CN106232355A - Demoulding polyimide film, the plywood of demoulding polyimide film with band adhesive linkage, plywood, with the single or multiple lift wiring plate of demoulding polyimide film of band adhesive linkage and the manufacture method of multiwiring board - Google Patents

Abstract

The present invention provides as need not etching after hot pressing process, can obtaining being suitable to the insulating barrier of the surface roughness of semi-additive process and can manufacture the demoulding polyimide film of material of the good single or multiple lift wiring plate of flatness.Specifically, the present invention provides a kind of demoulding polyimide film, and it has the release layer containing alkyd resin and amino resins at least one side of polyimide film.Additionally, the present invention also provides for the manufacture method of a kind of multiwiring board, comprising: by the demoulding polyimide film being not provided with on the face of polyimide film having adhesive linkage at above-mentioned release layer is laminated in single or multiple lift wiring plate, thus manufacture the operation of the single or multiple lift wiring plate of the demoulding polyimide film with band adhesive linkage；The operation of demoulding polyimide film is removed from the single or multiple lift wiring plate of the demoulding polyimide film with band adhesive linkage；And carry out the operation of circuit fabrication.

Description

Release polyimide film, laminated board with release polyimide film with adhesive layer, Laminate, single or multilayer wiring with release polyimide film with adhesive layer Board, and method for manufacturing multilayer wiring board

technical field

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 a release polyimide film with an adhesive layer A multilayer wiring board, and a method for manufacturing the multilayer wiring board.

Background technique

Conventionally, multilayer wiring boards have been manufactured through a heat-pressing process. This hot pressing process is performed by laminating a prepreg or a resin film and copper foil on a circuit board having an inner layer circuit on one or both sides, heating and pressing the prepreg impregnated with a resin composition. , obtained by coating on a fibrous base material, and the resin film does not contain a fibrous base material. In addition, the heat press process is widely used because of its high productivity.

Furthermore, in recent years, along with miniaturization and high integration of electronic equipment, finer wiring of multilayer wiring board materials has been demanded. As a method of forming fine wiring, a semi-additive method is suitable. This method is as follows: After electroless copper plating is performed on the surface where the circuit is to be formed, electrolytic copper plating is performed only on the required part, and unnecessary parts are removed by etching. Part of the copper plating forms the wiring. According to this method, the thinner the thickness of the copper layer to be etched away, that is, the thinner the copper plated layer is formed on the surface where the circuit is to be formed and the surface roughness is smaller, and then removed, the further finer the copper layer can be achieved. Wiring.

However, in the manufacture of multilayer wiring boards using a hot-pressing process, since copper foil is laminated between the surface on which the circuit is to be formed and the pressing board during the hot-pressing process, copper foil is required to perform the semi-additive method. The etching process (for example, refer to Patent Document 1). In addition, since the surface roughness of the copper foil is transferred to the surface where the multilayer circuit is to be formed, the surface roughness of the surface where the circuit is to be formed is as large as about 0.3 μm.

In order to solve this problem, the use of film materials such as polyethylene terephthalate (PET) with a small surface roughness instead of copper foil has been studied (for example, refer to Patent Document 2), but the cured product of the resin film, that is, the insulating layer It is affected by low heat resistance or thermal deformation, so there is room for further improvement.

In addition, as a release agent for such a film material, a silicone-based release agent excellent in releasability is widely used.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2003-251739

Patent Document 2: Japanese Patent No. 5212578

Contents of the invention

The problem to be solved by the invention

However, when a silicone-based mold release agent is used, there is a technical problem such as migration of low-molecular-weight components in the silicone composition to the insulating layer, resulting in a decrease in reliability.

The object of the present invention is to provide a mold-releasing polyimide film as a material that can obtain a film suitable for semi-finished products without the need for etching after the hot-pressing process required when using copper foil. The insulating layer with the surface roughness of the conventional method, the migration of the release agent component to the insulating layer is less, and a multilayer wiring board with good flatness can be produced.

means of solving problems

As a result of intensive studies to achieve the above object, the present inventors found that a polyimide film having a release layer shown below, that is, a release polyimide film can achieve the above object, and completed the present invention.

That is, the present invention provides the following materials.

[1] A release polyimide film having a release layer containing an alkyd resin (A) and an amino resin (B) on at least one surface of the polyimide film.

[2] The release polyimide film according to [1], wherein the release layer has a thickness of 0.01 to 10 μm.

