WO2015087884A1 - 離型ポリイミドフィルム、接着層付き離型ポリイミドフィルム付き積層板、積層板、接着層付き離型ポリイミドフィルム付き単層又は多層配線板及び多層配線板の製造方法 - Google Patents
離型ポリイミドフィルム、接着層付き離型ポリイミドフィルム付き積層板、積層板、接着層付き離型ポリイミドフィルム付き単層又は多層配線板及び多層配線板の製造方法 Download PDFInfo
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
-
- 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
-
- 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
-
- 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
-
- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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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
- H05K3/0011—Working of insulating substrates or insulating layers
- H05K3/0014—Shaping of the substrate, e.g. by moulding
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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
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
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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
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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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
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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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
- B32B2457/00—Electrical equipment
-
- 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
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- 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
- C09J2461/00—Presence of condensation polymers of aldehydes or ketones
- C09J2461/005—Presence of condensation polymers of aldehydes or ketones in the release coating
-
- 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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0326—Organic insulating material consisting of one material containing O
-
- 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
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Definitions
- the present invention relates to a release polyimide film, a laminate with a release polyimide film with an adhesive layer, a laminate, a single-layer or multilayer wiring board with a release polyimide film with an adhesive layer, and a method for producing a multilayer wiring board.
- This hot pressing step is a prepreg obtained by impregnating and coating a resin composition on a fiber substrate on a circuit board having an inner layer circuit on one side or both sides, or a resin film not containing a fiber substrate, and a copper foil. Are laminated, heated and pressurized. Moreover, the hot press process is often used because of its high productivity.
- the copper foil is laminated between the surface on which the circuit is formed and the press board during the hot press process. It was necessary (see, for example, Patent Document 1). Further, since the surface roughness of the copper foil is transferred to the surface on which the circuit to be multilayered is formed, the surface roughness of the surface on which the circuit is formed is as large as about 0.3 ⁇ m.
- a silicone mold release agent having excellent peelability is widely used as a mold release agent for such a film material.
- the object of the present invention is that the etching after the hot pressing process, which was necessary when using copper foil, is unnecessary, and an insulating layer having a surface roughness suitable for the semi-additive method is obtained. It is an object of the present invention to provide a release polyimide film as a material capable of producing a multilayer wiring board having a small amount of transfer of a release agent component to an insulating layer and having good flatness.
- a release polyimide film according to [1] wherein the release layer has a thickness of 0.01 to 10 ⁇ m.
- [5] The release polyimide film according to any one of [1] to [4], which has an adhesive layer on a surface of the release layer where no polyimide film is provided.
- [6] The release polyimide film according to [5], wherein the adhesive layer is made of a resin composition containing an epoxy resin and an epoxy resin curing agent.
- [7] A laminate with a release polyimide film with an adhesive layer obtained by laminating the adhesive layer side of the release polyimide film according to [5] or [6] on at least one surface of a prepreg or an insulating layer.
- [8] A laminate obtained by peeling off the release polyimide film of the laminate according to [7].
- the adhesive polyimide layer of the release polyimide film according to [5] or [6] is laminated on one surface of the prepreg or the insulating layer, and the other surface of the prepreg or the insulating layer is a single processed circuit.
- the manufacturing method of a multilayer wiring board including the process of removing a release polyimide film from a single layer with a release polyimide film with a layer, or a multilayer wiring board, and the process of processing a circuit.
- a multilayer wiring board when producing a multilayer wiring board by a molding method using a hot plate press, a roll laminator, a double press, etc., it is excellent in releasability from an insulating layer, and further, for example, 200 ° C. or more Insulating layer that has heat resistance that does not cause the film to melt even when used at high temperatures, has little transfer of the release agent component to the insulating layer, has low surface roughness, and excellent surface flatness
- a release polyimide film capable of obtaining a multilayer wiring board and a method for producing a multilayer wiring board using the same can be provided.
- Example 1 it is the result of having observed the surface state of the insulating layer after peeling a release polyimide film after a press with the high-precision three-dimensional surface shape roughness measuring system.
- Comparative Example 3 the surface state of the insulating layer after the electrolytic copper foil on the surface was removed by etching was observed with a high-precision three-dimensional surface shape roughness measurement system.
- the release polyimide film of the present invention has a release layer containing an alkyd resin (A) and an amino resin (B) on at least one surface of the polyimide film.
- “contains” means that the contained product does not react and is contained as it is, and at least a part of the contained product is contained in a reacted state. It means that it may be in any state.
- the polyimide film used as the base material of the release polyimide film of the present invention one having an appropriate strength and not causing tearing or the like when peeled is suitably used.
- an aromatic polyimide in which aromatic compounds are directly linked by an imide bond is preferable in terms of film strength, and an aromatic polyimide having a structural unit represented by the following formula (I) is more preferable.
- Z 1 is a tetravalent aromatic hydrocarbon group having 6 to 18 carbon atoms
- Z 2 is a divalent aromatic hydrocarbon group having 6 to 18 carbon atoms.
- the tetravalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by Z 1 is preferably a tetravalent aromatic hydrocarbon group having 6 to 12 carbon atoms.
- Preferred examples of the tetravalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by Z 1 include the following aromatic hydrocarbon groups.
- the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by Z 2 is preferably a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms.
- Preferred examples of the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by Z 2 include the following aromatic hydrocarbon groups.
- Examples of commercially available polyimide films include Ube Industries, Ltd., trade names: Upilex R, Upilex S, Upilex SGA, Toray DuPont Co., Ltd., trade names: Kapton H, Kapton V, Kapton E, Kapton EN, Kapton ENZT. , Manufactured by Kaneka Chemical Co., Ltd., trade names: Apical AH, Apical NPI, and the like.
- the surface of these commercially available films may be subjected to, for example, plasma treatment, corona discharge treatment or the like.
- the thickness of the polyimide film used as the substrate of the release polyimide film of the present invention may be selected depending on the purpose and application. From the viewpoint of the followability and peelability of the polyimide film, for example, the thickness of the polyimide film is preferably 10 to 100 ⁇ m, more preferably 20 to 50 ⁇ m, and more preferably 25 to 50 ⁇ m.
- the surface roughness (Ra) of the polyimide film used as the substrate of the release polyimide film of the present invention is, for example, preferably 0.2 ⁇ m or less from the viewpoint of improving the flatness of the insulating layer after peeling. More preferably, it is 0.1 ⁇ m or less, and further preferably 0.05 ⁇ m or less.
- surface roughness of the polyimide film indicates at least the surface roughness of the surface on the side where the release layer is formed.
- the polyimide film according to the present invention has a strength that does not melt in a high temperature range, so that it is preferably used at 150 to 300 ° C., for example, and does not exhibit a clear glass transition temperature in the range, and further has a storage modulus ( 10 Hz) preferably exceeds 1 GPa.
- the resin composition for forming the release layer of the release polyimide film of the present invention contains an alkyd resin (A) and an amino resin (B). It is a waste.
- the total content of the alkyd resin (A) and the amino resin (B) (however, when an organic solvent is contained, the total content is the solid content). Is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
- the release layer contains an alkyd resin (A) and an amino resin (B), a crosslinked structure is obtained in the release layer, and the release layer is compared with a silicone release agent. Migration of the resin composition component for an insulating layer to the insulating layer is suppressed, and good releasability is exhibited. By suppressing the transfer of the resin composition component for the release layer to the insulating layer, it is possible to suppress a decrease in heat resistance or the like of the insulating layer.
- the thickness of the release layer is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 5 ⁇ m, and further preferably 0.05 to 2 ⁇ m.
- the ratio (A / B) of the component (A) to the component (B) is preferably, for example, 95/5 to 10/90, and 90/10 to 40/60 in terms of solid content. It is more preferable.
- the ratio of the alkyd resin (A) is 95% by mass or less (that is, the ratio of the amino resin (B) is 5% by mass or more)
- a sufficient crosslinked structure is obtained in the release layer, and the peelability is reduced. It tends to be suppressed.
- the ratio of the alkyd resin (A) is 10% by mass or more (that is, the ratio of the amino resin (B) is 90% by mass or less)
- the release layer does not become too hard, and good peelability is obtained. There is a tendency.
- the alkyd resin (A) refers to a synthetic resin obtained by a condensation reaction between a polyhydric alcohol and a polybasic acid.
