terephthalate film, polyethylene naphthalate, polyimide, polyamideimide, polyamide, polytetrafluoroethylene, polycarbonate, and the like.
- Polyethylene terephthalate film and polyethylene naphthalate film are preferable, and inexpensive polyethylene terephthalate is particularly preferable. preferable.
- the surface of the support layer may be subjected to surface treatment such as corona treatment. Further, the surface of the support layer film on the side where no metal film layer or release layer is present may be subjected to surface treatment such as mat treatment or corona treatment.
- the support layer surface on the side where the release layer is formed has an arithmetic average roughness (Ra value) of 50 nm or less (0 or more and 50 nm or less), from the viewpoint of preventing cracks when producing a film with a metal film, It is preferably 40 nm or less, more preferably 35 nm or less, and further preferably 30 nm or less.
- the arithmetic average roughness of the surface of the support layer on the side where the release layer is not formed is preferably within the same range as described above.
- the arithmetic average roughness (Ra value) can be measured by using a known method, for example, by using a device such as a non-contact type surface roughness meter (for example, WYKO NT3300 manufactured by Beec Instruments). Can do. A commercially available support can also be used.
- a device such as a non-contact type surface roughness meter (for example, WYKO NT3300 manufactured by Beec Instruments). Can do.
- a commercially available support can also be used.
- T60 manufactured by Toray Industries, Inc., polyethylene terephthalate film
- A4100 manufactured by Toyobo Co., Ltd., polyethylene terephthalate film
- Q83 manufactured by Teijin DuPont Films, Inc.
- Polyethylene naphthalate film manufactured by Lintec Corporation, polyethylene terephthalate film with alkyd mold release agent (AL-5), Diafoil (registered trademark) B100 (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., polyethylene terephthalate film), etc.
- A-5 alkyd mold release agent
- Diafoil registered trademark
- B100 manufactured by Mitsubishi Chemical Polyester Film Co., Ltd., polyethylene terephthalate film
- the layer thickness of the support layer is preferably 10 to 70 ⁇ m, more preferably 15 to 70 ⁇ m. If the layer thickness is too small, the handleability tends to be poor, the peelability of the support layer tends to be lowered, and the formation of a smooth metal film layer tends to cause problems. Moreover, when the layer thickness is too large, the cost tends to be impractical.
- the film with a metal film and the adhesive film with a metal film in the present invention preferably have a release layer between the support layer and the metal film layer in order to efficiently transfer the metal film to the surface of the adherend.
- the release layer can be formed using a polymer release layer such as a fluororesin, alkyd resin, silicone resin, polyolefin resin, polyvinyl alcohol resin, acrylic resin, polyester resin, melamine resin, or cellulose resin.
- a polymer release layer such as a fluororesin, alkyd resin, silicone resin, polyolefin resin, polyvinyl alcohol resin, acrylic resin, polyester resin, melamine resin, or cellulose resin.
- the release layer can be a metal film or metal foil formed by vapor deposition, sputtering, ion plating, or the like.
- the metal include aluminum, zinc, lead, nickel and the like, but aluminum is preferable.
- the release layer is one or more water-soluble selected from water-soluble cellulose resin, water-soluble acrylic resin and water-soluble polyester resin from the viewpoint of uniformly transferring the metal film layer and the cost of forming the release layer. It is preferable to form with a polymer release layer. These water-soluble polymer release layers are easier to form on the support layer than the metal release layer, and are advantageous in terms of cost. Furthermore, after the curable resin composition as the adherend is cured, the support layer can be peeled off between the support layer and the release layer, the metal film layer is not easily damaged, and the release layer remaining on the metal film layer is Since it is easily removed with an aqueous solution, a metal film can be uniformly formed on the adherend.
- a water-soluble cellulose resin and a water-soluble polyester resin are more preferable, and a water-soluble cellulose resin is more preferable. These may be used alone or in combination of two or more.
- the water-soluble polymer release layer may have a multilayer structure formed from one or more layers different in water-soluble polymer used.
- a silicone resin, an alkyd resin, a fluororesin is used between the water-soluble polymer release layer and the support layer in order to improve the peelability between these layers.
- Other release layers may be present. That is, when a water-soluble polymer release layer is applied to the release layer, it is sufficient that at least the surface of the release layer that adheres to the metal film is formed of the water-soluble polymer release layer.
- the water-soluble polymer release layer and other release layers so that the surface to be bonded to the metal film is formed of the water-soluble polymer release layer. And a two-layer structure.
- the support can be peeled between the support layer and the release layer after the curable resin composition as the adherend is cured, and thereafter Since the release layer remaining on the metal film layer is easily removed with an aqueous solution, a metal film having excellent uniformity can be formed on the adherend.
- the peeling of the support between the support layer and the release layer is performed at the interface between the support and the water-soluble polymer release layer when the release layer is formed only of the water-soluble polymer release layer.
- the release layer is composed of two layers of another release layer such as an alkyd resin and the water-soluble polymer release layer, the release layer is performed at the interface between the other release layer and the water-soluble polymer release layer. Is called.
- the layer thickness of the release layer is preferably from 0.01 ⁇ m to 20 ⁇ m, more preferably from 0.05 ⁇ m to 10 ⁇ m, still more preferably from 0.1 ⁇ m to 5 ⁇ m, still more preferably from 0.1 ⁇ m to 3 ⁇ m. 1 ⁇ m or more and 2 ⁇ m or less is particularly preferable, 0.1 ⁇ m or more and 1 ⁇ m or less is particularly preferable, and 0.2 ⁇ m or more and 1 ⁇ m or less is particularly preferable.
- the “layer thickness” here is the thickness when the release layer is a single layer, and is the total thickness of the multilayer when it is a multilayer.
- the release layer when the release layer is composed of a water-soluble polymer release layer and other release layers such as silicone resin, alkyd resin, and fluorine resin, the total of these release layers
- the layer thickness is set in the above range.
- the layer thickness of the release layer other than the water-soluble polymer release layer is preferably in the range of 0.01 to 0.2 ⁇ m. If the release layer is too thick, when the curable resin composition layer is thermally cured, the metal film layer may be cracked or scratched due to the difference in thermal expansion coefficient between the metal film layer and the release layer. There is a risk of malfunction. On the other hand, when the layer thickness is too thin, the peelability of the support layer may be lowered.
- Water-soluble cellulose resin refers to a cellulose derivative that has been subjected to a treatment for imparting water-solubility to cellulose, and preferred examples include cellulose ether and cellulose ether ester.
- Cellulose ether is an ether formed by conversion of one or more hydroxyl groups present in one or more anhydroglucose repeat units of a cellulose polymer to give one or more ether linking groups to the cellulose polymer.
- the group includes an alkyl group optionally substituted by one or more substituents selected from a hydroxyl group, a carboxyl group, an alkoxy group (1 to 4 carbon atoms) and a hydroxyalkoxy group (1 to 4 carbon atoms). And C 1-4).
- hydroxyalkyl groups such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl; 2-methoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 2-ethoxy Alkoxy (C1-4) alkyl group (C1-4) such as ethyl; hydroxyalkoxy (C1-4) such as 2- (2-hydroxyethoxy) ethyl or 2- (2-hydroxypropoxy) propyl )
- the ether linking group in the polymer molecule may be a single species or a plurality of species. That is, it may be a cellulose ether having a single type of ether linking group or a cellulose ether having a plurality of types of ether linking groups.
- cellulose ether examples include, for example, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, hydroxybutyl methyl cellulose, hydroxyethyl ethyl cellulose, carboxymethyl cellulose, and water-soluble salts thereof (for example, alkali metal salts such as sodium salt). Is mentioned.
- the average number of moles of ether groups substituted per unit glucose ring in cellulose ether is not particularly limited, but is preferably 1-6.
- the molecular weight of the cellulose ether is preferably about 20000 to 60000 in weight average molecular weight.
- Cellulose ether esters are formed between one or more hydroxyl groups present in cellulose and one or more suitable organic acids or reactive derivatives thereof, thereby forming ester linking groups in the cellulose ether. That is.
- the “cellulose ether” herein is as described above, and the “organic acid” includes an aliphatic or aromatic carboxylic acid (having 2 to 8 carbon atoms), and the aliphatic carboxylic acid is acyclic (branched). Or unbranched) or cyclic, and may be saturated or unsaturated.
- aliphatic carboxylic acid examples include substituted or unsubstituted acyclic aliphatic dicarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, malonic acid, succinic acid, glutaric acid, fumaric acid, and maleic acid. Acids; acyclic hydroxy-substituted carboxylic acids such as glycolic acid or lactic acid; acyclic aliphatic hydroxy-substituted di- or tri-carboxylic acids such as malic acid, tartaric acid, and citric acid.
- the aromatic carboxylic acid is preferably an aryl carboxylic acid having 14 or less carbon atoms, and includes an aryl group such as a phenyl or naphthyl group having one or more carboxyl groups (for example, 1, 2 or 3 carboxyl groups).
- Aryl carboxylic acids are particularly preferred.
- the aryl group is substituted with one or more (for example, 1, 2 or 3) groups which may be the same or different and selected from hydroxy, alkoxy having 1 to 4 carbon atoms (for example, methoxy) and sulfonyl. May be.
- Preferable examples of the aryl carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid (1,2,4-benzenetricarboxylic acid) and the like.
- the organic acid has one or more carboxyl groups
- preferably only one carboxyl group of the acid forms an ester linkage to the cellulose ether.
- one carboxyl group of each succinate group forms an ester linkage with cellulose and the other carboxy group is present as a free acid.
- An “ester linking group” is formed by reaction of cellulose or cellulose ether with a suitable organic acid as described above or a reactive derivative thereof. Suitable reactive derivatives include, for example, acid anhydrides such as phthalic anhydride.
- the ester linking group in the polymer molecule may be single type or multiple types. That is, it may be a cellulose ether ester having a single type of ester linking group or a cellulose ether ester having a plurality of types of ester linking groups.
- hydroxypropyl methylcellulose acetate succinate is a mixed ester of hydroxypropyl methylcellulose having both succinate and acetate groups.
- Suitable cellulose ether esters are hydroxypropylmethylcellulose or esters of hydroxypropylcellulose, specifically hydroxypropylmethylcellulose acetate, hydroxypropylmethylcellulose succinate, hydroxypropylmethylcellulose acetate succinate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose Trimellitate, hydroxypropyl methylcellulose acetate phthalate, hydroxypropyl methylcellulose acetate trimellitate, hydroxypropyl cellulose acetate phthalate, hydroxypropyl cellulose butyrate phthalate, hydroxypropyl cellulose acetate phthalate succinate and Mud hydroxypropyl cellulose acetate trimellitate succinate, etc. These may be used alone or in combination. Among these, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate, and hydroxypropylmethylcellulose acetate phthalate are preferable.
- the average number of moles of ester groups substituted per unit glucose ring in the cellulose ether ester is not particularly limited, but is preferably about 0.5% to 2%, for example.
- the molecular weight of the cellulose ether ester is preferably about 20000 to 60000 in weight average molecular weight.
- Cellulose ethers and cellulose ether esters are well known in the art, and can be obtained by reacting an etherifying agent and an esterifying agent in accordance with a conventional method using natural cellulose (pulp) as a raw material. May be used. Examples thereof include “HP-55” and “HP-50” (both hydroxypropylmethylcellulose phthalate) manufactured by Shin-Etsu Chemical Co., Ltd.
- the “water-soluble polyester resin” as used in the present invention is synthesized by an ordinary polycondensation reaction using a polyvalent carboxylic acid or an ester-forming derivative thereof and a polyhydric alcohol or an ester-forming derivative thereof as main raw materials. It is a polyester resin made of a substantially linear polymer, and has a hydrophilic group introduced in the molecule or at the molecular end.
- examples of the hydrophilic group include an organic acid group such as a sulfo group, a carboxyl group, and a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof is preferable.