[3] The release polyimide film according to [1] or [2], wherein the polyimide film has a thickness of 10 to 100 μm.

[4] The mold release polyimide film according to any one of [1] to [3], wherein the surface roughness (Ra) of the surface of the polyimide film on which the mold release layer is formed is 0.2 μm or less.

[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 on which the polyimide film is not provided.

[6] The release polyimide film according to [5], wherein the adhesive layer is formed using a resin composition containing an epoxy resin and an epoxy resin curing agent.

[7] A laminate with an adhesive layer-attached release polyimide film, which is formed by laminating the adhesive layer side of the release polyimide film described in [5] or [6] At least one side of the prepreg or insulating layer.

[8] A laminate obtained by peeling off the release polyimide film of the laminate described in [7].

[9] A single-layer or multi-layer wiring board with a release polyimide film with an adhesive layer, which adheres the release polyimide film described in [5] or [6] The layer side is laminated on one side of the prepreg or insulating layer, and the other side of the prepreg or insulating layer is laminated on the single-layer or multi-layer wiring board processed by the circuit.

[10] A method for manufacturing a multilayer wiring board, comprising: laminating the release polyimide film described in [5] or [6] on a single-layer or multilayer wiring board, thereby manufacturing a Process of single-layer or multilayer wiring board of release polyimide film with adhesive layer; removal of release polyimide from single-layer or multi-layer wiring board with release polyimide film with adhesive layer The process of imide film; and the process of circuit processing.

Invention effect

According to the present invention, it is possible to provide a method of manufacturing a release polyimide film and a multilayer wiring board using the same, the release polyimide film being pressed by using, for example, a hot plate press, a roll laminator, a secondary press ( When manufacturing a multilayer wiring board using a molding method such as Doble Press), it has excellent peelability from the insulating layer, and also has a heat resistance that does not melt the film even when it is used at a high temperature such as 200°C or higher. The release agent component is There is little migration of the insulating layer, and the surface roughness is small, and an insulating layer and a multilayer wiring board having excellent surface flatness can be obtained.

Description of drawings

FIG. 1 shows the result of observing the surface state of the insulating layer after pressing and peeling off the release polyimide film by using a high-precision three-dimensional surface roughness measurement system in Example 1.

2 is a result of observing the surface state of the insulating layer after the electrolytic copper foil on the surface was removed by etching using a high-precision three-dimensional surface roughness measuring system in Comparative Example 3. FIG.

detailed description

[Mold release polyimide film]

First, the mold release polyimide film of this invention is demonstrated. The release polyimide film of this invention has the release layer containing an alkyd resin (A) and an amino resin (B) on at least one surface of a polyimide film.

It should be noted that, in this specification, "contains..." means that the contained substance may be contained in its original state without reacting, and at least a part of the contained substance may be contained. The state of the reaction is any of the states included.

As a polyimide film used as a base material of the release polyimide film of this invention, the polyimide film which has moderate intensity|strength and does not cause a crack etc. at the time of peeling is used suitably. For example, in terms of film strength, an aromatic polyimide in which an aromatic compound is directly bonded by an imide bond is preferable, and an aromatic polyimide having a structural unit represented by the following formula (I) is more preferable. imine.

[chemical 1]

(In the formula (I), Z1 is a tetravalent aromatic hydrocarbon group having ⁶ to 18 carbons, and Z2 is a divalent aromatic hydrocarbon group having ⁶ to 18 carbons.)

The tetravalent aromatic hydrocarbon group having 6 to 18 carbons represented by Z ¹ is preferably a tetravalent aromatic hydrocarbon group having 6 to 12 carbons.

As the tetravalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by Z ¹ , for example, the following aromatic hydrocarbon groups are preferably mentioned.

[Chem 2]

In addition, 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.

As the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by Z ² , for example, the following aromatic hydrocarbon groups are preferably mentioned.

[Chem 3]

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 Chung Yeon Chemical Industry Co., Ltd., trade names: Apical AH, Apical NPI, etc. For example, plasma treatment, corona discharge treatment, etc. can be given to the surface of these commercially available films in order to improve the adhesiveness with a mold release layer.

What is necessary is just to select the thickness of the polyimide film used as a base material of the release polyimide film of this invention according to the objective and use. From the viewpoint of followability and peelability of the polyimide film, for example, the thickness of the polyimide film is preferably 10 to 100 μm, more preferably 20 to 50 μm, and even more preferably 25 to 50 μm.