- a conversion product which is a condensate of a dibasic acid and a dihydric alcohol or an inconvertible alkyd modified with a non-drying oil fatty acid, and a condensate of a dibasic acid and a trihydric or higher alcohol. Any of the alkyds can be used.
- various commercially available resins may be used, or they may be synthesized according to a known method.
- Examples of the method for synthesizing the alkyd resin (A) include a method in which a polyhydric alcohol and a polybasic acid or a modifier is added thereto and subjected to heat condensation.
- Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol; trivalent compounds such as glycerin, trimethylolethane, and trimethylolpropane.
- Polyhydric alcohols such as diglycerin, triglycerin, pentaerythritol, pentaerythritol, dipentaerythritol, mannitol and sorbit can be used.
- polybasic acid examples include saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, and sebacic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic anhydride, and isophthalic acid.
- unsaturated polybasic acids such as acid and trimellitic anhydride; use of polybasic acids by Diels-Alder reaction such as cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, rosin-maleic anhydride adduct, etc. it can.
- Examples of the modifier include coconut oil, linseed oil, tung oil, castor oil, dehydrated castor oil, and fatty acids thereof, octylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and linoleic acid. Eleostearic acid, ricinoleic acid, dehydrated ricinoleic acid and the like can be used.
- the oil length (fatty acid content mass ratio) of the alkyd resin (A) is preferably, for example, 0 to 60%, and more preferably 20 to 40%.
- the acid value of the alkyd resin (A) is, for example, preferably 1 to 30 mgKOH / g, and more preferably 5 to 25 mgKOH / g.
- the hydroxyl value of the alkyd resin (A) is, for example, preferably 50 to 300 mgKOH / g, and more preferably 100 to 250 mgKOH / g.
- these alkyd resins (A) can be used by modifying or mixing, for example, acrylic resin, polyester resin, epoxy resin, phenol resin and the like.
- the amino resin (B) refers to a resin obtained by a condensation reaction between a compound containing an amino group and an aldehyde, and examples thereof include a melamine resin, an aniline aldehyde resin, a urea resin, and a benzoguanamine resin.
- the amino resin used in the present invention various commercially available amino resins may be used, or they may be synthesized according to known methods.
- As a synthesis method for example, various amino resins synthesized using a prepolymer containing methylol or an ether thereof as a raw material resin can be used.
- methylated melamine resin such as methylated melamine resin, butylated melamine resin, methylated urea resin, butylated urea resin, methylated benzoguanamine resin, butylated benzoguanamine resin
- a methylated melamine resin in particular, a methylated melamine resin containing at least one methylol group per triazine nucleus as a main component is preferable.
- a methylated melamine resin that is particularly preferably used as an amino resin is usually obtained by subjecting melamine to an addition reaction of formalin under basicity and further subjecting methanol to an ether reaction under acidic conditions.
- the amount of imino group, methylol group, and methyl ether group, which are functional groups of the amino resin, can be controlled by the difference in the amount of formalin added and the amount of etherified methanol.
- the amount of methylol group per triazine nucleus can be calculated by titration analysis and instrumental analysis. For example, it can be calculated by measuring with a nuclear magnetic resonance apparatus or elemental analysis apparatus.
- the release layer resin composition contains a silicone resin (C) from the viewpoint of releasability within a range where the migration of the release layer resin composition component to the insulating layer is suppressed. Also good.
- the content ratio of the silicone resin is such that the content ratio (C / (A + B)) of the silicone resin (C) to the total content of the alkyd resin (A) and the amino resin (B) is a solid content mass ratio. It is preferably 20/100 or less, and more preferably 10/100 or less.
- the silicone resin (C) refers to organopolysiloxane, silicone rubber, and silicone oil having a three-dimensional network structure mainly composed of dimethylpolysiloxane.
- silicone resin (C) used in the present invention various commercially available resins may be used, or they may be synthesized according to known methods.
- organopolysiloxane is preferable, and any structure of linear or branched structure can be used as long as a release layer excellent in heat resistance, gloss, releasability and surface condition can be obtained.
- those having excellent compatibility with the alkyd resin (A) and the amino resin (B) are preferably used for the resin composition for a release layer of the present invention.
- the organopolysiloxane can change properties such as flexibility and elasticity of the resin by changing the molar ratio between the organic group and the silicon atom. Specifically, as such an organopolysiloxane, the following formula (1):
- R 1 is a substituent having reactivity with at least one of alkyd resin and amino resin (including a reaction product of alkyd resin and amino resin), and the remainder is carbon number.
- 1 to 12 unsubstituted or substituted alkyl groups X is 15 to 500, preferably 25 to 100, Y is 15 to 500, preferably 25 to 100, and X + Y is 30 to 1000, preferably 50 to 200. 0.15 ⁇ Y / (X + Y) ⁇ 0.5.).
- the organic group bonded to the silicon atom in one molecule of the organopolysiloxane is preferably 15 to 50 mol%, more preferably 15 to 40 mol%.
- the amount of the phenyl group is 15 mol% or more, the compatibility with the alkyd resin (A) and the amino resin (B) tends to be good. Moreover, it exists in the tendency for the fall of peelability to be suppressed as the amount of phenyl groups is 50 mol% or less.
- At least one of the remaining organic groups other than the phenyl group is a functional group that is reactive with at least one of the alkyd resin and the amino resin.
- the functional group reactive with at least one of the alkyd resin and amino resin include a hydroxyl group-substituted organic group, an amino group-substituted organic group, a carboxyl group-substituted organic group, and a glycidyl group-substituted organic group.
- a hydroxyl group-substituted organic group is preferable from the viewpoint of ease of introduction into an aminoalkyd resin.
- hydroxyl group-substituted organic group When a hydroxyl group-substituted organic group is used, 1 to 20 hydroxyl group-substituted organic groups are preferably contained per silicone resin molecule, more preferably 1 to 10 groups.
- hydroxyl group-substituted organic group include the following formula (2):
- n is an average value of 1 to 3
- a hydroxyl group-substituted organic group represented by the following formula (3):
- R and R 2 are divalent hydrocarbon groups having 1 to 10 carbon atoms, and a is 0 or 1), and the like.
- the remaining unsubstituted or substituted alkyl group other than the organic group includes a linear alkyl group or a branched alkyl group having 1 to 12, preferably 1 to 8, more preferably 1 to 5 carbon atoms.
- the alkyl group include an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and an octyl group, or a carbon atom of these groups.
- Examples thereof include substituted alkyl groups such as a chloromethyl group, a trifluoropropyl group, and a cyanoethyl group in which part or all of the hydrogen atoms are substituted with halogen atoms such as fluorine, chlorine, bromine, and iodine, and cyano groups.
- halogen atoms such as fluorine, chlorine, bromine, and iodine, and cyano groups.
- a surfactant can be blended in the release layer resin composition used in the present invention.
- the term “surfactant” refers to a substance that exhibits surface activity even at a low concentration, which is used to control interfacial phenomena.
- Surfactants include anionic surfactants whose main active agent is an anion, cationic surfactants whose main active agent is a cation, amphoteric surfactants whose main active agent is amphoteric, ionization
- a cationic surfactant having antistatic properties is preferred from the standpoint of effects.
- Examples of the cationic surfactant include quaternary ammonium salts, tertiary ammonium salts, amide quaternary ammonium salts, and the like. In order to further enhance the antistatic effect, a quaternary ammonium salt is preferred.
- Examples of the quaternary ammonium salt include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, tetraalkyl ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl pyridinium salt, alkyl morpholinium salt, alkyl imidazolinium salt, amido ammonium salt.
- the addition amount of the cationic surfactant is 0.05 to 10 parts by mass, preferably 0. 10 parts by mass with respect to 100 parts by mass of the composition comprising the alkyd resin (A), amino resin (B), and silicone resin (C). 1 to 5 parts by mass.
- the addition amount is 0.05 parts by mass or more, good antistatic performance tends to be obtained.
- the addition amount is 10 parts by mass or less, good curability of the coating film is obtained, and a decrease in peelability tends to be suppressed.
- an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant can be used in combination with the cationic surfactant as long as the effects of the present invention are exhibited.
- anionic surfactant examples include alkyl phosphate salts, alkyl sulfone hydrochloride, alkyl benzene sulfonate, and the like.