- the water-soluble polyester resin those having a sulfo group or a salt thereof and / or a carboxyl group or a salt thereof are particularly preferable.
- polyvalent carboxylic acid component of the polyester resin include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, adipic acid, and the like. These may be used alone or in combination of two or more.
- hydroxycarboxylic acids such as p-hydroxybenzoic acid
- unsaturated carboxylic acids such as maleic acid, fumaric acid or itaconic acid may be used in a small amount.
- polyhydric alcohol component of the polyester resin include ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,6-hexane glycol, 1,4-cyclohexane methanol, and xylylene.
- examples thereof include glycol, dimethylolpropionic acid, glycerin, trimethylolpropane, and poly (tetramethylene oxide) glycol. These may be used alone or in combination of two or more.
- the introduction of a hydrophilic group into the molecule or the molecular end of the polyester resin may be carried out by a known and commonly used method.
- An ester-forming compound containing a hydrophilic group for example, an aromatic carboxylic acid compound, a hydroxy compound, etc.
- a mode of polymerization is preferred.
- sodium 5-sulfonate sodium isophthalic acid, 5-sulfonic acid ammonium isophthalic acid, 4-sulfonic acid sodium isophthalic acid, 4-methylsulfonic acid ammonium isophthalic acid, 2-sulfonic acid sodium terephthalic acid It is preferable to copolymerize one or two or more selected from potassium isosulfonate, 5-sulfonate, potassium isophthalate 4-sulfonate, potassium terephthalate 2-sulfonate, and the like.
- a carboxylic acid group for example, one or two kinds selected from trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, trimesic acid, cyclobutanetetracarboxylic acid, dimethylolpropionic acid and the like. It is preferable to copolymerize the above, and the carboxylate group can be introduced into the molecule by neutralization with an amino compound, ammonia or an alkali metal salt after a copolymerization reaction in the art.
- the molecular weight of the water-soluble polyester resin is not particularly limited, but the weight average molecular weight is preferably about 10,000 to 40,000. If the weight average molecular weight is less than 10,000, the layer formability tends to decrease, and if it exceeds 40000, the solubility tends to decrease.
- the water-soluble polyester resin a commercially available product can be used as the water-soluble polyester resin. 565 "(weight average molecular weight: about 25000) and the like.
- Water-soluble acrylic resin The “water-soluble acrylic resin” referred to in the present invention is an acrylic resin that is dispersed or dissolved in water by containing a carboxyl group-containing monomer as an essential component.
- the acrylic resin is a monomer component in which a carboxyl group-containing monomer and a (meth) acrylic acid ester are essential, and if necessary, other unsaturated monomers as monomer components.
- Acrylic polymer is a monomer component in which a carboxyl group-containing monomer and a (meth) acrylic acid ester are essential, and if necessary, other unsaturated monomers as monomer components.
- examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, monomethyl maleate, monobutyl maleate , Monomethyl itaconate, monobutyl itaconate and the like, and one or more of them can be used.
- (meth) acrylic acid is preferable.
- Examples of the (meth) acrylic acid ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid.
- alkyl methacrylates having 1 to 18 carbon atoms such as nonyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, etc. Species or two or more can be used.
- unsaturated monomers include, for example, aromatic alkenyl compounds, vinyl cyanide compounds, conjugated diene compounds, halogen-containing unsaturated compounds, hydroxyl group-containing monomers, and the like.
- aromatic alkenyl compound include styrene, ⁇ -methylstyrene, p-methylstyrene, p-methoxystyrene, and the like.
- vinyl cyanide compound include acrylonitrile and methacrylonitrile.
- conjugated diene compound include butadiene and isoprene.
- Examples of the halogen-containing unsaturated compound include vinyl chloride, vinylidene chloride, perfluoroethylene, perfluoropropylene, and vinylidene fluoride.
- Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl. Examples thereof include acrylate, 4-hydroxybutyl methacrylate, ⁇ -hydroxymethylethyl (meth) acrylate and the like. These can use 1 type (s) or 2 or more types.
- the release layer is preferably formed by a method in which a coating liquid containing water-soluble cellulose, water-soluble polyester or water-soluble acrylic resin is applied to the support layer and dried.
- a coating liquid containing water-soluble cellulose, water-soluble polyester or water-soluble acrylic resin is applied to the support layer and dried.
- the coating solution can be used in an emulsion form or an aqueous solution form.
- a core-shell type emulsion is preferable, and in the core-shell type emulsion, it is important that a carboxyl group is present in the shell of the core-shell particle.
- an acrylic resin containing a (meth) acrylic acid ester is preferable, and in the core-shell type emulsion, it is important that a carboxyl group is present in the shell of the core-shell particle.
- an acrylic resin containing a (meth) acrylic acid ester is an acrylic resin containing a (meth) acrylic acid ester.
- a commercially available product (emulsion) of such core-shell particles can be used.
- Jonkrill 7600 Tg: about 35 ° C
- 7630A Tg: about 53 ° C
- 538J Tg: about 66 ° C
- 352D Tg: about 56 ° C.
- the acrylic resin is an acrylic resin containing a carboxyl group-containing monomer and a (meth) acrylic acid ester, and it is important that the molecular weight is relatively low. Therefore, it is preferable that the weight average molecular weight is 1000 to 50,000, and if the weight average molecular weight is less than 1000, the layer forming property tends to be reduced. It becomes the tendency for the peelability of the support body layer after hardening to fall.
- a commercially available product can be used as such an aqueous solution of a water-soluble acrylic resin.
- the emulsion and aqueous solution of water-soluble acrylic resin are easy to be thinned because the emulsion has a higher molecular weight. Accordingly, a water-soluble acrylic resin emulsion is preferred.
- the metal used for the metal film layer is a single metal such as gold, platinum, silver, copper, aluminum, cobalt, chromium, nickel, titanium, tungsten, iron, tin, indium, or two or more kinds of metals such as nickel / chromium alloy.
- chromium, nickel, titanium, nickel / chromium alloy, aluminum, zinc, copper / nickel Alloys, copper / titanium alloys, gold, silver and copper are preferred, chromium, nickel, titanium, nickel / chromium alloys, aluminum, zinc, gold, silver and copper are more preferred, and copper is particularly preferred.
- the metal film layer may be a single layer or a multilayer structure in which two or more different metals are stacked.
- the thickness of the metal film layer is not particularly limited, but is preferably 10 nm to 5000 nm, more preferably 20 nm to 2000 nm, still more preferably 30 nm to 1000 nm, still more preferably 50 nm to 500 nm, still more preferably 50 nm to 400 nm, and even more preferably 50 nm to 300 nm is particularly preferred. If the layer thickness is too small, the metal film tends to crack after the production of the film with the metal film, and the metal film layer is dissolved in the desmear process and the like, and the insulating layer surface tends to be roughened. . On the other hand, if the layer thickness is too large, it takes a long time to form a metal film, which tends to be costly, and also tends to require time for laser processing.
- the adhesive film with a metal film in the present invention has a structure in which a curable resin composition layer is further formed on the metal film layer of the film with a metal film described above. That is, the adhesive film with a metal film in the present invention has a curable resin composition layer in addition to the support layer and the metal film layer. Moreover, it is preferable to have a release layer between a support body layer and a metal film layer like a film with a metal film.
- the curable resin composition used for the curable resin composition layer can be used without particular limitation as long as the cured product has sufficient hardness and insulation, It is preferable to contain (a) an epoxy resin, (b) a thermoplastic resin, and (c) a curing agent.
- an epoxy resin (b) a thermoplastic resin, and (c) a curing agent.
- rubber particles, flame retardants, various resin additives, maleimide compounds, bisallyl nadiimide compounds, vinyl benzyl resins, vinyl benzyl ether resins, bismaleimide-triazine resins, acrylic resins, and the like described above should be used. Can do.
- a bisphenol A type epoxy resin A bisphenol A type epoxy resin, a biphenyl type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a bisphenol F type epoxy resin, a phosphorus containing epoxy resin, a bisphenol S type epoxy Resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, epoxy resin having butadiene structure, cyclohexanedimethanol epoxy resin, glycidylamine Type epoxy resin, diglycidyl etherified product of bisphenol, diglycidyl etherified product of naphthalene diol, glycidyl etherified product of phenol, and diglycidized alcohol Etherate, and alkyl-substituted products of these epoxy resins, halides and hydrogenated products or the like. These may be used alone or in combination of two epoxy resin, diglycidyl ether
- epoxy resins are bisphenol A type epoxy resins, naphthol type epoxy resins, naphthalene type epoxy resins, biphenyl type epoxies from the viewpoints of heat resistance, insulation reliability, flexibility, and adhesion to metal films.
- a resin and an epoxy resin having a butadiene structure are preferred.
- liquid bisphenol A type epoxy resin (“Epicoat 828EL” manufactured by Japan Epoxy Resin Co., Ltd.), naphthalene type bifunctional epoxy resin (“HP4032”, “HP4032D” manufactured by Dainippon Ink and Chemicals, Inc.), Naphthalene type tetrafunctional epoxy resin (“HP4700” manufactured by Dainippon Ink and Chemicals, Inc.), naphthol type epoxy resin (“ESN-475V” manufactured by Tohto Kasei Co., Ltd.), epoxy resin having a butadiene structure (Daicel Chemical Industries ( "PB-3600” manufactured by Co., Ltd.), epoxy resins having a biphenyl structure ("NC3000H", “NC3000L” manufactured by Nippon Kayaku Co., Ltd., "YX4000” manufactured by Japan Epoxy Resin Co., Ltd.), and the like.
- Epicoat 828EL manufactured by Japan Epoxy Resin Co., Ltd.
- naphthalene type bifunctional epoxy resin (“HP4032
- the content of the component (a) in the curable resin composition is not particularly limited, but the upper limit value of the content of the component (a) in the curable resin composition is From the viewpoint of preventing a decrease in the flexibility of the film, 60% by mass is preferable, 50% by mass is more preferable, and 40% by mass is further based on 100% by mass of the nonvolatile content in the curable resin composition. preferable.
- the lower limit of the content of the component (a) in the curable resin composition is a non-volatile content in the curable resin composition from the viewpoint of improving the glass transition temperature of the insulating layer and reducing the linear thermal expansion coefficient. 5 mass% is preferable with respect to 100 mass% of minutes, 10 mass% is more preferable, and 15 mass% is still more preferable.
- thermoplastic resin A phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamideimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene ether resin, a polycarbonate resin, a poly resin
- thermoplastic resin A phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamideimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene ether resin, a polycarbonate resin, a poly resin
- ether ketone resins examples include ether ether ketone resins and polyester resins. These may be used alone or in combination of two or more.
- a phenoxy resin and a polyvinyl acetal resin are preferable from the viewpoint of imparting appropriate flexibility to the cured product.
- the thermoplastic resin preferably has a glass transition temperature of 80 ° C. or higher.
- the “glass transition temperature” here is determined according to the method described in JIS K 7197. When the glass transition temperature is higher than the decomposition temperature and the glass transition temperature is not actually observed, the decomposition temperature can be regarded as the glass transition temperature in the present invention.
- the decomposition temperature is defined as a temperature at which the mass reduction rate is 5% when measured according to the method described in JIS K 7120.
- the weight average molecular weight of the thermoplastic resin is preferably in the range of 5,000 to 200,000, more preferably in the range of 10,000 to 150,000, still more preferably in the range of 15,000 to 100,000, and 20,000 to 80,000.
- the range is even more preferable. If it is smaller than this range, the effect of improving the film forming ability and mechanical strength tends to be insufficient. If it is larger than this range, the compatibility with the cyanate ester resin and the epoxy resin is lowered, and the surface of the insulating layer is roughened. Later roughness tends to increase.
- the weight average molecular weight in this invention is measured by the gel permeation chromatography (GPC) method (polystyrene conversion).