From the viewpoint of improving the flatness of the insulating layer after peeling, the surface roughness (Ra) of the polyimide film used as the base material of the release polyimide film of the present invention is preferably, for example, 0.2 μm or less. , more preferably 0.1 μm or less, still more preferably 0.05 μm or less. In addition, "the surface roughness of a polyimide film" here means the surface roughness of the surface on the side where a mold release layer should be formed at least.

The polyimide film of the present invention has strength that does not undergo thermal fusion in a high temperature range, so it is preferably used at, for example, 150 to 300° C., and preferably does not show a clear glass transition temperature in this range and has a storage elastic modulus (10 Hz) exceeding 1GPa.

(release layer)

The resin composition for forming the release layer of the release polyimide film of the present invention (hereinafter, sometimes referred to as the resin composition for release layer) contains an alkyd resin (A) and an amino resin (B). combination. In the solid content of the resin composition for a release layer, the total content of the alkyd resin (A) and the amino resin (B) (wherein, when an organic solvent is contained, the total content of 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, particularly preferably 80% by mass or more.

By making the release layer a layer containing an alkyd resin (A) and an amino resin (B), a cross-linked structure is obtained in the release layer, and the release layer can be suppressed compared with a silicone-based release agent. It is used to transfer the components of the resin composition to the insulating layer, and shows good peelability. By suppressing the migration of the resin composition component for mold release layers to an insulating layer, the fall of the heat resistance of an insulating layer, etc. can be suppressed.

The thickness of the mold release layer is, for example, preferably 0.01 to 10 μm, more preferably 0.05 to 5 μm, even more preferably 0.05 to 2 μm. There exists a tendency for releasability to improve by making the thickness of a mold release layer into 0.01-10 micrometers.

The ratio (A/B) of the component (A) to the component (B) is, for example, preferably 95/5 to 10/90, more preferably 90/10 to 40/60 in terms of solid mass ratio.

When 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 mold release layer, and the decrease in peelability is suppressed. Propensity. In addition, when 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 tends to be obtained. .

In the present invention, the alkyd resin (A) refers to a synthetic resin obtained by a condensation reaction of a polyhydric alcohol and a polybasic acid. As the alkyd resin (A), condensates of dibasic acids and dihydric alcohols, non-converted alkyds modified with non-drying oil fatty acids, and condensates of dibasic acids and trihydric or higher alcohols can be used That is, any of the transforming alkyds.

In addition, the alkyd resin (A) used in this invention can use various commercial items, and can also synthesize|combine by a well-known method.

As a synthesis method of the alkyd resin (A), for example, a polyhydric alcohol, a polybasic acid, or a method of adding a modifying agent thereto, followed by thermal condensation, etc. may be mentioned.

As the polyhydric alcohol, for example: dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol; glycerin, trihydroxy triols such as methylethane and trimethylolpropane; polyalcohols such as diglycerin, triglycerin, pentaerythritol, monopentaerythritol, dipentaerythritol, mannitol, and sorbitol; and the like.

In addition, as the polybasic acid, for example: saturated polybasic acid such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, sebacic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, etc. acid, citraconic anhydride, isophthalic acid, trimellitic anhydride and other unsaturated polyacids; cyclopentadiene-maleic anhydride adducts, terpene-maleic anhydride adducts, rosin-maleic anhydride adducts, etc Diels-Alder reaction (Diels Alder reaction) polyacids, etc. In addition, benzoic acid can also be used together.

In addition, as modifiers, for example, coconut oil, linseed oil, tung oil, castor oil, dehydrated castor oil, and their fatty acids, caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, and linoleic acid can be used. , linolenic acid, lyric acid, ricinoleic acid, dehydrated ricinoleic acid, etc.

The fat-oil ratio (content ratio of fatty acid) of the alkyd resin (A) is preferably, for example, 0 to 60%, more preferably 20 to 40%.

The acid value of the alkyd resin (A) is, for example, preferably 1 to 30 mgKOH/g, more preferably 5 to 25 mgKOH/g.

Moreover, it is preferable that the hydroxyl value of an alkyd resin (A) is 50-300 mgKOH/g, for example, More preferably, it is 100-250 mgKOH/g.

In addition, among these alkyd resins (A), for example, acrylic resins, polyester resins, epoxy resins, phenol resins, etc. may be modified or mixed and used.

The amino resin (B) in the present invention refers to a resin obtained by a condensation reaction between a compound containing an amino group and an aldehyde, and examples thereof include melamine resins, aniline aldehyde resins, urea aldehyde resins, and benzoguanamine resins.