- Nonionic surfactants include, for example, glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester, N-hydroxyethyl-N-2-hydroxyalkylamine, alkyldiethanolamide and the like.
- amphoteric surfactants examples include alkyl betaines and alkyl imidazolinium betaines.
- Various commercially available surfactants may be used as the cationic surfactant, nonionic surfactant, anionic surfactant, and amphoteric surfactant.
- the release layer resin composition may contain an acidic catalyst.
- the acidic catalyst functions as a catalyst for the reaction between the alkyd resin (A) and the amino resin (B).
- the acidic catalyst include p-toluenesulfonic acid, oxalic acid, phosphoric acid and the like.
- the silicone resin (C) containing a functional group reactive with at least one of the alkyd resin (A) and the amino resin (B) is introduced into the release layer resin composition is to adjust the peelability. It is. In addition, when not introducing a silicone resin, the coating property at the time of forming an adhesive layer on a mold release layer becomes favorable.
- the resin composition (henceforth a silicone containing amino alkyd resin and an alkyd resin (A), an amino resin (B), and the silicone resin which has a functional group reactive with the compound which made the alkyd resin react with an amino resin) Can also be purchased commercially. For example, trade names, Tesfine 319, TA31-209E, etc., manufactured by Hitachi Chemical Polymer Co., Ltd.
- a resin composition containing an alkyd resin and an amino resin (hereinafter also referred to as non-silicone amino alkyd resin) can be purchased commercially.
- trade names, Tesfine 303, Tesfine 305, etc., manufactured by Hitachi Chemical Polymer Co., Ltd. may be mentioned.
- the release layer resin composition is finally in a state of a varnish in which each component is dissolved or dispersed in an organic solvent (hereinafter sometimes referred to as a release layer resin varnish).
- organic solvent used for forming the varnish examples include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.
- alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
- ketone solvents such as acetone, methyl
- Nitrogen atom-containing solvents such as dimethyl sulfoxide. These can be used individually by 1 type or in mixture of 2 or more types. Among these, for example, an aromatic solvent and a ketone solvent are preferable from the viewpoint of solubility and appearance at the time of coating, and a mixed solvent of toluene and methyl ethyl ketone (MEK) is more preferable.
- aromatic solvent and a ketone solvent are preferable from the viewpoint of solubility and appearance at the time of coating, and a mixed solvent of toluene and methyl ethyl ketone (MEK) is more preferable.
- MEK methyl ethyl ketone
- the content (solid content concentration) of the resin composition in the finally obtained varnish is, for example, preferably 1 to 40% by mass, more preferably 5 to 30% by mass, based on the entire varnish.
- an easy lubricant, an antistatic agent, etc. can be added to the release layer, that is, to the release layer resin composition.
- an antistatic agent is preferable, and the antistatic layer may be formed by application to a surface on which no release layer is formed.
- a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, or the like is used on the polyimide film, for example, 50 Examples include a method of drying at a temperature of from 200 ° C. to 200 ° C. for 10 seconds to 600 seconds.
- the release polyimide film of the present invention can have an adhesive layer on the surface of the release layer where no polyimide film is provided.
- the adhesive layer may be formed on the release layer surface using a resin composition containing an epoxy resin and an epoxy resin curing agent (hereinafter sometimes referred to as a resin composition for an adhesive layer).
- a resin composition for an adhesive layer containing an epoxy resin and an epoxy resin curing agent
- Epoxy resins are preferred because they are excellent in heat resistance, alkali resistance, and the like.
- the resin composition “comprising an epoxy resin and an epoxy resin curing agent” may contain an epoxy resin and an epoxy resin curing agent in an unreacted state or in a reacted state. It may be.
- the thickness of the adhesive layer is preferably from 0.01 to 10 ⁇ m, more preferably from 0.05 to 8 ⁇ m. By setting it within this range, it is possible to more easily remove the release polyimide film at the interface between the adhesive layer and the release layer after hot plate pressing.
- the “epoxy resin” is an epoxy resin having two or more epoxy groups in the molecule. Examples of the resin having two epoxy groups in the molecule include bisphenol A type epoxy resin and bisphenol F type epoxy resin. Moreover, you may use the polyfunctional epoxy resin which has an epoxy group larger than two on average in a molecule
- the polyfunctional epoxy resin examples include biphenyl aralkyl type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aralkyl type epoxy resins, naphthalene type epoxy resins, naphthalene novolak type epoxy resins and the like.
- the polyfunctional epoxy resin for example, an aralkyl novolac epoxy resin and a naphthalene novolac epoxy resin are preferable.
- the polyfunctional epoxy resin of the adhesive layer preferably has, for example, a biphenyl structure. These may be used alone or in admixture of two or more.
- an aralkyl novolak type epoxy resin having a biphenyl structure (biphenyl aralkyl type epoxy resin) is preferable.
- examples of commercially available aralkyl novolak epoxy resins having a biphenyl structure include NC-3000 and NC-3000-H manufactured by Nippon Kayaku Co., Ltd.
- epoxy resin curing agent examples include polyfunctional phenol compounds such as phenol novolak and cresol novolac; amine compounds such as dicyandiamide, diaminodiphenylmethane and diaminodiphenylsulfone; phthalic anhydride, pyromellitic anhydride, maleic anhydride, anhydrous Examples thereof include acid anhydrides such as maleic acid copolymers. These 1 type (s) or 2 or more types can be mixed and used.
- the resin composition for an adhesive layer may contain a curing accelerator.
- a curing accelerator for example, various imidazoles that are latent thermosetting agents, BF 3 amine complexes, and phosphorus-based curing accelerators can be used.
- the blending amount of the curing accelerator is preferably 0.1 to 5% by mass with respect to the blending amount of the epoxy resin. From the viewpoint of storage stability of the adhesive layer resin composition, handling property of the B-stage (semi-cured) adhesive layer resin composition, and solder heat resistance, imidazoles and phosphorus curing accelerators are preferable.
- imidazoles examples include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 2-ethyl-1-methylimidazole, 1, 2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethylimidazole, 2-cyanoethyl-2-ethylimidazole, 1-
- a curing accelerator that contains a phosphorus atom and accelerates the curing reaction of the epoxy resin is preferable.
- a phosphorus curing accelerator may be used alone, or one or more other curing accelerators may be used in combination.
- Examples of phosphorus curing accelerators include triphenylphosphine, diphenyl (alkylphenyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, tris (dialkylphenyl) phosphine, Tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiaryl Organic phosphines such as phosphine; Complexes of these organic phosphines and organic borons; Addition of tert
- the resin composition for an adhesive layer of the present invention can be arbitrarily selected from known inorganic fillers, organic fillers, thermoplastic resins, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, depending on the purpose.
- a fluorescent brightener, an adhesion improver, etc. can be used.
- inorganic fillers examples include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, boron nitride, calcium carbonate, and barium sulfate.
- glass powder such as E glass, T glass, D glass, or hollow glass beads can be used. These may be used alone or in admixture of two or more.
- content of an inorganic filler it is preferable that it is 10 mass% or less in the resin composition for contact bonding layers. When the blending amount is 10% by mass or less, a good surface shape after the roughening treatment can be maintained, and deterioration of plating characteristics and interlayer insulation reliability can be prevented.
- the organic filler examples include resin particles having a uniform structure made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc .; acrylate ester resins, methacrylate ester resins, conjugated diene resins And a core-shell resin particle having a glassy shell layer made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, a vinyl cyanide resin, etc. Can be mentioned.
- the content of the organic filler is, for example, preferably 0.5 to 300 parts by mass, and more preferably 1 to 250 parts by mass with respect to 100 parts by mass of the total resin components.
- thermoplastic resin examples include polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin, xylene resin, petroleum resin, and silicone resin.
- the flame retardant examples include halogen-containing flame retardants containing bromine and chlorine; phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, red phosphorus; sulfamic acid Nitrogen flame retardants such as guanidine, melamine sulfate, melamine polyphosphate and melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; and inorganic flame retardants such as antimony trioxide.
- halogen-containing flame retardants containing bromine and chlorine examples include halogen-containing flame retardants containing bromine and chlorine; phosphorus flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphate ester compounds, red phosphorus; sulfamic acid Nitrogen flame retardants such
- ultraviolet absorber examples include benzotriazole-based ultraviolet absorbers.
- antioxidant examples include hindered phenol-based and hindered amine-based antioxidants.