- GPC gel permeation chromatography
- the weight average molecular weight by the GPC method is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K manufactured by Showa Denko KK as a column. -804L is measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.
- phenoxy resin examples include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, Examples thereof include those having one or more skeletons selected from a trimethylcyclohexane skeleton. Two or more phenoxy resins may be mixed and used.
- the terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group.
- Examples of commercially available products include 1256 and 4250 (bisphenol A skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin Co., Ltd., YX8100 (bisphenol S skeleton-containing phenoxy resin) manufactured by Japan Epoxy Resin, and YX6954 (containing bisphenolacetophenone skeleton) manufactured by Japan Epoxy Resin. Phenoxy resin), FX280, FX293 manufactured by Toto Kasei Co., Ltd., YL7553, YL6954, YL6794, YL7213, YL7290, YL7482 manufactured by Japan Epoxy Resins Co., Ltd., and the like.
- polyvinyl acetal resin examples include those manufactured by Denki Kagaku Kogyo Co., Ltd., electrified butyral 4000-2, 5000-A, 6000-C, and 6000-EP, Sekisui Chemical Co., Ltd., ESREC BH series, BX series, and KS. Series, BL series, BM series, etc. are mentioned.
- polyimide resin examples include polyimide “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd.
- linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadienes, diisocyanate compounds and tetrabasic acid anhydrides (described in JP-A-2006-37083), polysiloxane skeleton-containing polyimides (JP-A-2002-2002).
- modified polyimides such as those described in JP-A No. 12667 and JP-A No. 2000-319386.
- polyamide-imide resin examples include polyamide-imide “Vilomax HR11NN” and “Vilomax HR16NN” manufactured by Toyobo Co., Ltd. Further, modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd. can be mentioned.
- polyethersulfone resin examples include polyethersulfone “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.
- polysulfone resin examples include polysulfone “P1700” and “P3500” manufactured by Solven Advanced Polymers Co., Ltd.
- the content of the thermoplastic resin (b) is not particularly limited, but is preferably 0.5 to 100% by mass with respect to 100% by mass of the nonvolatile content in the curable resin composition. It is 20% by mass, more preferably 1 to 10% by mass.
- (B) When the blending ratio of the thermoplastic resin is less than 0.5% by mass, since the resin composition viscosity is low, it tends to be difficult to form a uniform curable resin composition layer. When exceeding, the viscosity of a resin composition becomes high too much and it becomes the tendency for the embedding to the wiring pattern on a board
- the curing agent is not particularly limited, but an amine curing agent, a guanidine curing agent, an imidazole curing agent, a triazine skeleton-containing phenol curing agent, a phenol curing agent, a triazine skeleton-containing naphthol curing agent, Examples thereof include naphthol-based curing agents, acid anhydride-based curing agents or epoxy adducts and microencapsulated ones thereof, cyanate ester-based curing agents, active ester-based curing agents, and benzoxazine-based curing agents. From the viewpoint of improving the peel strength of the plating, the curing agent preferably has a nitrogen atom in the molecular structure.
- an imide skeleton-containing bifunctional phenol a triazine skeleton-containing phenol-based curing agent, a triazine skeleton-containing naphthol-based curing agent.
- an imide skeleton-containing bifunctional phenol and a triazine skeleton-containing phenol novolak resin are preferable. These may be used alone or in combination of two or more.
- phenol-based curing agent examples include, for example, MEH-7700, MEH-7810, MEH-7785 (manufactured by Meiwa Kasei Co., Ltd.), NHN, CBN, GPH. (Nippon Kayaku Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Toto Kasei), TD2090, LA7052, LA7054, LA3018, LA1356 Etc.).
- cyanate ester-based curing agent active ester-based curing agent, and benzoxazine-based curing agent, those described above can be used.
- the ratio of (a) the epoxy equivalent of the epoxy resin and (c) the active hydrogen equivalent of the curing agent is preferably (1: 0.2) to (1: 2), and (1: 0.3) to (1 : 1.5) is more preferable, and (1: 0.4) to (1: 1) is more preferable. If the equivalent ratio is out of the above range, the mechanical strength and water resistance of the cured product tend to decrease.
- a curing accelerator can be contained in the curable resin composition.
- the curing accelerator is not particularly limited, and examples thereof include a metal curing accelerator, an imidazole curing accelerator, an amine curing accelerator, an organic phosphine compound, and an organic phosphonium salt compound. As specific examples, those described above can be used.
- the curable resin composition may contain (e) an inorganic filler.
- the inorganic filler is not particularly limited, but silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, Examples thereof include barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica is preferable.
- amorphous silica, fused silica, crystalline silica, synthetic silica, pulverized silica, hollow silica, and spherical silica are preferable, and fused silica and spherical silica are more preferable. These may be used alone or in combination of two or more.
- the average particle diameter of the inorganic filler is not particularly limited, but is preferably 5 ⁇ m or less from the viewpoint of enabling the formation of fine wiring grooves in the insulating layer and improving the workability by laser. 0.5 ⁇ m or less is more preferable, 1 ⁇ m or less is further preferable, 0.7 ⁇ m or less is even more preferable, 0.5 ⁇ m or less is particularly preferable, and 0.45 ⁇ m or less is particularly preferable.
- the average particle size of the inorganic filler (e) becomes too small, when the curable resin composition is made into a resin varnish, the viscosity of the varnish increases and the handleability is prevented from being lowered, and dispersibility is prevented. From the viewpoint of improving the average particle size, the average particle size is preferably 0.02 ⁇ m or more, more preferably 0.05 ⁇ m or more, still more preferably 0.1 ⁇ m or more, and 0.2 ⁇ m or more. Is even more preferred.
- the average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter.
- an inorganic filler dispersed in water by ultrasonic waves can be preferably used.
- LA-500 manufactured by Horiba Ltd. can be used as a laser diffraction type particle size distribution measuring device.
- the upper limit of the amount of the inorganic filler added is that the cured product is prevented from becoming brittle, and the adhesive strength of the curable resin composition is prevented from being lowered.
- the nonvolatile content is 100% by mass, it is preferably 70% by mass or less, more preferably 65% by mass or less, still more preferably 60% by mass or less, still more preferably 55% by mass or less, and particularly preferably 50% by mass or less.
- the lower limit of the added amount of the inorganic filler is preferably 5% by mass when the nonvolatile content in the curable resin composition is 100% by mass from the viewpoint of lowering the coefficient of thermal expansion of the insulating layer. More preferably, it is more preferably 20% by weight, even more preferably 30% by weight, even more preferably 40% by weight, and particularly preferably 50% by weight.
- Inorganic fillers include silane coupling agents, acrylate silane coupling agents, sulfide silane coupling agents, vinyl silane coupling agents, mercaptosilane coupling agents, styryl silane coupling agents, and isocyanates.
- Surface treatment with surface treatment agents such as silane coupling agents, organosilazane compounds, epoxy silane coupling agents, amino silane coupling agents, ureido silane coupling agents, titanate coupling agents, etc. Improved ones are preferred. These may be used alone or in combination of two or more.
- the curable resin composition is not particularly limited, but preferably contains (a) component, more preferably contains (a) component and (b) component, and (a) component and (b) It is more preferable to contain a component and (c) component, and it is still more preferable to contain (a) component, (b) component, (c) component, and (d) component.
- the method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the components are mixed using a rotary mixer or the like after adding a solvent or the like as necessary. Especially, it is preferable to perform the dispersion
- a known stirring and heating dissolution apparatus can be used to adjust the suspension, but a stirring and heating dissolution apparatus equipped with a high-speed rotary blade such as a homogenizer or a disperser blade is preferable in order to dissolve uniformly and quickly.
- Specific examples of the stirring and heating dissolution apparatus include T.W. K homomixer, T.W. K. Homo disperse, T.W. K. Combimix, T. K.
- Hibis Disper Mix (above, product name manufactured by Primix Co., Ltd.), CLEARMIX (product name manufactured by M Technique Co., Ltd.), vacuum emulsification stirring device (product name manufactured by Mizuho Industry Co., Ltd.), vacuum mixing device “Nerimaze” DX "(trade name, manufactured by Mizuho Kogyo Co., Ltd.), BDM twin screw mixer, CDM concentric twin screw mixer, PD mixer (above, trade name manufactured by Inoue Seisakusho Co., Ltd.).
- the stirring temperature varies depending on the solvent used, but is preferably in the range of 30 ° C to 80 ° C.
- the viscosity of the suspension is preferably 10 to 1000 mPa ⁇ s, more preferably 100 to 500 mPa ⁇ s. When the viscosity is high, diffusion of particles at the collision site is suppressed due to the liquid viscosity, and the whole tends to be non-uniformly dispersed.
- the viscosity can be measured with a rotational viscometer such as an E-type viscometer.
- the content of the inorganic filler in the suspension is preferably 30 to 60% by mass and more preferably 40 to 60% by mass with respect to 100% by mass of the suspension.
- the chance of collision between the particles of the inorganic filler is reduced, a sufficient shearing force cannot be obtained, and the dispersion treatment by the high-pressure homogenizer tends to be insufficient. If it exceeds 60% by mass, the amount of the inorganic filler that collides per unit area of the collision site increases, so that the dispersion treatment by the high-pressure homogenizer becomes insufficient, and at the same time, the wear of the collision site of the high-pressure homogenizer tends to become severe.
- the suspension prepared as described above is dispersed by a high-pressure homogenizer.
- the high-pressure homogenizer refers to an apparatus that pressurizes a raw material to a high pressure and performs pulverization / dispersion / emulsification using a shearing force when passing through a slit (gap).
- the material of the portion where the inorganic filler collides at high pressure is made of tungsten carbide or diamond in order to prevent foreign matter from being mixed due to collision wear.
- the high-pressure homogenizer is not a batch-type dispersion method but a continuous dispersion method, which can improve productivity and reduce the risk of organic solvent vapor being released, thereby reducing the cost and environmental burden. You can also.
- Specific examples of the high-pressure homogenizer include a high-pressure homogenizer manufactured by Sanwa Engineering Co., Ltd., a high-pressure homogenizer manufactured by Izumi Food Machinery Co., Ltd., and a high-pressure homogenizer manufactured by Niro Soabi (Italy).
- the dispersion pressure of the high-pressure homogenizer is preferably 10 to 300 MPa, more preferably 15 to 100 MPa, and still more preferably 20 to 60 MPa.
- the liquid temperature after the dispersion treatment is preferably 60 ° C. or lower. Moreover, it is preferable to make a liquid temperature rapidly 40 degrees C or less using a cooling device after a dispersion process.
- Examples of the apparatus for mixing the suspension subjected to the dispersion treatment with the high-pressure homogenizer and the temperature-sensitive component such as an epoxy curing agent as the remaining resin composition include, for example, a disper blade, a turbine blade, a paddle blade, and a propeller blade.
- a known stirring and mixing device equipped with an anchor blade or the like can be used.
- Specific examples of the stirring and mixing device include planetary mixer, trimix, butterfly mixer (trade name, manufactured by Inoue Seisakusho Co., Ltd.), VMIX stirring tank, Max Blend, SWIXER mixing system (manufactured by Izumi Food Machinery Co., Ltd.).
- the resin composition varnish is fed by a metering pump and filtered by passing it alone or continuously through a cartridge filter, a capsule filter or the like.
- the filtration pressure (differential pressure) at that time is preferably 0.4 MPa or less so that the filter mesh does not open.
- the mesh size for filtration is preferably 10 ⁇ m to 30 ⁇ m.
- the curable resin composition layer may be a prepreg impregnated with the above curable resin composition in a sheet-like fiber base material.
- the sheet-like fiber base material for example, those commonly used as prepreg fibers, such as glass cloth and aramid fibers, can be used.