The amino resin used in the present invention can use various commercially available amino resins, and can also be synthesized according to a known method.

As a synthesis method, for example, various amino resins synthesized using a prepolymer containing a methylol group or an ether thereof as a raw material resin can be used.

More specifically, for example, methylated melamine resin, butylated melamine resin, methylated urea resin, butylated urea resin, methylated benzoguanamine resin, butylated benzoguanamine resin, etc. can be used Various known amino resins. From the viewpoint of reusability, it is preferable to use a methylated melamine resin, especially a methylated melamine resin containing one or more methylol groups per triazine nucleus, as a main component.

In the present invention, the methylated melamine resin used particularly preferably as an amino resin is usually obtained by addition reaction of formalin and melamine under basic conditions, and further ether reaction of methanol 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 etherification of methanol.

It should be noted that the amount of methylol groups 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 device, an elemental analysis device, and the like.

In addition, in the present invention, the resin composition for a mold release layer may contain a silicone resin (C) from the viewpoint of releasability within the range in which the migration of the resin composition components for a mold release layer to the insulating layer is suppressed. .

At this time, regarding the content ratio of the silicone resin, the content ratio (C/(A+B)) of the silicone resin (C) relative to the total amount of the alkyd resin (A) and the amino resin (B) is expressed in terms of solid content mass The ratio is preferably 20/100 or less, more preferably 10/100 or less. When the component (C) is 20 parts by mass or less with respect to the total of 100 parts by mass of the above-mentioned component (A) and the above-mentioned component (B), good curability is obtained, and migration of the silicone resin (C) tends to hardly occur. .

It should be noted that the silicone resin (C) in the present invention refers to organopolysiloxane, silicone rubber, and silicone oil having a three-dimensional network structure mainly composed of dimethylpolysiloxane. The silicone resin (C) used in the present invention can use various commercial products, and can also be synthesized according to a known method.

As the silicone resin (C), organopolysiloxane is preferable, and as long as it is a silicone resin capable of obtaining a mold release layer excellent in heat resistance, gloss, releasability, and surface condition, it may be linear or branched. Arbitrary structures in the silicone resin excellent in compatibility with the said alkyd resin (A) and amino resin (B) are used suitably for the resin composition for mold release layers of this invention.

It should be noted that the organopolysiloxane can change the softness, elasticity and other properties of the resin by changing the molar ratio of the organic group to the silicon atom. As such an organopolysiloxane, the organopolysiloxane represented by following formula (1) is mentioned specifically,.

[chemical 4]

(In the formula, at least ^one of R1 is a substituent having reactivity with at least one of alkyd resin and amino resin (including the reactant of alkyd resin and amino resin), and the rest are carbon numbers 1 to 10. 12 unsubstituted or substituted alkyl, X is 15-500, preferably 25-100, Y is 15-500, preferably 25-100, X+Y is 30-1000, preferably 50-200, 0.15≤Y /(X+Y)≤0.5.)

Of the organic groups bonded to silicon atoms in one molecule of the organopolysiloxane, preferably 15 to 50 mol% are phenyl groups, and more preferably 15 to 40 mol% are phenyl groups. There exists a tendency for the compatibility with an alkyd resin (A) and an amino resin (B) to become favorable that the amount of a phenyl group is 15 mol% or more. Moreover, when the amount of phenyl groups is 50 mol% or less, there exists a tendency for the fall of peelability to be suppressed.

In order for the release layer to sufficiently have releasable performance, it is preferable that at least one of the remaining organic groups other than the phenyl group be a functional group reactive with at least one of alkyd resin and amino resin. Examples of functional groups reactive with at least one of alkyd resins and amino resins include hydroxyl-substituted organic groups, amino-substituted organic groups, carboxyl-substituted organic groups, and glycidyl-substituted organic groups. Among them, a hydroxyl group-substituted organic group is preferable from the viewpoint of easiness of the method of introducing the amino alkyd resin.

When a hydroxy-substituted organic group is used, the silicone resin preferably contains 1 to 20 such hydroxy-substituted organic groups, and more preferably contains 1 to 10 such hydroxy-substituted organic groups per molecule of the silicone resin. As a hydroxy-substituted organic group, the hydroxy-substituted organic group represented by following formula (2), the hydroxy-substituted organic group represented by following formula (3), etc. are mentioned, for example.

[chemical 5]

-CH ₂ CH ₂ CH ₂ -O(C ₂ H ₄ O) _n H (2)

(In the formula, n is an average value of 1 to 3.)