- photopolymerization initiator examples include benzophenones, benzyl ketals, and thioxanthone photopolymerization initiators.
- fluorescent brightener examples include stilbene derivatives.
- adhesion improver examples include urea compounds such as urea silane; coupling agents such as silane, titanate, and aluminate.
- the resin composition for the adhesive layer is preferably finally in a state of a varnish in which each component is dissolved or dispersed in an organic solvent (hereinafter, sometimes referred to as a resin varnish for the adhesive layer).
- organic solvent used for forming the varnish examples include alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ester solvents such as butyl acetate and propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene; dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc.
- alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
- ketone solvents such as acetone, methyl
- a nitrogen atom-containing solvent; a sulfur atom-containing solvent such as dimethyl sulfoxide and the like can be mentioned, and one kind can be used alone or two or more kinds can be mixed and used.
- These organic solvents are appropriately selected from the viewpoint of the solubility of the resin and the appearance after coating.
- ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
- nitrogen atom-containing solvents such as dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone
- ketone solvents and nitrogen atom-containing solvents are preferred from the viewpoint of the solubility of the resin and the appearance after coating.
- the resin composition in the varnish finally obtained is, for example, preferably 1 to 60% by mass, more preferably 2 to 50% by mass with respect to the entire varnish.
- the content of the resin composition in the varnish is preferably 1 to 60% by mass from the viewpoint of film thickness accuracy during coating and appearance.
- the adhesive layer of the present invention is a coating of a reverse coater, gravure coater, air doctor coater, die coater, lip coater, etc. on the release layer of the release polyimide film with the resin composition for the adhesive layer (or the varnish containing it). For example, it can be obtained by drying at 80 to 230 ° C. for 30 seconds to 600 seconds using an apparatus.
- an adhesive layer may be provided on the surface of the release polyimide film where the release layer is not provided, and in this state, it can also be used in a hot plate pressing step.
- the surface flatness of the insulating layer after the hot pressing process is improved. As shown in the result of observing the surface state of the insulating layer in FIGS. 1 and 2 with a high-precision three-dimensional surface shape roughness measurement system, the surface flatness is obtained when the copper foil shown in FIG. 2 is used. In the case of using the release polyimide film of the present invention, almost no undulation is seen as shown in FIG. This swell is presumed to be caused by a difference in thermal expansion coefficient between an insulating layer having a low thermal expansion coefficient and a copper foil having a high thermal expansion coefficient during the hot pressing process.
- the laminated board with a release polyimide film with an adhesive layer of the present invention is formed by laminating the adhesive layer side of the release polyimide film with an adhesive layer on at least one surface of a prepreg or an insulating layer.
- the laminated plate with a release polyimide film with an adhesive layer of the present invention is obtained by stacking a release polyimide film with an adhesive layer on one or both sides of a prepreg or an insulating layer so that the adhesive layer is on the inside, and further stacking an end plate on the outside. Can be press-molded and manufactured.
- the laminated board with a release polyimide film with an adhesive layer of the present invention is formed by, for example, stacking a release polyimide film with an adhesive layer on one side or both sides of a prepreg or an insulating layer so that the adhesive layer is on the inside. It can be manufactured by heating and pressurizing with a laminator using a sheet and then heating and curing after the lamination.
- the heating temperature (temperature of the hot plate) in the press molding is preferably 150 to 260 ° C.
- the pressure during the pressurization is preferably 0.5 to 10 MPa.
- the heating temperature in the laminator using the heat resistant rubber sheet is preferably 80 to 150 ° C.
- the pressure during pressurization is preferably 0.3 to 10 MPa.
- the release polyimide film can be appropriately peeled off to obtain a laminate.
- the single-layer or multilayer wiring board with the release polyimide film (release polyimide film with an adhesive layer) of the present invention is laminated on one side of the prepreg or insulating layer of the release polyimide film with an adhesive layer,
- the other surface of the prepreg or insulating layer is laminated on a single-layer or multilayer wiring board formed by circuit processing.
- the prepreg may be a prepreg before curing, or a prepreg that is at least partially cured.
- “being circuit-processed” includes a case where a process that can be normally performed in the manufacture of a wiring board is performed after the circuit is processed. Specifically, after the circuit is processed, plating is performed. Including cases where processing is performed.
- a single-layer wiring board refers to a wiring board having a single circuit layer when a prepreg or insulating layer is laminated on only one side, and when a prepreg or insulating layer is laminated on both sides.
- Each of the wiring boards has one circuit layer (that is, a total of two circuit layers).
- a multilayer wiring board is a core on which at least one surface is processed, and at least one prepreg or insulating layer is laminated on the surface of the core on which the circuit is processed. The circuit is processed on the layer.
- the manufacturing method of the multilayer wiring board of this invention manufactures the single layer or multilayer wiring board with a release polyimide film with an adhesive layer by laminating
- a release agent composition containing an alkyd resin (A) and an amino resin (B) is applied on one surface of the polyimide film and released.
- a step of forming a layer (release polyimide film manufacturing step), a step of forming an adhesive layer on the surface of the release layer where the polyimide film is not provided, and manufacturing a release polyimide film having the adhesive layer (adhesive layer) It is preferable to include an attached mold release polyimide film manufacturing process).
- the release polyimide film manufacturing process and the release polyimide film manufacturing process with an adhesive layer are as described above. Below, a single layer or multilayer wiring board manufacturing process with a release polyimide film with an adhesive layer and a release polyimide film removal process will be described.
- the adhesive layer functions as an insulating layer of the multilayer wiring board.
- the release polyimide film of the present invention having an adhesive layer formed thereon is used as a prepreg or an insulating layer so that the adhesive layer is on the inside.
- the circuit board is overlaid on one side or both sides of the circuit board.
- the end plate is stacked on the outside and press-molded. By removing the end plate, a single-layer or multilayer wiring board in which the release polyimide film of the present invention is disposed on one side or both sides is manufactured. Thereafter, the release polyimide film of the present invention is peeled and removed (release polyimide film removal step), and a multilayer wiring board is obtained through a circuit processing step.
- the heating temperature (temperature of the hot plate) in the press molding is preferably 180 to 300 ° C., and more preferably 200 to 250 ° C., for example.
- the pressure during pressurization is preferably 1 to 4 MPa.
- a generally used material that is not particularly limited can be applied as a material of the prepreg and the insulating layer used in the method for manufacturing a multilayer wiring board of the present invention.
- a polyfunctional epoxy resin, an epoxy resin curing agent, a curing accelerator, a solvent and, if necessary, a mixture of inorganic fillers may be used as the material for the insulating layer, and further, the glass cloth for laminated plates may be impregnated or A prepreg obtained by coating may be used.
- Commercially available products may be used as the prepreg, and examples of commercially available products include GEA-67N, GEA-679F, GEA-679GT, and GEA-700G manufactured by Hitachi Chemical Co., Ltd.
- An inner layer circuit board in a single-layer wiring board or multilayer wiring board formed by circuit processing is, for example, an inner layer board on which a first circuit layer (inner layer wiring) is formed, and an ordinary wiring board as an inner layer board
- an inner layer board on which a first circuit layer (inner layer wiring) is formed
- an ordinary wiring board as an inner layer board
- the known laminates used in U.S.A. such as glass cloth-epoxy resin, paper-phenol resin, paper-epoxy resin, glass cloth or glass paper-epoxy resin.
- a BT substrate impregnated with a bismaleimide-triazine resin, a polyimide film substrate using a polyimide film as a base material, and the like can also be used.
- circuit forming method such as a semi-additive method in which a circuit is formed using a plating process or an additive method in which a circuit is formed by electroless plating at a necessary portion of an insulating substrate can be used.
- the roughening liquid in this case include an oxidizing roughening liquid such as a chromium / sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, and a borofluoric acid roughening liquid.
- an oxidizing roughening liquid such as a chromium / sulfuric acid roughening liquid, an alkaline permanganic acid roughening liquid, a sodium fluoride / chromium / sulfuric acid roughening liquid, and a borofluoric acid roughening liquid.
- an aqueous solution of diethylene glycol monobutyl ether and NaOH is first heated to 70 ° C., and the laminate or single layer or multilayer wiring board is immersed for 5 minutes.
- an aqueous solution of KMnO 4 and NaOH is heated to 80 ° C. and immersed for 10 minutes.