- the prepreg can be formed by impregnating a curable resin composition into a sheet-like fiber base material by a hot melt method or a solvent method and semi-curing by heating. In the hot melt method, without dissolving the resin composition in an organic solvent, the resin composition is once coated on the resin composition and coated paper having good peelability, and then laminated on the sheet-like fiber substrate. Or it is the method of manufacturing a prepreg by coating directly with a die coater.
- the solvent method is a method in which a sheet-like fiber base material is immersed in a varnish obtained by dissolving a resin composition in an organic solvent, the varnish is impregnated into the sheet-like fiber base material, and then dried.
- the thickness of the curable resin composition layer varies depending on the thickness of the inner circuit conductor layer, etc., but is 10 to 150 ⁇ m from the viewpoint of improving the insulation reliability between the layers. Is preferable, and 15 to 80 ⁇ m is more preferable.
- a metal film layer is formed on the support layer.
- a release layer is formed on the surface of the support layer, and a metal film layer is formed on the surface of the release layer.
- the method for forming the release layer is not particularly limited, and a known lamination method such as hot pressing, hot roll lamination, extrusion lamination, coating / drying of a coating solution can be adopted, but a simple and highly uniform layer can be formed. From the viewpoint of easy formation, a method of applying and drying a coating liquid containing a material used for the release layer is preferable.
- the metal film layer is preferably formed by one or more methods selected from a vapor deposition method, a sputtering method and an ion plating method, and particularly preferably formed by a vapor deposition method and / or a sputtering method. These methods can be used in combination, but either method can be used alone.
- vapor deposition method vacuum vapor deposition method
- the support is placed in a vacuum vessel and the metal is heated and evaporated to release the metal on the support (if a release layer is provided, the release layer). Film formation can be performed on the top).
- a known method can be used. For example, a support is placed in a vacuum vessel, an inert gas such as argon is introduced, a DC voltage is applied, and the ionized inert gas is applied to the target metal. Film formation can be performed on the support (on the release layer in the case of having a release layer) by the metal that has been struck and struck.
- an inert gas such as argon
- a DC voltage is applied
- the ionized inert gas is applied to the target metal.
- Film formation can be performed on the support (on the release layer in the case of having a release layer) by the metal that has been struck and struck.
- a well-known method can also be used for the ion plating method.
- the support is placed in a vacuum vessel, the metal is heated and evaporated in a glow discharge atmosphere, and the ionized evaporated metal is used on the support (release layer). Can be formed on the release layer.
- the adhesive film with a metal film can be produced by forming a curable resin composition layer on the surface of the metal film layer after the formation process of the metal film layer of the film with the metal film.
- a known method can be used as a method for forming the curable resin composition layer.
- a resin varnish obtained by dissolving a resin composition in an organic solvent is prepared, and this resin varnish is attached to a metal film using a die coater or the like. It can be produced by coating on a metal film layer of the film and further drying the organic solvent by heating or blowing hot air to form a resin composition layer.
- organic solvent examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol.
- ketones such as acetone, methyl ethyl ketone and cyclohexanone
- acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, and carbitols such as cellosolve and butyl carbitol.
- Aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. You may use an organic solvent
- Drying conditions are not particularly limited, but the content of the organic solvent in the resin composition layer is preferably 10% by mass or less, and more preferably 5% by mass or less.
- the resin composition layer is formed by drying the varnish containing 30 to 60% by mass of the organic solvent at 50 to 150 ° C. for 3 to 10 minutes. Is preferred.
- the adhesive film with a metal film is prepared separately from the film with a metal film by forming an adhesive film having a curable resin composition layer formed on a support, and the metal film with the adhesive film and the adhesive film are combined with the metal film layer. It can also be produced by a method of bonding under heating conditions so that the curable resin composition layer is in contact.
- the curable resin composition layer is a prepreg
- the prepreg can be laminated on the support layer by, for example, a vacuum laminating method.
- the adhesive film can be produced by a known method.
- the support layer and the curable resin composition layer of the adhesive film are the same as described above.
- Bonding is performed by heat pressing using a hot press, a hot roll, or the like.
- the heating temperature is preferably 60 to 140 ° C, more preferably 80 to 120 ° C.
- the pressing pressure is preferably in the range of 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2 ), and 2 to 7 kgf / cm 2 (19.6 ⁇ 10 4 to 68.68. The range of 6 ⁇ 10 4 N / m 2 is more preferable.
- a multilayer printed wiring board can be manufactured using the film with a metal film or the adhesive film with a metal film manufactured as described above. An example of the method will be described next.
- the “inner circuit board” has a conductive layer patterned on one or both sides of a glass epoxy board, metal board, polyester board, polyimide board, BT resin board, thermosetting polyphenylene ether board, Further, it refers to an intermediate product on which an insulating layer and a conductor layer are to be formed.
- the curable resin composition layer may be laminated on the inner circuit board as an adhesive surface.
- a metal film layer is laminated
- a known method can be used to form the curable resin composition layer on the inner layer circuit board.
- an adhesive film in which the curable resin composition layer is formed on the support layer as described above is used as the inner layer circuit.
- a curable resin composition layer can be formed on the inner circuit board by laminating the substrate and removing the support layer.
- the lamination conditions for the adhesive film are the same as those for the adhesive film with a metal film, which will be described later.
- a prepreg is used as the curable resin composition layer, a single prepreg or a prepreg which is a surface layer on one or both sides of a laminate obtained by laminating a multilayer prepreg obtained by stacking a plurality of prepregs on a substrate, The metal film layer of the film-attached film can be stacked so as to be in contact with the prepreg surface.
- the film is laminated on the surface of the adherend by rolls or press-bonding from the viewpoint of easy workability and uniform contact. Especially, it is suitable to laminate
- the lamination method may be a batch method or a continuous method using a roll.
- the heating temperature is preferably 60 to 140 ° C, more preferably 80 to 120 ° C.
- the pressing pressure is preferably in the range of 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2 ), and 2 to 7 kgf / cm 2 (19.6 ⁇ 10 4 to 68.68. A range of 6 ⁇ 10 4 N / m 2 ) is particularly preferred.
- the lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.
- Vacuum lamination can be performed using a commercially available vacuum laminator.
- a commercially available vacuum laminator for example, a batch type vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd. MVLP-500, a vacuum applicator manufactured by Nichigo Morton Co., Ltd., a roll dry coater manufactured by Hitachi Industries, Ltd., Examples include a vacuum laminator manufactured by Hitachi IC Corporation.
- the lamination process for heating and pressurizing under reduced pressure can be performed using a general vacuum hot press machine.
- a general vacuum hot press machine For example, it can be performed by pressing a metal plate such as a heated SUS plate from the support layer side.
- the degree of vacuum is preferably 1 ⁇ 10 ⁇ 2 MPa or less, and more preferably 1 ⁇ 10 ⁇ 3 MPa or less.
- heating and pressurization can be carried out in one stage, it is preferable to carry out the conditions separately in two or more stages from the viewpoint of controlling the oozing of the resin.
- the first stage press has a temperature of 70 to 150 ° C. and the pressure is in a range of 1 to 15 kgf / cm 2
- the second stage press has a temperature of 150 to 200 ° C. and a pressure of 1 to 40 kgf / cm 2 It is preferable to carry out.
- the time for each stage is preferably 30 to 120 minutes.
- Examples of commercially available vacuum hot press machines include MNPC-V-750-5-200 (manufactured by Meiki Seisakusho), VH1-1603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like.
- the curable resin composition layer is cured to form an insulating layer.
- the curing conditions vary depending on the type of curable resin, the curing temperature is preferably 120 to 200 ° C., and the curing time is preferably 15 to 90 minutes.
- the removal of the support layer is generally performed by mechanical peeling with a manual or automatic peeling apparatus.
- the support layer can also be removed by etching.
- the support layer is preferably removed after the insulating layer is formed by the curing treatment of the curable resin composition layer. When the support layer is removed before the curing treatment, the metal film layer tends not to adhere sufficiently, and the metal film layer tends to crack after the curable resin composition layer is cured.
- the release layer is removed.
- the removal of the support layer and / or the release layer may be performed either before or after the step of forming the wiring groove by laser, but is preferably performed before the step of forming the wiring groove by laser.
- the release layer is preferably removed by an etching solution that dissolves the metal if it is a metal release layer, and is preferably removed by an aqueous solution if it is a water-soluble polymer release layer.
- the release layer is dissolved and removed.
- the aqueous solution for this purpose includes an alkaline aqueous solution in which sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide and the like are dissolved in water at a concentration of 0.5 to 10% by mass.
- Alcohols such as methanol, ethanol, and isopropyl alcohol may be contained in the aqueous solution as long as there is no problem in manufacturing a circuit board or the like.
- the method of dissolving and removing is not particularly limited, and examples thereof include a method of removing the support layer by immersing the substrate in the aqueous solution and dissolving and removing, and a method of dissolving and removing the aqueous solution by spraying it in a spray or mist form.
- the temperature of the aqueous solution is preferably room temperature to 80 ° C.
- the treatment time is preferably 10 seconds to 10 minutes with an aqueous solution such as water immersion or spraying.
- the alkaline aqueous solution include an alkaline developing solution (for example, 0.5 to 2 mass% sodium carbonate aqueous solution, 25 ° C.
- Stripping solution for example, 1-5 mass% sodium hydroxide aqueous solution, 40-60 ° C.
- swelling liquid used in desmear process for example, alkaline aqueous solution containing sodium carbonate, sodium hydroxide, 60-80 ° C.
- desmear process for example, alkaline aqueous solution containing sodium carbonate, sodium hydroxide, 60-80 ° C.
- a fine wiring groove can be formed by forming a metal film layer on the insulating layer and irradiating with a laser beam from above the metal film layer.
- a via can also be formed using a laser.
- the fine wiring groove can be formed more easily by including an inorganic filler having an average particle size of 0.02 to 5 ⁇ m in the insulating layer.
- the insulating layer is formed by using a laser from the support layer before removing the support layer or from the metal film layer after removing the support layer.
- a fine wiring groove it is possible to form a fine wiring groove in the insulating layer using a laser from the metal film layer after removing the support layer from the viewpoint of preventing the processing speed from slowing down. preferable. Further, when the release layer remains after the support layer is removed, a fine wiring groove can be formed in the insulating layer using a laser from above the release layer. Since the release layer is thin, it has little effect on the processing speed.
- a carbon dioxide gas laser, a UV-YAG laser, an excimer laser, or the like is generally used.
- the processing speed can be increased by adding a laser-absorbing component to the release layer.
- the laser absorbing component include metal compound powder, carbon powder, metal powder, and black dye.
- the blending amount of the laser energy absorbing component is preferably 0.05 to 40% by mass, more preferably 0.1 to 20% by mass, and still more preferably 1 to 10% by mass in all components constituting the release layer.
- the component is contained in a release layer formed from a water-soluble polymer resin, the total content including the water-soluble polymer resin and the component is 100% by mass, and the above content is added. preferable.
- Examples of the carbon powder include carbon black powder such as furnace black, channel black, acetylene black, thermal black, and anthracene black, graphite powder, and a powder of a mixture thereof.
- titania such as titanium oxide, magnesia such as magnesium oxide, iron oxide such as iron oxide, nickel oxide such as nickel oxide, zinc oxide such as manganese dioxide and zinc oxide, silicon dioxide, Aluminum oxide, rare earth oxide, cobalt oxide such as cobalt oxide, tin oxide such as tin oxide, tungsten oxide such as tungsten oxide, silicon carbide, tungsten carbide, boron nitride, silicon nitride, titanium nitride, aluminum nitride, sulfuric acid Examples thereof include powders of barium, rare earth oxysulfides, or mixtures thereof.
- metal powder examples include silver, aluminum, bismuth, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, antimony, silicon, tin, titanium, vanadium, tungsten, zinc, or an alloy or a mixture thereof. Is mentioned.