[chemical 6]

-R-(S) _a -R ² -OH (3)

(In the formula, R and R ² are divalent hydrocarbon groups with 1 to 10 carbons, and a is 0 or 1.)

By having such a substituent reactive with at least one of the alkyd resin and the amino resin, at least one of the alkyd resin and the amino resin reacts with the silicone resin to form a chemically bonded structure in the release layer, thereby enabling While improving peelability, it suppresses the transfer of silicone to the insulating layer.

Examples of the remaining unsubstituted or substituted alkyl groups other than the aforementioned organic groups include linear or branched alkyl groups having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 5 carbon atoms. Examples of the alkyl group include unsubstituted alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, and octyl; Alkyl groups such as chloromethyl groups, trifluoropropyl groups, cyanoethyl groups, etc. substituted by halogen atoms such as fluorine, chlorine, bromine, and iodine, cyano groups, etc., in which part or all of the combined hydrogen atoms are substituted. In addition, a methyl group is preferable from a viewpoint of obtaining higher peelability.

A surfactant may be blended in the resin composition for a mold release layer used in the present invention.

The surfactant in the present invention refers to a substance that regulates surface phenomena and exhibits surface activity even at a low concentration. As surfactants, there are anionic surfactants in which the main active agent is anionic, cationic surfactants in which the main active agent is cationic, amphoteric surfactants in which the main active agent is amphoteric, and non-ionic nonionic surfactants. The surfactant is preferably a cationic surfactant having antistatic properties from the viewpoint of its effect.

As a cationic surfactant, a quaternary ammonium salt, a tertiary ammonium salt, an amide quaternary ammonium salt, etc. are mentioned, for example. In order to further improve the antistatic effect, quaternary ammonium salts are preferred. As quaternary ammonium salts, for example, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, tetraalkyl ammonium salts, alkyl dimethyl benzyl ammonium salts, alkyl pyridinium salts, alkyl ammonium salts, Phyllinium salts, alkyl imidazolinium salts, amide ammonium salts, 5,5,7,7-tetramethyl-2-octenylmethylammonium chloride, quaternary ammonium salts of polyethyleneimine, benzyl Tris(dimethylamino)phosphonium chloride, hexadecyltris(dimethylamino)phosphonium chloride, and the like.

The amount of the cationic surfactant to be added is 0.05 to 10 parts by mass, preferably 0.1 to 5 parts by mass relative to 100 parts by mass of the composition containing the alkyd resin (A), the amino resin (B) and the silicone resin (C) . When the addition amount is 0.05 parts by mass or more, favorable antistatic performance tends to be obtained. Moreover, when the addition amount is 10 mass parts or less, favorable curability of a coating film will be obtained, and there exists a tendency for the fall of peelability to be suppressed. In addition, in the present invention, in addition to cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants may be used in combination within the range of exhibiting the effects of the present invention. As an anionic surfactant, an alkyl phosphate, an alkyl sulfonate, an alkylbenzene sulfonate, etc. are mentioned, for example. Examples of nonionic surfactants include glycerin fatty acid esters, sorbitan fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene alkylamine fatty acid esters, N-hydroxyethyl-N-2 -Hydroxyalkylamines, alkyldiethanolamides, etc. Moreover, as an amphoteric surfactant, an alkyl betaine, an alkylimidazolium betaine, etc. are mentioned, for example. In addition, various commercial items can be used as said cationic surfactant, nonionic surfactant, anionic surfactant, and amphoteric surfactant.

Moreover, in this invention, you may make the resin composition for mold release layers contain an acidic catalyst. This acidic catalyst functions as a catalyst for the reaction between the alkyd resin (A) and the amino resin (B). By using an acidic catalyst, coating at a low temperature is possible and productivity is improved. As an acidic catalyst, p-toluenesulfonic acid, oxalic acid, phosphoric acid etc. are mentioned, for example.

In order to adjust releasability, the silicone resin (C) containing the functional group reactive with at least one of the above-mentioned alkyd resin (A) and amino resin (B) is introduced into the resin composition for mold release layers. In addition, when the silicone resin was not introduced, the applicability at the time of forming the adhesive layer on the mold release layer was favorable.

It should be noted that a resin composition (hereinafter, sometimes also referred to as a silicone-containing amino alkyd resin) containing a silicone resin having a combination with an alkyd resin (A), The compound obtained by reacting an amino resin (B) and an alkyd resin and an amino resin has a reactive functional group. For example, Hitachi Kasei Polymer Co., Ltd. product names: Tesfine 319, TA31-209E, etc. are mentioned.