- neutralizing solution for example, a method of neutralizing by immersion for 5 minutes at room temperature to an aqueous hydrochloric acid solution of stannous chloride (SnCl 2) and the like.
- a plating catalyst application treatment for adhering palladium is performed.
- the plating catalyst treatment is performed by immersing in a palladium chloride plating catalyst solution.
- an electroless plating treatment is performed in which an electroless plating layer (conductor layer) having a thickness of 0.3 to 1.5 ⁇ m is deposited on the entire surface of the plating process primer layer by dipping in an electroless plating solution.
- electroplating is performed to form a circuit with a desired thickness at a desired location.
- the electroless plating solution used for the electroless plating treatment a known electroless plating solution can be used, and there is no particular limitation.
- the plating resist a known plating resist can be used, and there is no particular limitation.
- the electroplating treatment can be performed by a known method and is not particularly limited. These platings are preferably copper platings.
- the outer layer circuit can be formed by etching away the electroless plating layer at unnecessary portions.
- the surface of the circuit layer is surface-treated in a state suitable for adhesion, but this method is not particularly limited.
- a copper oxide needle crystal is formed on the surface of the circuit layer 1 with an alkaline aqueous solution of sodium hypochlorite, and the formed copper oxide needle crystal is immersed in a dimethylamine borane aqueous solution for reduction. Manufacturing methods can be used.
- a multilayer wiring board having a large number of layers can be manufactured by repeating the same process.
- Acrylic rubber manufactured by Nagase ChemteX Corporation, trade name: HTR-860P-3, weight average molecular weight 800,000, glass transition point: 13 ° C.
- HTR-860P-3 weight average molecular weight 800,000, glass transition point: 13 ° C.
- 1-cyanoethyl-2-phenylimidazole Shikoku
- Curesol 2PZ-CN trade name: Curesol 2PZ-CN
- alumina filler CAI Kasei Co., Ltd., trade name: NanoTek
- a disperser Yoshida Kikai Kogyo Co., Ltd., trade name: Resin varnish B for adhesive layer (solid content concentration of about 25) using Nanomizer To give the amount%).
- Example 1 Release polyimide film with adhesive layer: Ube Industries, Ltd., Upilex 25SGA (trade name), thickness of 25 ⁇ m, and surface roughness Ra of less than 0.05 ⁇ m were used as the polyimide film.
- the resin varnish A for release layer prepared in Preparation Example 3 was applied using a die coater and dried at 160 ° C. for 40 seconds to obtain a release layer having a thickness of 0.2 ⁇ m.
- the adhesive layer resin varnish A prepared in Preparation Example 1 is applied to the release layer surface of the obtained release polyimide film, dried at 140 ° C. for 5 minutes to form an adhesive layer having a thickness of 5 ⁇ m, and an adhesive layer is provided.
- a release polyimide film was obtained.
- Laminated board Four prepregs (manufactured by Hitachi Chemical Co., Ltd., GEA-700G, product name, 0.10 mm thickness) are stacked, and the upper and lower layers are stacked so that the polyimide film surface of the release polyimide film with the adhesive layer is on the outside. And the cushion paper was piled up, and it heat-cured at 3.0 MPa and 240 degreeC for 1 hour using the press machine, and obtained the laminated board.
- Example 2 As the polyimide film, a release polyimide film with an adhesive layer and a laminated board were used in the same manner as in Example 1 except that Kapton 100H (trade name) manufactured by Toray DuPont Co., Ltd., thickness 25 ⁇ m, surface roughness Ra less than 0.05 ⁇ m was used. Obtained.
- Example 3 Release layer with adhesive layer as in Example 1, except that the resin varnish B for release layer prepared in Preparation Example 4 was used as the release layer and the varnish B for adhesive layer prepared in Preparation Example 2 was used as the adhesive layer. A polyimide film and a laminate were obtained.
- Example 4 Release layer with adhesive layer as in Example 1, except that the resin varnish C for release layer prepared in Preparation Example 5 was used as the release layer, and the varnish B for adhesive layer prepared in Preparation Example 2 was used as the adhesive layer. A polyimide film and a laminate were obtained.
- Example 5 Release layer with adhesive layer as in Example 1 except that the resin varnish D for release layer prepared in Preparation Example 6 was used as the release layer, and the varnish B for adhesive layer prepared in Preparation Example 2 was used as the adhesive layer. A polyimide film and a laminate were obtained.
- Example 1 In the same manner as in Example 1, except that a polyethylene terephthalate film with a release layer (Unipeel TR1, manufactured by Unitika Ltd., product name, thickness 38 ⁇ m) was used instead of the polyimide film with a release layer. A mold film and a laminate were obtained.
- a polyethylene terephthalate film with a release layer (Unipeel TR1, manufactured by Unitika Ltd., product name, thickness 38 ⁇ m) was used instead of the polyimide film with a release layer.
- a mold film and a laminate were obtained.
- Example 4 A laminate was obtained in the same manner as in Example 1 except that a silicone release agent (manufactured by Shin-Etsu Chemical Co., Ltd., KS-774, trade name) was used in place of the resin varnish A for the release layer.
- a silicone release agent manufactured by Shin-Etsu Chemical Co., Ltd., KS-774, trade name
- the characteristics of the release polyimide film of the present invention and the laminate with the adhesive layer can be easily peeled off after hot plate pressing at a high temperature of 240 ° C. as shown in Examples 1 to 5.
- An insulating layer having a flat surface could be obtained.
- Comparative Example 1 using a film other than a polyimide film the polyethylene terephthalate film is fused to the end plate, the release film alone cannot be easily peeled off, and an insulating layer having a good surface state cannot be obtained. was confirmed.
- Comparative Example 2 it was confirmed that the polyimide film was torn and the polyimide film could not be peeled alone.
- Comparative Example 3 the copper foil was broken, and it was confirmed that the copper foil alone could not be peeled off.
- Comparative Example 4 when magic ink was applied to the insulating layer, ink repelling was observed, and it was confirmed that the release layer component was transferred to the insulating layer.
- the observation result of the surface flatness of Example 1 is shown in FIG. 1 and the observation result of the surface flatness of Comparative Example 3 is shown in FIG. 2, when these are confirmed, the release polyimide film of the present invention in FIG. It was confirmed that the surface of the used insulating layer was flatter.
- the release polyimide film of the present invention can be effectively used as a release film when a multilayer wiring board is produced by a molding method using a hot plate press, a roll laminator, a double press or the like.