- Black dyes include azo (monoazo, disazo, etc.) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketone imine dyes, fluorone dyes, nitro dyes, xanthene dyes, acenaphthene dyes, quinophthalone dyes, aminoketone dyes, methine dyes, perylenes And dyes, coumarin dyes, perinone dyes, triphenyl dyes, triallylmethane dyes, phthalocyanine dyes, incrophenol dyes, azine dyes, or mixtures thereof.
- azo monoazo, disazo, etc.
- the black dye is preferably a solvent-soluble black dye in order to improve the dispersibility in the water-soluble polymer resin.
- These laser energy absorbing components may be used alone or in combination with different types.
- the laser energy absorbing component is preferably carbon powder, particularly carbon black, from the viewpoint of conversion efficiency of laser energy into heat, versatility, and the like.
- a desmear process can be further performed. It is preferable to perform a desmear process after forming a wiring groove using a laser.
- the desmear process can be performed by a known method such as a dry method such as plasma or a wet method using an oxidizing agent treatment such as an alkaline permanganate solution.
- the desmear process is a process of removing resin residues mainly generated by the formation of blind vias or wiring grooves, and the wall surfaces of vias and wiring grooves can be roughened.
- desmear with an oxidizing agent is preferable in that it can remove the smear of the via bottom and the wiring groove, and at the same time, the via wall surface can be roughened with the oxidizing agent to improve the plating adhesion strength.
- the desmear process using an oxidizing agent it is preferable to perform a swelling process using a swelling liquid, a roughening process using an oxidizing agent, and a neutralizing process using a neutralizing liquid in this order.
- the swelling liquid include an alkaline solution and a surfactant solution, and an alkaline solution is preferable.
- the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution.
- Examples of the swelling liquid that is commercially available include Swelling Dip Securigans P (Swelling Dip Securiganth SBU), Swelling Dip Securiganth SBU (Swelling Dip Securiganth SBU) manufactured by Atotech Japan Co., Ltd. be able to.
- Examples of the oxidizing agent include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide.
- the roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by applying the oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes.
- the concentration of permanganate in the alkaline permanganate solution is generally about 5 to 10% by weight.
- examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact CP and Dosing Solution Securigans P manufactured by Atotech Japan Co., Ltd.
- the neutralizing solution is preferably an acidic aqueous solution, and a commercially available product is Reduction Sholysin Securigant P (neutralizing solution) manufactured by Atotech Japan Co., Ltd.
- an electroless plating process can be further performed. It is preferable to perform an electroless plating process after the desmear process.
- an electroless plating layer can be formed on the surface of the insulating layer.
- the electroless plating process can be performed by a known method. For example, the surface of the insulating layer is treated with a surfactant and the like, and after applying a plating catalyst such as palladium, the electroless plating solution is impregnated with the electroless plating solution. A layer can be formed.
- an electrolytic plating process can be further performed. It is preferable to perform an electrolytic plating process after the electroless plating process.
- a conductor layer can be formed by an electrolytic plating process.
- the electrolytic plating step can be performed by a known method. For example, after forming an electroless plating layer (plating seed layer) 0.1 to 2 ⁇ m on the insulating layer, a conductor layer is formed by electrolytic plating.
- the conductor layer is preferably copper, and the thickness is preferably 3 to 35 ⁇ m, more preferably 5 to 25 ⁇ m, although it depends on the depth of the groove processed by laser processing and the height of the wiring groove to be formed.
- a step of further removing the conductor layer can be performed. It is preferable to perform the process of removing a conductor layer after an electroplating process. Since the copper layer is formed on the entire surface of the insulating layer by the electroless plating process and the electrolytic plating process, the step of removing the conductor layer on the surface until the insulating layer is exposed to the surface, the trench type wiring Can be formed. A schematic diagram of a trench type circuit board is shown in FIG.
- the step of removing the conductor layer on the surface can be performed by a known method, for example, by mechanical removal and / or etching away with a solution in which copper is dissolved.
- part means “part by mass”.
- MIT folding resistance is evaluated as “X” when the folding number is less than 50 times, evaluated as “ ⁇ ” when it is less than 50 to 100 times, and “ ⁇ ” when it is less than 100 to 200 times. The case was evaluated as “ ⁇ ” when it was 200 to less than 300 times, and “ ⁇ ”when it was 300 times or more.
- the PET film is peeled off from the laminated adhesive film, the resin composition is cured under a curing condition of 180 ° C. for 30 minutes, an insulating layer is formed, and the unevenness difference (Rt: maximum peak ⁇ on the insulating layer) to-valley) using a non-contact type surface roughness meter (WYKO NT3300, manufactured by Beeco Instruments Co., Ltd.) by a numerical value obtained with a measurement range of 1.2 mm ⁇ 0.91 mm using a VSI contact mode and a 10 ⁇ lens. It was. And it determined as follows. ⁇ : No appearance of voids in the appearance after lamination, and unevenness difference on the insulating layer is less than 5 ⁇ m. ⁇ : No appearance of voids in appearance after lamination, and an unevenness difference on the insulation layer of 5 ⁇ m or more. X: A void is generated after lamination, and the unevenness on the insulating layer cannot be measured.
- the adhesive films obtained in Examples and Comparative Examples were thermally cured at 190 ° C. for 90 minutes to obtain a sheet-like cured product.
- the cured product was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer manufactured by Rigaku Corporation (Thermo Plus TMA8310). After mounting the test piece on the apparatus, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min.
- the average linear thermal expansion coefficient from 25 ° C. to 150 ° C.
- the glass transition temperature (° C.) was calculated from the point at which the slope of the dimensional change signal in the second measurement changed.
- Example 1 14 parts of liquid bisphenol A type epoxy resin (epoxy equivalent 180, “jER828EL” manufactured by Japan Epoxy Resins Co., Ltd.) and 14 parts biphenyl aralkyl type epoxy resin (epoxy equivalent 269, “NC3000L” manufactured by Nippon Kayaku Co., Ltd.) 5 parts of biphenyl type epoxy resin (epoxy equivalent, “YX4000H” manufactured by Japan Epoxy Resin Co., Ltd.), phenoxy resin (“YL7553BH30” manufactured by Japan Epoxy Resin Co., Ltd., MEK and cyclohexanone having a solid content of 30% by mass 1: 1 solution), 20 parts of an imide skeleton-containing bifunctional phenol resin (phenolic hydroxyl group equivalent 252, manufactured by Japan Epoxy Resins Co., Ltd., described in the above general formula (7)), and DMAc 15 parts, While stirring to 15 parts of cyclohexanone It was heated and dissolved.
- biphenyl aralkyl type phenol resin phenolic hydroxyl group equivalent 242, “MEH7851-4H” manufactured by Meiwa Kasei Co., Ltd., cyclohexanone solution having a solid content of 50 mass%)
- dicyandiamide (“DICY7” manufactured by Japan Epoxy Resin Co., Ltd.) 2
- curing catalyst (Shikoku Kasei Kogyo Co., Ltd., “2E4MZ”) 0.1 part
- spherical silica average particle size 0.5 ⁇ m, manufactured by Admatechs Co., Ltd.
- “SOC2” aminosilane treated product) 50 parts were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. Next, it was applied on polyethylene terephthalate (thickness 38 ⁇ m, hereinafter abbreviated as “PET”) with a die coater so that the resin thickness after drying was 40 ⁇ m, and the temperature was 80 to 120 ° C. (average 100 ° C.). It was dried for 7 minutes (residual solvent amount of about 2% by mass). Subsequently, it wound up in roll shape, bonding a 15-micrometer-thick polypropylene film on the surface of a resin composition. The roll-like adhesive film was slit to a width of 507 mm, and a sheet-like adhesive film having a size of 507 ⁇ 336 mm was obtained therefrom.
- PET polyethylene terephthalate
- Example 2 50 parts of spherical silica of Example 1 (average particle size of 0.5 ⁇ m, aminosilane-treated product of “SOC2” manufactured by Admatechs Co., Ltd.) was added to spherical silica (average particle size of 0.25 ⁇ m, manufactured by Admatechs Co., Ltd. “SOC1”. An adhesive film was obtained in the same manner as in Example 1 except that the product was changed to “aminosilane-treated product”.
- Example 1 10 parts of the imide skeleton-containing bifunctional phenol resin of Example 1 (phenolic hydroxyl group equivalent 252 manufactured by Japan Epoxy Resin Co., Ltd., described in the above general formula (7)) was used as an imide skeleton-containing polyfunctional phenol resin (DIC).
- An adhesive film was obtained in exactly the same manner as in Example 1, except that the product was changed to 60 parts (“V-8003”, DMAc solution having a solid content of 16% by mass).
- Comparative Example 2 10 parts of an imide skeleton-containing bifunctional phenol resin of Example 1 (phenolic hydroxyl group equivalent 252; manufactured by Japan Epoxy Resin Co., Ltd., described in the above general formula (7)) was mixed with a bifunctional phenol resin (Tokyo Chemical Industry ( An adhesive film was obtained in the same manner as in Example 1 except that the product was changed to 10 parts “Bisphenol A” manufactured by the same company.
- Example 1 it can be seen that the present invention has been achieved. From Comparative Example 1, it can be seen that even if the resin has an imide skeleton, if it contains a polyfunctional phenolic hydroxyl group, the crosslink density increases and the laminating property deteriorates. This is a fatal defect in the production of printed wiring boards. In addition, it can be seen from Comparative Examples 2 and 3 that when a bifunctional phenol resin having no imide skeleton is used, the coefficient of linear thermal expansion increases and the number of folding times decreases.
- Example 3 ⁇ Production of film with metal film> Methyl ethyl ketone (hereinafter referred to as “MEK”) having a solid content of 10% by weight of hydroxypropylmethylcellulose phthalate (“HP-55” manufactured by Shin-Etsu Chemical Co., Ltd.) on a 38 ⁇ m thick polyethylene terephthalate (hereinafter referred to as “PET”) film.
- MEK Methyl ethyl ketone
- HP-55 hydroxypropylmethylcellulose phthalate
- PET polyethylene terephthalate
- DMF N, N-dimethylformamide
- the solvent was removed by heating, and an about 0.6 ⁇ m hydroxypropylmethylcellulose phthalate layer was formed on the PET film.
- a copper film layer having a thickness of about 200 nm was formed on the hydroxypropylmethylcellulose phthalate layer by sputtering to produce a film with a metal film.
- ⁇ Preparation of adhesive film having curable resin composition layer 28 parts of liquid bisphenol F type epoxy resin (epoxy equivalent 170, “Epicoat 806H” manufactured by Japan Epoxy Resin Co., Ltd.) and naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, “HP4700” manufactured by Dainippon Ink & Chemicals, Inc.) ) 28 parts, 20 parts of phenoxy resin (1: 1 solution of MEK and cyclohexanone with a non-volatile content of 30% by mass “YX6954BH30” manufactured by Japan Epoxy Resins Co., Ltd.) was dissolved in 15 parts of MEK and 15 parts of cyclohexanone with stirring. .
- the varnish is coated on a PET film with a thickness of 38 ⁇ m with an alkyd mold release agent (AL-5) (manufactured by Lintec Corporation) using a die coater, the solvent is removed using a hot air drying furnace, and a curable resin composition layer is formed.
- An adhesive film having a thickness of 50 ⁇ m was prepared.
- Atotech Japan Co., Ltd. a concentrate compact of Atotech Japan Co., Ltd. is used as a roughening liquid. It was immersed in P (KMnO 4 : 60 g / L, NaOH: 40 g / L aqueous solution) at 80 ° C. for 20 minutes, and finally, neutralized solution at 40 ° C. in the Reduction Sholyshin Securigant P of Atotech Japan Co., Ltd. Soaked for 5 minutes. Then, it was washed with water and dried.
- P KMnO 4 : 60 g / L, NaOH: 40 g / L aqueous solution
- Electroless copper plating (using an electroless copper plating process using Atotech Japan Co., Ltd. pharmaceutical solution) was performed on the insulating layer obtained by etching the copper film layer.