In addition, a resin composition containing an alkyd resin and an amino resin (hereinafter, may also be referred to as a non-silicone-based amino alkyd resin) is also commercially available. For example, the brand names of Hitachi Kasei Polymer Co., Ltd.: Tesfine 303, Tesfine 305 etc. are mentioned.

The resin composition for a release layer is preferably in a final state of a varnish (hereinafter, may be referred to as a resin varnish for a release layer) in which each component is dissolved or dispersed in an organic solvent.

As the organic solvent used when making a varnish, for example: alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl Ketone solvents such as 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 Nitrogen atom-containing solvents such as dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.; sulfur atom-containing solvents such as dimethyl sulfoxide, etc. These solvents can be used individually by 1 type or in mixture of 2 or more types.

Among these, aromatic solvents and ketone solvents are preferable, and a mixed solvent of toluene and methyl ethyl ketone (MEK) is more preferable in terms of solubility and appearance during coating.

The content (solid content concentration) of the resin composition in the finally obtained varnish is, for example, preferably 1 to 40% by mass of the entire varnish, more preferably 5 to 30% by mass. By setting the content (solid content concentration) of the resin composition in the varnish to 1 to 40% by mass, it becomes easy to control the film thickness at the time of application.

Moreover, you may add a slip agent, an antistatic agent, etc. to a mold release layer, ie, to the resin composition for mold release layers, as needed. In the hot pressing process, since static electricity is frequently generated, a method of adding an antistatic agent is preferable, and an antistatic layer can be formed by applying to a surface on which a release layer is not formed.

As a method of forming a mold release layer with a desired thickness on at least one side of the polyimide film, there may be mentioned: on the polyimide film, using a reverse roll coater, a gravure coater, a bar coater, an air A knife coater etc., for example, a method of drying at 50° C. to 200° C. for 10 seconds to 600 seconds.

(adhesive layer)

The mold release polyimide film of this invention may have an adhesive layer on the surface which the polyimide film of this mold release layer is not provided.

The above-mentioned adhesive layer is preferably formed on the release surface using a resin composition (hereinafter, sometimes referred to as an adhesive layer resin composition) containing an epoxy resin and an epoxy resin curing agent. Epoxy resins are preferable because they are excellent in heat resistance, alkali resistance, and the like. It should be noted that the resin composition "containing epoxy resin and epoxy resin curing agent" may contain epoxy resin and epoxy resin curing agent in an unreacted state, or may contain epoxy resin in a reacted state. Resin and epoxy resin curing agent.

The thickness of the adhesive layer is preferably 0.01 to 10 μm, more preferably 0.05 to 8 μm. By setting the thickness of the adhesive layer within this range, it becomes easier to remove the release polyimide film at the interface between the adhesive layer and the release layer after hot plate pressing.

Here, an "epoxy resin" is an epoxy resin having two or more epoxy groups in a molecule. As resin which has two epoxy groups in a molecule|numerator, bisphenol A type epoxy resin, bisphenol F type epoxy resin, etc. are mentioned, for example. In addition, a polyfunctional epoxy resin having an average of more than 2 epoxy groups in the molecule can also be used.

Examples of polyfunctional epoxy resins include biphenyl aralkyl epoxy resins, phenol novolak epoxy resins, cresol novolak epoxy resins, aralkyl epoxy resins, naphthalene ring epoxy resins, and polyfunctional epoxy resins. Oxygen resin, naphthalene novolac epoxy resin, etc. Among them, as the polyfunctional epoxy resin, for example, an aralkyl novolac epoxy resin and a naphthalene novolac epoxy resin are preferable. Moreover, it is preferable that the multifunctional epoxy resin of an adhesive layer is resin which has a biphenyl structure, for example from a viewpoint of the adhesive force with copper plating.

These can be used individually or in mixture of 2 or more types.

Among these, for example, an aralkyl novolak type epoxy resin (biphenyl aralkyl type epoxy resin) having a biphenyl structure is preferable. As a commercial item of the aralkyl novolak type epoxy resin which has a biphenyl structure, Nippon Kayaku Co., Ltd. NC-3000, NC-3000-H, etc. are mentioned, for example.