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Abstract
Description
本発明の目的は、こうした現状に鑑み、銅箔を用いた場合には必要であった熱プレス工程後のエッチングが不要であり、セミアディティブ法に好適な表面粗さの絶縁層が得られ、離型剤成分の絶縁層への移行が少なく、さらに平坦性の良好な多層配線板を製造可能な材料としての離型ポリイミドフィルムを提供することである。
〔1〕ポリイミドフィルムの少なくとも一方の面上に、アルキド樹脂(A)及びアミノ樹脂(B)を含有してなる離型層を有する離型ポリイミドフィルム。
〔2〕前記離型層の厚みが0.01~10μmである上記〔1〕に記載の離型ポリイミドフィルム。
〔3〕前記ポリイミドフィルムの厚みが10~100μmである〔1〕又は〔2〕に記載の離型ポリイミドフィルム。
〔4〕前記ポリイミドフィルムの前記離型層が形成される側の面の表面粗さ(Ra)が0.2μm以下である〔1〕~〔3〕のいずれかに記載の離型ポリイミドフィルム。
〔5〕前記離型層のポリイミドフィルムの設けられていない面上に接着層を有する〔1〕~〔4〕のいずれかに記載の離型ポリイミドフィルム。
〔6〕前記接着層が、エポキシ樹脂及びエポキシ樹脂硬化剤を含む樹脂組成物を用いてなる〔5〕に記載の離型ポリイミドフィルム。
〔7〕〔5〕又は〔6〕に記載の離型ポリイミドフィルムの接着層側を、プリプレグ又は絶縁層の少なくとも一方の面に積層成形してなる接着層付き離型ポリイミドフィルム付き積層板。
〔8〕〔7〕に記載の積層板の離型ポリイミドフィルムを剥離してなる積層板。
〔9〕〔5〕又は〔6〕に記載の離型ポリイミドフィルムの接着層側をプリプレグ又は絶縁層の一方の面に積層し、プリプレグ又は絶縁層のもう一方の面を回路加工されてなる単層又は多層配線板に積層してなる、接着層付き離型ポリイミドフィルム付き単層又は多層配線板。
〔10〕〔5〕又は〔6〕に記載の離型ポリイミドフィルムを単層又は多層配線板に積層することによって、接着層付き離型ポリイミドフィルム付き単層又は多層配線板を製造する工程、接着層付き離型ポリイミドフィルム付き単層又は多層配線板から離型ポリイミドフィルムを除去する工程、及び回路加工する工程を含む、多層配線板の製造方法。
まず、本発明の離型ポリイミドフィルムについて説明する。本発明の離型ポリイミドフィルムは、ポリイミドフィルムの少なくとも一方の面上に、アルキド樹脂(A)及びアミノ樹脂(B)を含有してなる離型層を有するものである。
なお、本明細書において、「含有してなる」とは、含有されたものが反応せずそのままの状態で含有されている状態と、含有されたものの少なくとも一部が反応した状態で含有されている状態のいずれであってもよいことを意味する。
本発明の離型ポリイミドフィルムの基材として用いられるポリイミドフィルムとしては、適度な強度を有し、剥離する際に破れ等を引き起こさないものが好適に用いられる。例えば、芳香族化合物が直接イミド結合で連結された芳香族ポリイミドがフィルム強度の点で好ましく、下記式(I)で表される構造単位を有する芳香族ポリイミドがより好ましい。
Z1が表す炭素数6~18の4価の芳香族炭化水素基としては、例えば、下記の芳香族炭化水素基が好ましく挙げられる。
Z2が表す炭素数6~18の2価の芳香族炭化水素基としては、例えば、下記の芳香族炭化水素基が好ましく挙げられる。
本発明の離型ポリイミドフィルムの離型層を形成するための樹脂組成物(以降、離型層用樹脂組成物と呼ぶことがある)は、アルキド樹脂(A)及びアミノ樹脂(B)を含むものである。該離型層用樹脂組成物の固形分において、アルキド樹脂(A)及びアミノ樹脂(B)の合計含有量(但し、有機溶媒を含有する場合には、固形分の合計含有量である。)は、好ましくは50質量%以上、より好ましくは60質量%以上、さらに好ましくは70質量%以上、特に好ましくは80質量%以上である。
離型層を、アルキド樹脂(A)及びアミノ樹脂(B)を含有してなるものとすることで、離型層中に架橋構造が得られ、シリコーン系離型剤と比較して離型層用樹脂組成物成分の絶縁層への移行が抑制され、且つ良好な剥離性を示す。離型層用樹脂組成物成分の絶縁層への移行が抑制されることで、絶縁層の耐熱性等の低下を抑制するこができる。
離型層の厚さは、例えば、0.01~10μmが好ましく、0.05~5μmがより好ましく、0.05~2μmがさらに好ましい。離型層の厚さが0.01~10μmであることで剥離性が向上する傾向にある。
前記成分(B)に対する前記成分(A)の比率(A/B)が、固形分質量比で、例えば、95/5~10/90であることが好ましく、90/10~40/60であることがより好ましい。
アルキド樹脂(A)の比率が95質量%以下(即ち、アミノ樹脂(B)の比率が5質量%以上)であると、離型層中に十分な架橋構造が得られ、剥離性の低下が抑制される傾向にある。また、アルキド樹脂(A)の比率が10質量%以上(即ち、アミノ樹脂(B)の比率が90質量%以下)であると、離型層が硬くなりすぎず、良好な剥離性が得られる傾向にある。
また、本発明において使用されるアルキド樹脂(A)は各種市販のものを用いてもよく、公知の方法に従って合成してもよい。
多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、トリメチレングリコール、テトラメチレングリコール、ネオペンチルグリコール等の二価アルコール;グリセリン、トリメチロールエタン、トリメチロールプロパン等の三価アルコール;ジグリセリン、トリグリセリン、ペンタエリスリトール、ペンタエリトリット、ジペンタエリトリット、マンニット、ソルビット等の多価アルコールなどを使用できる。
アルキド樹脂(A)の酸価は、例えば、1~30mgKOH/gであることが好ましく、5~25mgKOH/gであることがより好ましい。
また、アルキド樹脂(A)の水酸基価は、例えば、50~300mgKOH/gであることが好ましく、100~250mgKOH/gであることがより好ましい。
また、これらアルキド樹脂(A)に、例えば、アクリル樹脂、ポリエステル樹脂、エポキシ樹脂、フェノール樹脂等を変性又は混合して使用することも可能である。
本発明において使用されるアミノ樹脂は、各種市販のアミノ樹脂を用いてもよく、公知の方法に従って合成してもよい。
合成方法としては、例えば、メチロール又はそのエーテルを含むプレポリマーを原料樹脂として合成された各種アミノ樹脂を使用できる。
より具体的には、例えば、メチル化メラミン樹脂、ブチル化メラミン樹脂、メチル化尿素樹脂、ブチル化尿素樹脂、メチル化ベンゾグアナミン樹脂、ブチル化ベンゾグアナミン樹脂等、各種公知のものを使用できる。繰り返し使用性の観点からはメチル化メラミン樹脂、特にメチロール基をトリアジン核あたり1個以上含有するメチル化メラミン樹脂を主成分とするものが好ましい。
本発明において、アミノ樹脂として特に好ましく用いられるメチル化メラミン樹脂は、通常メラミンに塩基性下でホルマリンを付加反応させ、さらに酸性下でメタノールをエーテル反応させることで得られる。ホルマリンの付加量やメタノールのエーテル化量の違いによりアミノ樹脂の官能基であるイミノ基、メチロール基、メチルエーテル基量をコントロールすることができる。
なお、このトリアジン核あたりのメチロール基量は、滴定分析及び機器分析により算出することができ、例えば、核磁気共鳴装置や元素分析装置等で測定することにより算出することができる。
その場合において、シリコーン樹脂の含有比率は、アルキド樹脂(A)とアミノ樹脂(B)との合計含有量に対するシリコーン樹脂(C)の含有比率(C/(A+B))が、固形分質量比で20/100以下であることが好ましく、10/100以下であることがより好ましい。前記成分(A)と前記成分(B)の合計100質量部に対して、成分(C)が20質量部以下であると、良好な硬化性が得られ、シリコーン樹脂(C)の移行が生じにくい傾向にある。
なお、本発明においてシリコーン樹脂(C)とは、ジメチルポリシロキサンを主成分とする三次元的な網状構造を持ったオルガノポリシロキサン、シリコーンゴム、シリコーン油をいう。本発明で用いられるシリコーン樹脂(C)は各種市販のものを用いてもよく、公知方法に従って合成してもよい。
なお、オルガノポリシロキサンは有機基とケイ素原子のモル比を変化させることにより樹脂の柔軟性、弾性等の性質を変化させることができる。このようなオルガノポリシロキサンとしては具体的には、下記式(1):