- the film thickness of the electroless copper plating was 0.8 ⁇ m.
- the electrolytic copper plating was about 25 ⁇ m thick, and the groove of the wiring was filled with copper, and then unnecessary copper (conductor layer) on the outermost surface was removed by mechanical polishing until the insulating layer appeared on the surface to obtain a circuit board.
- the line (wiring) / space (interval) 8/8 ⁇ m.
- Example 4 After removing the support, the release layer, and the copper film layer, SEM observation of the wiring groove was performed in the same manner as in Example 3 except that laser processing was performed. An SEM photograph of the wiring trench is shown in FIG. Furthermore, when a circuit board was obtained in the same manner as in Example 3 and the wiring shape was observed in a cross-section, the upper portion of the space (interval) spread to 12 ⁇ m or more and was not a desired shape.
- Example 3 it was found that the fine wiring groove can be formed in the insulating layer by using the method of the present invention. Furthermore, even after the desmear process, it is possible to maintain a good wiring groove shape by protecting the uppermost portion of the insulating layer with the copper film layer.
- the resin composition containing a resin having an imide skeleton-containing bifunctional phenol resin of the present invention is excellent in laminating properties when used in an adhesive film, and has a linear thermal expansion coefficient of an insulating layer obtained by curing the resin composition. It is possible to provide a resin composition having a low flexibility and excellent flexibility, and an adhesive film, a prepreg, and a multilayer printed wiring board using the resin composition. Furthermore, electric products such as computers, mobile phones, digital cameras, and televisions, and vehicles such as motorcycles, automobiles, trains, ships, and airplanes equipped with these can be provided.
- the fine wiring groove forming method of the present invention can be provided, and furthermore, a circuit board containing the fine wiring groove, and further, an electric product such as a computer, a mobile phone, a digital camera, a television, etc., equipped with these.
- Vehicles such as motorcycles, automobiles, trains, ships, and aircraft can also be provided.
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Abstract
Description
[1](A)イミド骨格含有2官能フェノール樹脂を含有することを特徴とする樹脂組成物。
[2](A)イミド骨格含有2官能フェノール樹脂の含有量が、樹脂組成物中の不揮発分100質量%に対し、0.1~30質量%であることを特徴とする上記[1]に記載の樹脂組成物。
[3]更に(B)無機充填材を含有することを特徴とする上記[1]~[2]のいずれかに記載の樹脂組成物。
[4]更に(C)エポキシ樹脂を含有することを特徴とする上記[1]~[3]のいずれかに記載の樹脂組成物。
[5]絶縁層に用いる樹脂組成物であって、耐折回数が50回以上であることを特徴とする上記1~4のいずれかに記載の樹脂組成物。
[6]絶縁層に用いる樹脂組成物であって、線熱膨張率が4~40ppmであることを特徴とする、上記[1]~[5]のいずれかに記載の樹脂組成物。
[7]上記[1]~[6]のいずれかに記載の樹脂組成物が支持フィルム上に層形成されていることを特徴とする接着フィルム。
[8]上記[1]~[6]のいずれかに記載の樹脂組成物が繊維からなるシート状繊維基材中に含浸されていることを特徴とするプリプレグ。
[9]上記[1]~[6]のいずれかに記載の樹脂組成物の硬化物により絶縁層が形成されていることを特徴とする回路基板。
[10]樹脂組成物に平均粒径0.02~5μmの無機充填材を含有させることを特徴とする、絶縁層の微細配線溝形成方法。
[11]絶縁層の上部からレーザー照射することを特徴とする、上記[10]記載の絶縁層の微細配線溝形成方法。
[12]絶縁層上に金属膜層が形成されていることを特徴とする、上記[10]~[11]のいずれかに記載の絶縁層の微細配線溝形成方法。
[13]金属膜層の厚みが50~500nmであることを特徴とする、上記[12]に記載の絶縁層の微細配線溝形成方法。
[14]金属膜層が銅であることを特徴とする、上記[12]~[13]のいずれかに記載に絶縁層の微細配線溝形成方法。
[15]上記[10]~[14]のいずれかに記載の絶縁層の微細配線溝形成方法を含有することを特徴とする、トレンチ型回路基板の製造方法。
[16]更に、デスミア工程を含有することを特徴とする、上記[15]に記載のトレンチ型回路基板の製造方法。
[17]更に、メッキ工程を含有することを特徴とする、上記[15]~[16]のいずれかに記載にトレンチ型回路基板の製造方法。
[18]更に、銅層を除去する工程を含有することを特徴とする、上記[15]~[17]のいずれかに記載のトレンチ型回路基板の製造方法。
本発明において使用される(A)イミド骨格含有2官能フェノール樹脂は、特に限定されるものではなく、一分子中に2個のフェノール性水酸基とイミド骨格を有するものであれば良い。一分子中にフェノール性水酸基が2個だけ存在することで、樹脂組成物の硬化後の絶縁層が適度な架橋密度となり、耐折性能とラミネート性能が同時に発揮される。例えば、下記一般式(1)、下記一般式(4)が好ましく、下記一般式(2)、下記一般式(5)がより好ましく、下記一般式(3)、下記一般式(6)が更に好ましく、下記一般式(7)が更に一層好ましい。
本発明の樹脂組成物には、当該樹脂組成物から得られる絶縁層の熱膨張率をさらに低下させるために無機充填材を含有させる事ができる。無機充填材としては、特に制限はないが、シリカ、アルミナ、硫酸バリウム、タルク、クレー、雲母粉、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、窒化ホウ素、ホウ酸アルミニウム、チタン酸バリウム、チタン酸ストロンチウム、チタン酸カルシウム、チタン酸マグネシウム、チタン酸ビスマス、酸化チタン、ジルコン酸バリウム、ジルコン酸カルシウムなどが挙げられ、なかでもシリカが好ましい。これらの中でも無定形シリカ、溶融シリカ、結晶シリカ、合成シリカ、粉砕シリカ、中空シリカ、球状シリカが好ましく、溶融シリカ、球状シリカがより好ましい。これらは1種又は2種以上組み合わせて使用してもよい。
本発明の樹脂組成物には、当該樹脂組成物から得られる絶縁層の耐熱性、絶縁信頼性、屈曲性、金属膜との密着性を向上させるためにエポキシ樹脂を含有させる事ができる。エポキシ樹脂としては、特に制限はないが、ビスフェノールA型エポキシ樹脂、ビフェニル型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、リン含有エポキシ樹脂、ビスフェノールS型エポキシ樹脂、脂環式エポキシ樹脂、脂肪族鎖状エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビスフェノールAノボラック型エポキシ樹脂、ブタジエン構造を有するエポキシ樹脂、シクロヘキサンジメタノール型エポキシ樹脂、グリシジルアミン型エポキシ樹脂、ビスフェノールのジグリシジルエーテル化物、ナフタレンジオールのジグリシジルエーテル化物、フェノール類のグリシジルエーテル化物、及びアルコール類のジグリシジルエーテル化物、並びにこれらのエポキシ樹脂のアルキル置換体、ハロゲン化物及び水素添加物等が挙げられる。これらは1種又は2種以上組み合わせて使用してもよい。
本発明の樹脂組成物には、当該樹脂組成物から得られる絶縁層の耐熱性を向上させ、絶縁信頼性を向上させ、誘電正接を低下させる等のために(D)成分を含有させる事ができる。(D)成分としては、エポキシ樹脂を硬化する機能を有するものであれば特に限定されず、具体的には、フェノール系硬化剤、ナフトール系硬化剤、活性エステル系硬化剤、ベンゾオキサジン系硬化剤、シアネートエステル系硬化剤等が挙げられる。これらは1種又は2種以上組み合わせて使用してもよい。
本発明の樹脂組成物には、当該樹脂組成物を効率よく硬化させるという観点から、(E)硬化促進剤を含有させる事ができる。(E)硬化促進剤としては、特に限定されるものではなく、金属系硬化促進剤、イミダゾール系硬化促進剤、アミン系硬化促進剤、有機ホスフィン化合物、有機ホスホニウム塩化合物等が挙げられる。
本発明の樹脂組成物には、硬化物の機械強度や接着フィルムの形態で使用する場合のフィルム成型能を向上させるという観点から、(F)熱可塑性樹脂を含有させる事ができる。このような(F)熱可塑性樹脂としては、フェノキシ樹脂、ポリビニルアセタール樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレンエーテル樹脂、ポリカーボネート樹脂、ポリエーテルエーテルケトン樹脂、ポリエステル樹脂等を挙げることができる。なかでも、ポリビニルアセタール樹脂、フェノキシ樹脂が好ましい。これらは1種又は2種以上を組み合わせて使用してもよい。