In addition, as the epoxy resin curing agent, for example, polyfunctional phenolic compounds such as phenol novolac and cresol novolac; amine compounds such as dicyandiamide, diaminodiphenylmethane, and diaminodiphenylsulfone; Anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride copolymer, etc. These can be used 1 type or in mixture of 2 or more types.

The resin composition for an adhesive layer may contain a hardening accelerator. As the curing accelerator, for example, various imidazoles, BF ₃ amine complexes, phosphorus-based curing accelerators, etc., which are latent thermosetting agents, can be used.

It is preferable that the compounding quantity of a hardening accelerator is 0.1-5 mass % with respect to the compounding quantity of an epoxy resin.

In view of the storage stability of the resin composition for an adhesive layer, the handleability of the resin composition for a B-stage (semi-cured) resin composition for an adhesive layer, and solder heat resistance (handa heat resistance), imidazoles, Phosphorus curing accelerator.

Examples of imidazoles 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 Imidazole, 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-ethyl-4-methylimidazole, 2-phenyl-4, 5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')] Ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]ethyl-s-triazine and other imidazole compounds; Addition reactant of triacid; Addition reactant of above-mentioned imidazole compound and isocyanuric acid; Addition reactant of above-mentioned imidazole compound and hydrobromic acid; Addition reactant of above-mentioned imidazole compound and epoxy resin; Above-mentioned imidazole Addition reaction products of compounds and cyanate resins, etc. Among them, 2-phenylimidazole and 2-ethyl-4-methylimidazole are preferable.

As the phosphorus-based curing accelerator, one containing a phosphorus atom and accelerating the curing reaction of the epoxy resin is preferable. For example, a phosphorus-based curing accelerator may be used alone, or one or two or more other curing accelerators may be used in combination. Examples of phosphorus-based curing accelerators include triphenylphosphine, diphenyl(alkylphenyl)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, tri(alkylphenyl)phosphine, - alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, Organic phosphines such as tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine; these organic phosphines and Complexes of organic borons; adducts of tertiary phosphine and quinones, etc.

In addition, the resin composition for an adhesive layer of the present invention can optionally use known inorganic fillers, organic fillers, thermoplastic resins, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent Whitening agent and adhesion improving agent, etc.

Examples of inorganic fillers include silica, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, and boron nitride. , calcium carbonate, barium sulfate, aluminum borate, potassium titanate, and E glass, T glass, D glass and other glass powder or hollow glass beads. These can be used individually or in mixture of 2 or more types.

As content of an inorganic filler, it is preferable that it is 10 mass % or less in the resin composition for adhesive layers. When the compounding quantity is 10 mass % or less, the favorable surface shape after a roughening process can be maintained, and the fall of plating characteristics and insulation reliability between layers can be prevented.

Examples of organic fillers include: resin particles with a uniform structure formed of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc.; The core layer in the rubber state formed by acrylate resin, conjugated diene resin, etc. and the core layer formed by acrylate resin, methacrylate resin, aromatic vinyl resin, vinyl cyanide resin, etc. Resin particles with a core-shell structure of a glassy shell layer, etc.

The content of the organic filler is, for example, preferably 0.5 to 300 parts by mass, more preferably 1 to 250 parts by mass with respect to 100 parts by mass of the total of the resin components.

Examples of thermoplastic resins include polyphenylene ether resins, phenoxy resins, polycarbonate resins, polyester resins, polyamide resins, polyimide resins, polyamideimide resins, xylene resins, petroleum resins, and Silicone resin, etc.

Examples of flame retardants include: halogen-containing flame retardants containing bromine and chlorine; triphenyl phosphate, tricresyl phosphate, tris(dichloropropyl) phosphate, phosphoric acid ester compounds, red phosphorus Flame retardants; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine cyanurate; phosphazene-based flame retardants such as cyclophosphazene and polyphosphazene; inorganic systems such as antimony trioxide flame retardant etc.

Moreover, as a ultraviolet absorber, a benzotriazole type ultraviolet absorber etc. are mentioned, for example. As an antioxidant, a hindered phenolic antioxidant, a hindered amine antioxidant, etc. are mentioned, for example. As a photoinitiator, the photoinitiator of a benzophenone system, a benzil ketal system, a thioxanthone system, etc. are mentioned, for example. As a fluorescent whitening agent, a stilbene derivative etc. are mentioned, for example. Examples of the adhesiveness improving agent include urea compounds such as urea silane; coupling agents such as silane-based, titanate-based, aluminate-based, and the like.