オルガノポリシロキサン1分子中における、ケイ素原子に結合する有機基は、15~50mol%がフェニル基であることが好ましく、15~40mol%であることがさらに好ましい。フェニル基量が15mol%以上であると、アルキド樹脂(A)及びアミノ樹脂(B)との相溶性が良好となる傾向にある。また、フェニル基量が50mol%以下であると剥離性の低下が抑制される傾向にある。
本発明において界面活性剤とは、界面現象の調節に用いられる、低濃度でも表面活性を示す物質をいう。界面活性剤としては、活性剤の主体が陰イオンになるアニオン系界面活性剤、活性剤の主体が陽イオンになるカチオン系界面活性剤、活性剤の主体が両性になる両性界面活性剤、電離しないノニオン系界面活性剤があるが、効果の点から帯電防止性を有するカチオン系界面活性剤が好ましい。
なお、アルキド樹脂(A)、アミノ樹脂(B)、及びアルキド樹脂とアミノ樹脂を反応させた化合物と反応性を有する官能基を有するシリコーン樹脂を含む樹脂組成物(以下、シリコーン含有アミノアルキド樹脂と呼ぶこともある)は、商業的に購入できる。例えば、日立化成ポリマー株式会社製の商品名、テスファイン319、TA31-209E等が挙げられる。
また、アルキド樹脂とアミノ樹脂を含む樹脂組成物(以下、非シリコーン系アミノアルキド樹脂と呼ぶこともある)も、商業的に購入できる。例えば、日立化成ポリマー株式会社製の商品名、テスファイン303、テスファイン305等が挙げられる。
これらの中で、例えば、溶解性と塗工時の外観の点から、芳香族系溶媒、ケトン系溶媒が好ましく、さらには、トルエンとメチルエチルケトン(MEK)との混合溶媒が好ましい。
本発明の離型ポリイミドフィルムは、該離型層のポリイミドフィルムの設けられていない面上に接着層を有することができる。
前記接着層は、エポキシ樹脂及びエポキシ樹脂硬化剤を含有してなる樹脂組成物(以降、接着層用樹脂組成物と呼ぶことがある)を用いて、離型層面上に形成されてなることが好ましい。エポキシ樹脂は、耐熱性、耐アルカリ性等に優れる点で好ましい。なお、「エポキシ樹脂及びエポキシ樹脂硬化剤を含有してなる」樹脂組成物は、エポキシ樹脂とエポキシ樹脂硬化剤とを未反応の状態のまま含有していてもよいし、反応した状態で含有していてもよい。
接着層の厚さは、0.01~10μmが好ましく、0.05~8μmがより好ましい。この範囲にすることで、熱板プレス後に、接着層と離型層の界面で離型ポリイミドフィルムを除去することがより容易にできる。
ここで、「エポキシ樹脂」とは、分子中に2つ以上のエポキシ基を有するエポキシ樹脂である。分子中に2つのエポキシ基を有する樹脂としては、例えば、ビスフェノールA型エポキシ樹脂やビスフェノールF型エポキシ樹脂等が挙げられる。また、分子中に、平均で2個よりも大きなエポキシ基を有する多官能エポキシ樹脂を使用してもよい。
多官能エポキシ樹脂としては、例えば、ビフェニルアラルキル型エポキシ樹脂や、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、アラルキル型エポキシ樹脂、ナフタレン型エポキシ樹脂、ナフタレンノボラック型エポキシ樹脂等が挙げられる。なかでも、多官能型エポキシ樹脂としては、例えば、アラルキルノボラック型エポキシ樹脂、ナフタレンノボラック型エポキシ樹脂が好ましい。また、めっき銅との接着力の観点から、接着層の多官能型エポキシ樹脂は、例えば、ビフェニル構造を有するものが好ましい。
これらは単独でも、2種以上を混合して使用してもよい。
これらの中で、例えば、ビフェニル構造を有するアラルキルノボラック型エポキシ樹脂(ビフェニルアラルキル型エポキシ樹脂)が好ましい。ビフェニル構造を有するアラルキルノボラック型エポキシ樹脂の市販品としては、例えば、日本化薬株式会社製のNC-3000、NC-3000-H等が挙げられる。
硬化促進剤の配合量は、エポキシ樹脂の配合量に対して0.1~5質量%であることが好ましい。
接着層用樹脂組成物の保存安定性やBステージ状(半硬化状)の接着層用樹脂組成物の取扱性及びはんだ耐熱性の点から、イミダゾール類、リン系硬化促進剤が好ましい。
無機充填材の含有量としては、接着層用樹脂組成物中10質量%以下であることが好ましい。配合量が10質量%以下であると、粗化処理後の良好な表面形状を維持することができ、めっき特性及び層間の絶縁信頼性の低下を防ぐことができる。
有機充填剤の含有量は、例えば、樹脂成分の総和100質量部に対して、0.5~300質量部であることが好ましく、1~250質量部であることがより好ましい。
これらの有機溶媒は、樹脂の溶解性及び塗工後の外観の観点から適宜選定される。
これらの中で、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶媒;ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等の窒素原子含有溶媒;ケトン系溶媒と窒素原子含有溶媒との混合系溶媒が、樹脂の溶解性及び塗工後の外観の観点から好ましい。
本発明の接着層付き離型ポリイミドフィルム付き積層板は、接着層付き離型ポリイミドフィルムの接着層側を、プリプレグ又は絶縁層の少なくとも一方の面に積層成形してなるものである。
また、本発明の接着層付き離型ポリイミドフィルム付き積層板は、例えば、接着層付き離型ポリイミドフィルムを、接着層が内側となるようにプリプレグ又は絶縁層の片面又は両面に重ね、耐熱性ゴムシートを用いたラミネーターで加熱及び加圧して積層し、積層後に加熱して硬化させ、製造できる。
いずれの方法においても、積層成形した後に、適宜、離型ポリイミドフィルムを剥離し、積層板を得ることができる。
ここで、「回路加工されてなる」とは、回路加工された後に、配線板の製造において通常行われ得る処理が施される場合を含んでおり、具体的には、回路加工された後にめっき処理等が施される場合を含む。また、単層配線板とは、プリプレグ又は絶縁層が片面のみに積層される場合には1層の回路層を有する配線板のことをいい、プリプレグ又は絶縁層が両面に積層される場合にはそれぞれに対して1層の回路層(つまり合計2層の回路層)を有する配線板のことをいう。一方、多層配線板とは、少なくとも一方の面が回路加工されたコアと、該回路加工されたコアの面上に、少なくとも1層のプリプレグ又は絶縁層を積層し、積層されたプリプレグ上又は絶縁層上に回路が加工されているものをいう。
上記工程のうち、離型ポリイミドフィルム製造工程、接着層付き離型ポリイミドフィルム製造工程については既述のとおりである。
以下では、接着層付き離型ポリイミドフィルム付き単層又は多層配線板製造工程及び離型ポリイミドフィルム除去工程について説明する。
なお、接着層付き離型ポリイミドフィルム付き単層又は多層配線板から離型ポリイミドフィルムを除去した後は、当該接着層は多層配線板の絶縁層として機能する。
次にめっきレジストを形成した後に、電気めっき処理を行い所望な箇所に所望の厚みの回路を形成する。無電解めっき処理に使用する無電解めっき液は、公知の無電解めっき液を使用することができ特に制限はない。めっきレジストも公知のめっきレジストを使用することができ、特に制限はない。また、電気めっき処理についても公知の方法によることができ特に制限はない。これらのめっきは銅めっきであることが好ましい。さらに不要な箇所の無電解めっき層をエッチング除去して外層回路を形成することができる。
(調製例1)
クレゾールノボラック型エポキシ樹脂(新日化エポキシ製造株式会社製、商品名:YDCN-700-10)27.5gにフェノールアラルキル樹脂(三井化学株式会社製、商品名:XLC-LL)22.5gを加え、シクロヘキサノンを850g加えて攪拌混練した。これにアクリルゴム(ナガセケムテックス株式会社製、商品名:HTR-860P-3、重量平均分子量80万、ガラス転移点:13℃)100g、硬化促進剤として1-シアノエチル-2-フェニルイミダゾール(四国化成工業株式会社製、商品名:キュアゾール2PZ-CN)0.25g加え、攪拌して、接着層用樹脂ワニスA(固形分濃度約15質量%)を得た。
(調製例2)
ポリアミド(日本化薬株式会社製、商品名:BPAM-155)18gに、N,N-ジメチルアセトアミド(DMAc)を159g配合した後、続いてビフェニルアラルキル型エポキシ樹脂(日本化薬株式会社製、商品名:NC3000H)50g、ビスフェノールAノボラック型フェノール樹脂(三菱化学株式会社製、商品名:YLH129)20gを加え、更に硬化促進剤として2-フェニルイミダゾール(四国化成工業株式会社製、商品名:2PZ)0.5gを添加し、DMAc及びメチルエチルケトンからなる混合溶剤で希釈した後、アルミナフィラー(シーアイ化成株式会社製、商品名:NanoTek)5gを加え、分散機(吉田機械興業株式会社製、商品名:ナノマイザー)を用いて接着層用樹脂ワニスB(固形分濃度約25質量%)を得た。