本発明の樹脂組成物には、硬化物の機械強度を高め、応力緩和効果を向上させるという観点から、(G)ゴム粒子を含有させる事ができる。(G)ゴム粒子は、樹脂組成物を調製する際の有機溶媒にも溶解せず、エポキシ樹脂等の樹脂組成物中の成分とも相溶せず、樹脂組成物のワニス中では分散状態で存在するものが好ましい。このようなゴム粒子は、一般には、ゴム成分の分子量を有機溶剤や樹脂に溶解しないレベルまで大きくし、粒子状とすることで調製される。ゴム粒子としては、例えば、コアシェル型ゴム粒子、架橋アクリルニトリルブタジエンゴム粒子、架橋スチレンブタジエンゴム粒子、アクリルゴム粒子などが挙げられる。コアシェル型ゴム粒子は、粒子がコア層とシェル層を有するゴム粒子であり、例えば、外層のシェル層がガラス状ポリマー、内層のコア層がゴム状ポリマーで構成される2層構造、または外層のシェル層がガラス状ポリマー、中間層がゴム状ポリマー、コア層がガラス状ポリマーで構成される3層構造のものなどが挙げられる。ガラス状ポリマー層は例えば、メタクリル酸メチルの重合物などで構成され、ゴム状ポリマー層は例えば、ブチルアクリレート重合物(ブチルゴム)などで構成される。コアシェル型ゴム粒子の具体例としては、スタフィロイドAC3832、AC3816N、(ガンツ化成(株)商品名)、メタブレンKW−4426(三菱レイヨン(株)商品名)が挙げられる。アクリロニトリルブタジエンゴム(NBR)粒子の具体例としては、XER−91(平均粒径0.5μm、JSR(株)製)などが挙げられる。スチレンブタジエンゴム(SBR)粒子の具体例としては、XSK−500(平均粒径0.5μm、JSR(株)製)などが挙げられる。アクリルゴム粒子の具体例としては、メタブレンW300A(平均粒径0.1μm)、W450A(平均粒径0.5μm)(三菱レイヨン(株)製)を挙げることができる。これらは1種又は2種以上を組み合わせて使用してもよい。
本発明の樹脂組成物は、難燃性向上の観点から、(H)難燃剤をさらに含有することができる。(H)難燃剤としては、例えば、有機リン系難燃剤、有機系窒素含有リン化合物、窒素化合物、シリコーン系難燃剤、金属水酸化物等が挙げられる。有機リン系難燃剤としては、三光(株)製のHCA、HCA−HQ、HCA−NQ等のフェナントレン型リン化合物、昭和高分子(株)製のHFB−2006M等のリン含有ベンゾオキサジン化合物、味の素ファインテクノ(株)製のレオフォス30、50、65、90、110、TPP、RPD、BAPP、CPD、TCP、TXP、TBP、TOP、KP140、TIBP、北興化学工業(株)製のPPQ、クラリアント(株)製のOP930、大八化学(株)製のPX200等のリン酸エステル化合物、東都化成(株)製のFX289、FX305等のリン含有エポキシ樹脂、東都化成(株)製のERF001等のリン含有フェノキシ樹脂、ジャパンエポキシレジン(株)製のYL7613等のリン含有エポキシ樹脂等が挙げられる。有機系窒素含有リン化合物としては、四国化成工業(株)製のSP670、SP703等のリン酸エステルミド化合物、大塚化学(株)社製のSPB100、SPE100、(株)伏見製作所製FP−series等のホスファゼン化合物等が挙げられる。金属水酸化物としては、宇部マテリアルズ(株)製のUD65、UD650、UD653等の水酸化マグネシウム、巴工業(株)社製のB−30、B−325、B−315、B−308、B−303、UFH−20等の水酸化アルミニウム等が挙げられる。これらは1種又は2種以上を組み合わせて使用してもよい。
本発明の接着フィルムは、当業者に公知の方法、例えば、有機溶剤に樹脂組成物を溶解した樹脂ワニスを調製し、この樹脂ワニスを、ダイコーターなどを用いて、支持体に塗布し、更に加熱、あるいは熱風吹きつけ等により有機溶剤を乾燥させて樹脂組成物層を形成させることにより製造することができる。
上記のようにして製造した接着フィルムを用いて多層プリント配線板を製造することができる。その方法の一例を次に説明する。樹脂組成物層が保護フィルムで保護されている場合はこれらを剥離した後、樹脂組成物層を内層回路基板に直接接するように、内層回路基板の片面又は両面にラミネートする。本発明の接着フィルムにおいては真空ラミネート法により減圧下で内層回路基板にラミネートする方法が好適に用いられる。ラミネートの方法はバッチ式であってもロールでの連続式であってもよい。またラミネートを行う前に接着フィルム及び内層回路基板を必要により加熱(プレヒート)しておいてもよい。
本発明のプリプレグは、本発明の樹脂組成物をシート状繊維基材にホットメルト法又はソルベント法により含浸させ、加熱して半硬化させることにより製造することができる。すなわち、本発明の樹脂組成物がシート状繊維基材に含浸した状態となるプリプレグとすることができる。シート状繊維基材としては、ガラスクロスやアラミド繊維等のプリプレグ用繊維として常用されている繊維からなるものを用いることが好ましい。
上記のようにして製造したプリプレグを用いて多層プリント配線板を製造することができる。その方法の一例を次に説明する。内層回路基板に本発明のプリプレグを1枚あるいは必要により数枚重ね、離型フィルムを介して金属プレートで挟み、加圧・加熱条件下でプレス積層する。加圧・加熱条件は、好ましくは、圧力が5~40kgf/cm2(49×104~392×104N/m2)、温度が120~200℃で20~100分である。また接着フィルムと同様に、プリプレグを真空ラミネート法により回路基板にラミネートした後、加熱硬化することも可能である。その後、上記で記載した方法と同様にして、硬化したプリプレグ表面を粗化した後、導体層をメッキにより形成して多層プリント配線板を製造することができる。
さらに本発明の多層プリント配線板を用いることで半導体装置を製造することができる。多層プリント配線板上の接続用電極部分に半導体素子を接合することにより、半導体装置を製造する。半導体素子の搭載方法は、特に限定されないが、例えば、ワイヤボンディング実装、フリップチップ実装、異方性導電フィルム(ACF)による実装、非導電性フィルム(NCF)による実装などが挙げられる。
支持体層は自己支持性を有するフィルム乃至シート状物であり、金属箔、プラスチックフィルム等を用いることができ、特にプラスチックフィルムが好適に用いられる。金属箔としては、アルミニウム箔、銅箔等が挙げられる。支持体層として金属箔を用いる場合で金属膜付きフィルムが離型層を有しない場合は、形成される金属膜層とは別の金属からなる金属箔が採用される。プラスチックフィルムとしては、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレート、ポリイミド、ポリアミドイミド、ポリアミド、ポリテトラフルオロエチレン、ポリカーボネート等が挙げられ、ポリエチレンテレフタレートフィルム、ポリエチレンナフタレートフィルムが好ましく、中でも、安価なポリエチレンテレフタレートが特に好ましい。また支持体層表面は、コロナ処理等の表面処理が施してあってもよい。また金属膜層や離型層が存在しない側の支持体層フィルム表面にも、マット処理、コロナ処理等の表面処理が施してあってもよい。離型層が形成される側の支持体層表面は、金属膜付きフィルムを製造する際のクラック防止の観点から、算術平均粗さ(Ra値)を50nm以下(0以上50nm以下)、さらには40nm以下、さらには35nm以下、さらには30nm以下とするのが好ましい。また離型層が形成されない側の支持体層表面の算術平均粗さも、上記と同じ範囲内とするのが好ましい。算術平均粗さ(Ra値)の測定は、公知の方法を用いることができ、例えば、非接触型表面粗さ計(例えば、ビーコインスツルメンツ社製WYKO NT3300等)などの装置を用いて測定することができる。支持体は市販のものを用いることもでき、例えば、T60(東レ(株)製、ポリエチレンテレフタレートフィルム)、A4100(東洋紡(株)製、ポリエチレンテレフタレートフィルム)、Q83(帝人デュポンフィルム(株)製、ポリエチレンナフタレートフィルム)、リンテック(株)製、アルキッド型離型剤(AL−5)付きポリエチレンテレフタレートフィルム、ダイアホイル(登録商標)B100(三菱化学ポリエステルフィルム(株)製、ポリエチレンテレフタレートフィルム)等が挙げられる。
本発明における金属膜付きフィルム及び金属膜付き接着フィルムは、金属膜を被着体表面に効率的に転写するため、支持体層と金属膜層間に離型層を有するのが好ましい。
本発明でいう「水溶性セルロース樹脂」とは、セルロースに水溶性を付与するための処理を施したセルロース誘導体のことであり、好適には、セルロースエーテル、セルロースエーテルエステル等が挙げられる。
本発明でいう「水溶性ポリエステル樹脂」とは、多価カルボン酸またはそのエステル形成性誘導体と多価アルコールまたはそのエステル形成性誘導体を主たる原料とする通常の重縮合反応によって合成されるような、実質的に線状のポリマーからなるポリエステル樹脂であって、分子中または分子末端に親水基が導入されたものである。ここで、親水基としては、スルホ基、カルボキシル基、燐酸基等の有機酸基またはその塩等が挙げられ、好ましくは、スルホン酸基またはその塩、カルボン酸基またはその塩である。水溶性ポリエステル樹脂としては、特にスルホ基もしくはその塩及び/又はカルボキシル基もしくはその塩を有するものが好ましい。
本発明でいう「水溶性アクリル樹脂」とは、カルボキシル基含有単量体を必須成分として含有することで、水に分散乃至溶解するアクリル樹脂である。
金属膜層に使用する金属としては、金、白金、銀、銅、アルミニウム、コバルト、クロム、ニッケル、チタン、タングステン、鉄、スズ、インジウム等の金属単体やニッケル・クロムアロイ等の2種類以上の金属の固溶体(アロイ)を使用することができるが、金属膜形成の汎用性、コスト、エッチングによる除去の容易性等の観点から、クロム、ニッケル、チタン、ニッケル・クロムアロイ、アルミニウム、亜鉛、銅・ニッケルアロイ、銅・チタンアロイ、金、銀及び銅が好ましく、クロム、ニッケル、チタン、ニッケル・クロムアロイ、アルミニウム、亜鉛、金、銀及び銅がより好ましく、銅が特に好ましい。また、金属膜層は単層であっても、異なる金属が2層以上積層した複層構造であってもよい。
本発明における金属膜付き接着フィルムは、上述した金属膜付きフィルムの金属膜層上に更に硬化性樹脂組成物層が形成された構造を有する。すなわち、本発明における金属膜付き接着フィルムは、支持体層、金属膜層に加え、さらに硬化性樹脂組成物層を有する。また金属膜付きフィルムと同様、支持体層と金属膜層間に離型層を有するのが好ましい。金属膜付き接着フィルムにおいて、硬化性樹脂組成物層に使用する硬化性樹脂組成物は、その硬化物が、十分な硬度と絶縁性を有するものであれば、特に限定なく使用でき、なかでも、(a)エポキシ樹脂、(b)熱可塑性樹脂及び(c)硬化剤を含有することが好ましい。その他にも、上記で記載したゴム粒子、難燃剤、各種樹脂添加剤、マレイミド化合物、ビスアリルナジイミド化合物、ビニルベンジル樹脂、ビニルベンジルエーテル樹脂、ビスマレイミド−トリアジン樹脂、アクリル樹脂等を使用することができる。
本発明で使用する金属膜付きフィルム及び金属膜付き接着フィルムの製造方法は、特に制限されないが、以下の方法が好適である。
上記のようにして製造した金属膜付きフィルム又は金属膜付き接着フィルムを用いて多層プリント配線板を製造することができる。その方法の一例を次に説明する。
まずは各種測定方法・評価方法について説明する。
実施例及び比較例で作成した接着フィルムを、190℃、90分で硬化し、カッターを用いて110mm×15mmの評価用サンプルを5本作成した。(株)東洋精機製作所製、MIT耐折疲労試験機「MIT−DA」を使用して、JIS C−5016に準拠して、荷重2.5N、折曲げ角度135度、折曲げ速度175回/分、曲率半径0.38mmと設定してMIT耐折性試験を行い、耐折回数を測定した。5本の評価用サンプルの耐折回数の平均値を求めた。MIT耐折性は、耐折回数が50回未満の場合を「×」と評価し、50~100回未満の場合を「△」と評価し、100~200回未満の場合を「○」と評価し、200~300回未満の場合を「◎」と評価し、300回以上の場合を「◎○」と評価した。
実施例及び比較例で作製した接着フィルムを、バッチ式真空加圧ラミネーターMVLP−500(名機(株)製商品名)を用いて、導体厚35μmでL(ライン:配線幅)/S(スペース:間隔幅)=160μm/160μmの櫛歯状の導体パターン上にラミネートした。ラミネートは、30秒間減圧して気圧を13hPa以下とし、その後30秒間、100℃、圧力0.74MPaでプレスすることにより行った。ラミネート後の樹脂組成物層の外観検査を行った。また、ラミネートされた接着フィルムからPETフィルムを剥離し、180℃、30分の硬化条件で樹脂組成物を硬化して、絶縁層を形成し、絶縁層上の凹凸差(Rt:最大のpeak−to−valley)の値を非接触型表面粗さ計(ビーコインスツルメンツ社製WYKO NT3300)を用いて、VSIコンタクトモード、10倍レンズにより測定範囲を1.2mm×0.91mmとして得られる数値により求めた。そして以下のように判定を行った。
○:ラミネート後の外観にボイドの発生が無く、絶縁層上の凹凸差が5μm未満のもの
△:ラミネート後の外観にボイドの発生が無く、絶縁層上の凹凸差が5μm以上のもの、
×:ラミネート後にボイドが発生し、絶縁層上の凹凸差の測定ができないもの