(調製例3)
非シリコーン系アミノアルキド樹脂〔テスファイン303、日立化成ポリマー株式会社製、固形分48.7%〕31.5gに、酸性触媒としてp-トルエンスルホン酸〔ドライヤー900、日立化成ポリマー株式会社製、固形分50%〕を1.5g配合し、次いでトルエン1050g、MEK450gで希釈し、離型層用樹脂ワニスAを得た。
(調製例4)
非シリコーン系アミノアルキド樹脂〔テスファイン305、日立化成ポリマー株式会社製、商品名、固形分48.7%〕31.5gに、酸性触媒としてp-トルエンスルホン酸〔ドライヤー900、日立化成ポリマー株式会社製、商品名)、固形分50%〕を1.5g配合し、次いでトルエン1050g、MEK450gで希釈し、離型層用樹脂ワニスBを得た。
(調製例5)
シリコーン含有アミノアルキド樹脂〔テスファイン319、日立化成ポリマー株式会社製、固形分48.7%〕31.5gに、酸性触媒としてp-トルエンスルホン酸〔ドライヤー900、日立化成ポリマー株式会社製、商品名、固形分50%〕を1.5g配合し、次いでトルエン1050g、MEK450gで希釈し、離型層用樹脂ワニスCを得た。
(調製例6)
シリコーン含有アミノアルキド樹脂〔TA31-209E、日立化成ポリマー株式会社製、商品名、固形分48.7%〕31.5gに、酸性触媒としてp-トルエンスルホン酸〔ドライヤー900、日立化成ポリマー株式会社製、商品名、固形分50%〕を1.5g配合し、次いでトルエン1050g、MEK450gで希釈し、離型層用樹脂ワニスDを得た。
・接着層付き離型ポリイミドフィルム:
ポリイミドフィルムとして宇部興産株式会社製、ユーピレックス25SGA(商品名)、厚み25μm、表面粗さRa0.05μm未満を用いた。このポリイミドフィルム上に調製例3で調製した離型層用樹脂ワニスAを、ダイコーターを用いて塗布し、160℃で40秒間乾燥させ、厚み0.2μmの離型層を得た。
得られた離型ポリイミドフィルムの離型層面に調製例1で調製した接着層用樹脂ワニスAを塗布し、140℃で5分間乾燥させ、厚さ5μmの接着層を形成して、接着層付き離型ポリイミドフィルムを得た。
プリプレグ(日立化成株式会社製、GEA-700G、商品名、0.10mm厚)を4枚重ね、その上下に上記接着層付き離型ポリイミドフィルムのポリイミドフィルム面が外側になるように重ね、さらに鏡板と、クッション紙を重ねて、プレス機を用いて、3.0MPa、240℃で1時間加熱硬化させ積層板を得た。
ポリイミドフィルムとして、東レ・デュポン株式会社製、カプトン100H(商品名)、厚み25μm、表面粗さRa0.05μm未満を用いた以外、実施例1と同様に接着層付き離型ポリイミドフィルム及び積層板を得た。
離型層として、調製例4で調製した離型層用樹脂ワニスB、接着層として、調製例2で調製した接着層用ワニスBを用いた以外、実施例1と同様に接着層付き離型ポリイミドフィルム及び積層板を得た。
離型層として、調製例5で調製した離型層用樹脂ワニスC、接着層として、調製例2で調製した接着層用ワニスBを用いた以外、実施例1と同様に接着層付き離型ポリイミドフィルム及び積層板を得た。
離型層として、調製例6で調製した離型層用樹脂ワニスD、接着層として、調製例2で調製した接着層用ワニスBを用いた以外、実施例1と同様に接着層付き離型ポリイミドフィルム及び積層板を得た。
離型層付きのポリイミドフィルムの代わりに、離型層付きポリエチレンテレフタレートフィルム(ユニピールTR1、ユニチカ株式会社製、商品名、厚さ38μm)を用いた以外は実施例1と同様に、接着層付き離型フィルム及び積層板を得た。
ポリイミドフィルムに離型層を形成しなかった以外は実施例1と同様に、ポリイミドフィルム面上に接着層を塗布形成させ、接着層付き離型フィルム及び積層板を得た。
離型ポリイミドフィルムの代わりに、電解銅箔(古河サーキットフォイル株式会社製、GTS-18、厚さ18μm)の光沢面に接着層を塗布形成させ、実施例1と同様に、積層板を得た。
離型層用樹脂ワニスAの代わりにシリコーン系離型剤(信越化学工業株式会社製、KS-774、商品名)を用いた以外は、実施例1と同様に積層板を得た。
プレス後に、離型フィルムの変形、融着、破れが起きずにフィルムを単独で剥離することができるかどうかを確認した。さらに、プレス後の積層サンプルから離型フィルムを剥離したときに、離型層との界面で剥離できているかどうかを目視により確認した。
A:界面で容易に剥離できる。
C:界面で容易に剥離できない。
「界面で容易に剥離できない」とは、フィルムを単独で剥離できない場合、又は剥離後、離型フィルムに接着層の樹脂組成物が付着している場合をいう。
プレスをし、フィルムを剥離した後の絶縁層の表面粗さは、表面形状測定装置(Veeco社製、商品名:WykoNT9100)を用いて、下記測定条件にて測定した。
-測定条件-
内部レンズ:1倍
外部レンズ:50倍
測定範囲:0.125×0.095mm
測定深度:10μm
測定方式:垂直走査型干渉方式(VSI方式)
プレス後の積層板からポリイミドフィルムを剥離した後、絶縁層上に寺西化学工業株式会社製のマジックインキ(登録商標)No.500(黒)を塗布し、該インキのはじき具合を観察した。インキをはじく現象は、離型層成分の絶縁層への移行を示すため、はじくものを「C」、はじかないものを「A」として評価した。
高精度3次元表面形状粗さ測定システム(Veeco社製、WYKO NT9100)を用いて、プレス後の絶縁層の表面形状を観察した。図1及び図2は、X軸:125μm、Y軸:95μmの形状範囲について表面観察した結果を示している。
一方、表2から、ポリイミドフィルム以外のフィルムを用いた比較例1ではポリエチレンテレフタレートフィルムが鏡板に融着し、離型フィルム単独容易に剥離できず、良好な表面状態の絶縁層が得られないことが確認できた。さらに、比較例2ではポリイミドフィルムが破れ、ポリイミドフィルムを単独で剥離できないことが確認された。比較例3では銅箔が破れ、銅箔単独では剥離できないことが確認された。比較例4では、絶縁層にマジックインキを塗布すると、インキのはじきが観察され、離型層成分が絶縁層に移行していることが確認された。
また、実施例1の表面平坦性の観察結果を図1に、比較例3の表面平坦性の観察結果を図2に示すが、これらを確認すると、図1の本発明の離型ポリイミドフィルムを用いた絶縁層の方が、表面が平坦であることが確認された。
Claims (10)
- ポリイミドフィルムの少なくとも一方の面上に、アルキド樹脂(A)及びアミノ樹脂(B)を含有してなる離型層を有する離型ポリイミドフィルム。
- 前記離型層の厚みが0.01~10μmである請求項1に記載の離型ポリイミドフィルム。
- 前記ポリイミドフィルムの厚みが10~100μmである請求項1又は2に記載の離型ポリイミドフィルム。
- 前記ポリイミドフィルムの前記離型層が形成される側の面の表面粗さ(Ra)が0.2μm以下である請求項1~3のいずれか一項に記載の離型ポリイミドフィルム。
- 前記離型層のポリイミドフィルムの設けられていない面上に接着層を有する請求項1~4のいずれか一項に記載の離型ポリイミドフィルム。
- 前記接着層が、エポキシ樹脂及びエポキシ樹脂硬化剤を含む樹脂組成物を用いてなる請求項5に記載の離型ポリイミドフィルム。
- 請求項5又は請求項6に記載の離型ポリイミドフィルムの接着層側を、プリプレグ又は絶縁層の少なくとも一方の面に積層成形してなる接着層付き離型ポリイミドフィルム付き積層板。
- 請求項7に記載の積層板の離型ポリイミドフィルムを剥離してなる積層板。
- 請求項5又は請求項6に記載の離型ポリイミドフィルムの接着層側をプリプレグ又は絶縁層の一方の面に積層し、プリプレグ又は絶縁層のもう一方の面を回路加工されてなる単層又は多層配線板に積層してなる、接着層付き離型ポリイミドフィルム付き単層又は多層配線板。
- 請求項5又は請求項6に記載の離型ポリイミドフィルムを単層又は多層配線板に積層することによって、接着層付き離型ポリイミドフィルム付き単層又は多層配線板を製造する工程、接着層付き離型ポリイミドフィルム付き単層又は多層配線板から離型ポリイミドフィルムを除去する工程、及び回路加工する工程を含む、多層配線板の製造方法。
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