実施例および比較例で得られた接着フィルムを190℃で90分熱硬化させてシート状の硬化物を得た。その硬化物を、幅約5mm、長さ約15mmの試験片に切断し、(株)リガク製熱機械分析装置(Thermo Plus TMA8310)を使用して、引張加重法で熱機械分析を行った。試験片を前記装置に装着後、荷重1g、昇温速度5℃/分の測定条件にて連続して2回測定した。2回目の測定における25℃から150℃までの平均の線熱膨張率を算出した。線熱膨張率の値が41ppm以上の場合を「×」とし、37ppm以上41ppm未満の場合を「△」とし、37ppm未満の場合を「○」とした。また2回目の測定における寸法変化シグナルの傾きが変化する点からガラス転移温度(℃)を算出した。
液状ビスフェノールA型エポキシ樹脂(エポキシ当量180、ジャパンエポキシレジン(株)製「jER828EL」)14部と、ビフェニルアラルキル型エポキシ樹脂(エポキシ当量269、日本化薬(株)製「NC3000L」)14部、ビフェニル型エポキシ樹脂(エポキシ当量、ジャパンエポキシレジン(株)製「YX4000H」)5部、フェノキシ樹脂(重量平均分子量38000、ジャパンエポキシレジン(株)製「YL7553BH30」、固形分30質量%のMEKとシクロヘキサノンの1:1溶液)20部、イミド骨格含有2官能フェノール樹脂(フェノール性水酸基当量252、ジャパンエポキシレジン(株)製、上記一般式(7)に記載のもの)10部とを、DMAc15部、シクロヘキサノン15部に撹拌しながら加熱溶解させた。そこへ、ビフェニルアラルキル型フェノール樹脂(フェノール性水酸基当量242、明和化成(株)製「MEH7851−4H」、固形分50質量%のシクロヘキサノン溶液)40部、ジシアンジアミド(ジャパンエポキシレジン(株)製「DICY7」)2部、硬化触媒(四国化成工業(株)製、「2E4MZ」)0.1部、球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」のアミノシラン処理品)、50部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した。次に、ポリエチレンテレフタレート(厚さ38μm、以下「PET」と略称する。)上に、乾燥後の樹脂厚みが40μmとなるようにダイコーターにて塗布し、80~120℃(平均100℃)で7分間乾燥した(残留溶媒量約2質量%)。次いで樹脂組成物の表面に厚さ15μmのポリプロピレンフィルムを貼り合わせながらロール状に巻き取った。ロール状の接着フィルムを幅507mmにスリット(slit)し、これより507×336mmサイズのシート状の接着フィルムを得た。
実施例1の球形シリカ(平均粒径0.5μm、(株)アドマテックス製「SOC2」のアミノシラン処理品)50部を、球状シリカ(平均粒径0.25μm、(株)アドマテックス製「SOC1」のアミノシラン処理品)に変更した以外は実施例1と全く同様にして接着フィルムを得た。
実施例1のイミド骨格含有2官能フェノール樹脂(フェノール性水酸基当量252、ジャパンエポキシレジン(株)製、上記一般式(7)に記載のもの)10部を、イミド骨格含有多官能フェノール樹脂(DIC(株)製「V−8003」、固形分16質量%のDMAc溶液)60部に変更した以外は実施例1と全く同様にして接着フィルムを得た。
実施例1のイミド骨格含有2官能フェノール樹脂(フェノール性水酸基当量252、ジャパンエポキシレジン(株)製、上記一般式(7)に記載のもの)10部を、2官能フェノール樹脂(東京化成工業(株)製「ビスフェノールA」)10部に変更した以外は実施例1と全く同様にして接着フィルムを得た。
実施例1のイミド骨格含有2官能フェノール樹脂(フェノール性水酸基当量252、ジャパンエポキシレジン(株)製、上記一般式(7)に記載のもの)10部を、2官能フェノール樹脂(東京化成工業(株)製「ビスフェノールS」)10部に変更した以外は実施例1と全く同様にして接着フィルムを得た。
<金属膜付きフィルムの作製>
厚み38μmのポリエチレンテレフタレート(以下、「PET」と略す)フィルム上に、ヒドロキシプロピルメチルセルロースフタレート(信越化学工業(株)製「HP−55」)の固形分10重量%のメチルエチルケトン(以下、「MEK」と略す)とN,N−ジメチルホルムアミド(以下、「DMF」と略す)の1:1溶液をダイコータにより塗布し、熱風乾燥炉を用いて室温から140℃まで昇温速度3℃/秒で昇温することで溶剤を除去し、PETフィルム上に約0.6μmのヒドロキシプロピルメチルセルロースフタレート層を形成させた。次いで、ヒドロキシプロピルメチルセルロースフタレート層上にスパッタリングにより、銅膜層約200nmを形成して、金属膜付きフィルムを作製した。
液状ビスフェノールF型エポキシ樹脂(エポキシ当量170、ジャパンエポキシレジン(株)製「エピコート806H」)28部と、ナフタレン型4官能エポキシ樹脂(エポキシ当量163、大日本インキ化学工業(株)製「HP4700」)28部、フェノキシ樹脂(ジャパンエポキシレジン(株)製「YX6954BH30」不揮発分30質量%のMEKとシクロヘキサノンの1:1溶液)20部とをMEK15部、シクロヘキサノン15部に撹拌しながら加熱溶解させた。そこへ、トリアジン含有フェノールノボラック樹脂(水酸基当量125、DIC(株)製「LA7054」、不揮発分60質量%のMEK溶液)27部、ナフトール系硬化剤(水酸基当量215、東都化成(株)製「SN−485」)の固形分50質量%のMEK溶液27部、硬化触媒(四国化成工業(株)製、「2E4MZ」)0.1部、球形シリカ(平均粒径0.25μm、(株)アドマテックス製「SOC1」のアミノシラン処理品)70部、ポリビニルブチラール樹脂(積水化学工業(株)製「KS−1」)の固形分15質量%のエタノールとトルエンの1:1溶液30部を混合し、高速回転ミキサーで均一に分散して、樹脂ワニスを作製した。厚み38μmのアルキッド型離型剤(AL−5)付きPETフィルム(リンテック(株)製)上に上記ワニスをダイコータにより塗布し、熱風乾燥炉を用いて溶剤を除去し、硬化性樹脂組成物層の厚みが50μmである接着フィルムを作製した。
上記接着フィルムの硬化性樹脂組成物層と金属膜付きフィルムの銅膜層が接触するように、90℃で貼り合わせて巻取り、金属膜付き接着フィルムを得た。
両面に18μm厚の銅回路が形成されているガラスエポキシ基板の銅回路上をCZ8100(アゾール類の銅錯体、有機酸を含む表面処理剤(メック(株)製))処理にて粗化を施した。次に、上記金属膜付き接着フィルムのアルキッド型離型剤(AL−5)付きPETフィルムを剥離し、硬化性樹脂組成物層が銅回路表面と接するようにし、バッチ式真空加圧ラミネーターMVLP−500((株)名機製作所製商品名)を用いて、基板の両面に積層した。積層は30秒間減圧して気圧を13hPa以下で行った。その後、160℃で30分間熱硬化し絶縁層を形成した。
支持体層であるPETフィルムを剥離した後、UV−YAGレーザーを使用して配線溝(ライン(配線)/スペース(間隔)=8/8μm。深さ12μm)およびトップ径70μmの層間接続用ビアを形成した。次いで、ヒドロキシプロピルメチルセルロースフタレート層を1重量%炭酸ナトリウム水溶液で溶解除去した。次に、デスミア工程として、膨潤液であるアトテックジャパン(株)のスエリングディップ・セキュリガントPに80℃で10分間浸漬し、次に、粗化液として、アトテックジャパン(株)のコンセントレート・コンパクトP(KMnO4:60g/L、NaOH:40g/Lの水溶液)に80℃で20分間浸漬し、最後に中和液として、アトテックジャパン(株)のリダクションショリューシン・セキュリガントPに40℃で5分間浸漬した。その後、水洗、乾燥させた。
上記基板を、塩化第二銅水溶液に25℃で1分間浸漬させ、絶縁層上の銅膜層をエッチング除去し、ビア底銅回路表面のエッチングを行い、その後、水洗し、配線溝を(株)日立ハイテクノロジーズ製「S—4800」を用いて、倍率2000倍で、SEM観察を行った。その写真を図2に示す。
上記銅膜層をエッチングした絶縁層上に無電解銅めっき(アトテックジャパン(株)製薬液を使用した無電解銅めっきプロセスを使用)を行った。無電解銅めっきの膜厚は0.8μmとなった。その後、電解銅めっき約25μm厚で、配線の溝を銅で埋め込み、その後、最表面の不要な銅(導体層)を機械研磨により絶縁層が表面に出るまで除去し、回路基板を得た。配線形状を断面観察したところ、ライン(配線)/スペース(間隔)=8/8μmの良好なものであった。
支持体と離型層と銅膜層を除去した後、レーザー加工をしたこと以外は実施例3とまったく同様にして配線溝のSEM観察を行った。配線溝のSEM写真を図3に示す。さらに、実施例3と同様にして回路基板を得て、配線形状を断面観察したところ、スペース(間隔)の上部は12μm以上に広がり、所望の形状ではなかった。
また、本発明の微細配線溝形成方法を提供できるようになり、更には、微細配線溝を含有した回路基板、更にこれらを搭載した、コンピューター、携帯電話、デジタルカメラ、テレビ、等の電気製品や、自動二輪車、自動車、電車、船舶、航空機、等の乗物も提供できるようになった。
2 絶縁層
3 内層回路基板
Claims (20)
- (A)イミド骨格含有2官能フェノール樹脂を含有することを特徴とする樹脂組成物。
- (A)イミド骨格含有2官能フェノール樹脂の含有量が、樹脂組成物中の不揮発分100質量%に対し、0.1~30質量%であることを特徴とする請求項1に記載の樹脂組成物。
- (A)イミド骨格含有2官能フェノール樹脂の重量平均分子量が、200~1500であることを特徴とする請求項1又は2に記載の樹脂組成物。
- 更に(B)無機充填材を含有することを特徴とする請求項1~3のいずれか1項に記載の樹脂組成物。
- (B)無機充填材の平均粒径が0.02μm~5μmであることを特徴とする請求項4に記載の樹脂組成物。
- 樹脂組成物の硬化物の耐折回数が50回以上10000回以下であることを特徴とする請求項1~5のいずれか1項に記載の樹脂組成物。
- 樹脂組成物の硬化物の線熱膨張率が4~40ppmであることを特徴とする、請求項1~6のいずれか1項に記載の樹脂組成物。
- 請求項1~7のいずれか1項に記載の樹脂組成物が支持フィルム上に層形成されていることを特徴とする接着フィルム。
- 請求項1~7のいずれか1項に記載の樹脂組成物が繊維からなるシート状繊維基材中に含浸されていることを特徴とするプリプレグ。
- 請求項1~7のいずれか1項に記載の樹脂組成物の硬化物により絶縁層が形成されていることを特徴とする回路基板。
- 請求項10に記載の回路基板を用いることを特徴とする半導体装置。
- 請求項5に記載の樹脂組成物を硬化した絶縁層上に金属膜層を形成し、金属膜層上部からレーザー照射することを特徴とする、微細配線溝形成方法。
- 請求項12に記載の微細配線溝形成方法を含有することを特徴とする、トレンチ型回路基板の製造方法。
- 絶縁層上に金属膜層を形成し、金属膜層上部からレーザー照射することを特徴とする、微細配線溝形成方法。
- 絶縁層に平均粒径0.02~5μmの無機充填材を含有させることを特徴とする、請求項14に記載の微細配線溝形成方法。
- 金属膜層の厚みが50~500nmであることを特徴とする、請求項14又は15に記載の微細配線溝形成方法。
- 請求項14~16のいずれか1項に記載の微細配線溝形成方法を含有することを特徴とする、トレンチ型回路基板の製造方法。
- 更に、デスミア工程を含有することを特徴とする、請求項17に記載のトレンチ型回路基板の製造方法。
- 更に、メッキ工程を含有することを特徴とする、請求項17~18のいずれか1項に記載のトレンチ型回路基板の製造方法。
- 更に、導体層を除去する工程を含有することを特徴とする、請求項17~19のいずれか1項に記載のトレンチ型回路基板の製造方法。
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JP7128375B1 (ja) | 2021-09-24 | 2022-08-30 | 積水化学工業株式会社 | 炭素繊維強化複合材料及び炭素繊維強化複合材料の製造方法 |
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KR20130037661A (ko) | 2013-04-16 |
TWI564338B (zh) | 2017-01-01 |
KR101906687B1 (ko) | 2018-12-05 |
JP5870917B2 (ja) | 2016-03-01 |
TW201422706A (zh) | 2014-06-16 |
JPWO2011111847A1 (ja) | 2013-06-27 |
JP5773007B2 (ja) | 2015-09-02 |
JP2014131072A (ja) | 2014-07-10 |
TWI643895B (zh) | 2018-12-11 |
TW201202334A (en) | 2012-01-16 |
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