The resin composition for an adhesive layer is preferably in the final state of a varnish (hereinafter, sometimes referred to as a resin varnish for an adhesive layer) in which each component is dissolved or dispersed in an organic solvent.

As the organic solvent used when making a varnish, for example: alcohol solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl Ketone solvents such as 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 Nitrogen atom-containing solvents such as dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide, etc. These solvents can be used alone or in combination 2 or more.

These organic solvents are appropriately selected from the viewpoint of the solubility of the resin and the appearance after coating.

Among them, from the viewpoint of the solubility of the resin and the appearance after coating, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; dimethylformamide, N,N- Nitrogen atom-containing solvents such as dimethylacetamide and N-methylpyrrolidone; mixed solvents of ketone-based solvents and nitrogen-atom-containing solvents.

The resin composition in the finally obtained varnish is, for example, preferably 1 to 60% by mass of the entire varnish, more preferably 2 to 50% by mass. The content of the resin composition in the varnish is preferably 1 to 60% by mass from the viewpoint of film thickness accuracy and appearance at the time of coating.

The adhesive layer of the present invention is coated with the resin composition for the adhesive layer (or a varnish containing it) using a reverse coater, gravure coater, air knife coater, die coater, die lip coater, etc. The cloth device is obtained by coating on the release layer of the release polyimide film and drying at, for example, 80 to 230° C. for 30 seconds to 600 seconds.

In addition, in this invention, the surface which the mold release polyimide film is not provided with a mold release layer may have an adhesive layer, and you may use it in the hot plate press process in this state.

By using the mold release polyimide film of this invention, the surface flatness of the insulating layer after a hot press process improves. This surface flatness is as shown by the results of observing the surface state of the insulating layer in Figures 1 and 2 with a high-precision three-dimensional surface roughness measurement system. In the case of using the copper foil shown in Figure 2, the surface will be Although waviness occurred, when using the mold release polyimide film of this invention, as shown in FIG. 1, waviness was hardly observed. It is presumed that the waviness is caused by the difference in thermal expansion between the insulating layer with a low thermal expansion rate and the copper foil with a high thermal expansion rate during the hot pressing process.

[Laminated sheet with release polyimide film with adhesive layer, laminated sheet with release polyimide film peeled off laminated sheet, release polyimide film with adhesive layer single-layer or multilayer wiring board, and method for manufacturing multilayer wiring board]

The laminate with the 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 a prepreg or an insulating layer. A laminate made of at least one side.

The laminate with the release polyimide film with an adhesive layer of the present invention can be laminated on a prepreg with the release polyimide film with an adhesive layer so that the adhesive layer is on the inside Or one or both sides of the insulating layer, and laminated panels on the outside are pressed and formed.

In addition, the laminate with the release polyimide film with an adhesive layer of the present invention can be formed, for example, by overlapping the release polyimide film with an adhesive layer with the adhesive layer on the inside. One or both sides of the prepreg or insulating layer are laminated by heating and pressurizing with a laminator using a heat-resistant rubber sheet, and heated and cured after lamination.

The heating temperature (temperature of the hot plate) for the press molding is preferably 150 to 260°C. The pressure at the time of pressurization is preferably 0.5 to 10 MPa. In addition, the heating temperature of the laminator using the heat-resistant rubber sheet is preferably 80 to 150°C. The pressure at the time of pressurization is preferably 0.3 to 10 MPa.

In any method, the mold release polyimide film can be peeled off suitably after lamination molding, and a laminated board can be obtained.

The single-layer or multilayer wiring board with the above-mentioned release polyimide film (release polyimide film with an adhesive layer) of the present invention is that the release polyimide film with an adhesive layer The adhesive layer side is laminated on one side of the prepreg or insulating layer, and the other side of the prepreg or insulating layer is laminated on a single-layer or multi-layer wiring board formed by circuit processing. The prepreg may be a prepreg before curing or may be at least partially cured.

Here, "processed by circuit processing" includes the case of performing a process that can be generally performed in the manufacture of a wiring board after circuit processing, and specifically includes the case of performing plating treatment or the like after circuit processing. In addition, in the case of a single-layer wiring board, when a prepreg or an insulating layer is laminated on only one side, it refers to a wiring board having one circuit layer, and a prepreg or an insulating layer is laminated on both sides. In this case, it refers to a wiring board having one circuit layer (that is, a total of two circuit layers) on both sides. On the other hand, a multilayer wiring board means that at least one layer of prepreg or insulating layer is laminated on at least one side of the circuit-processed core (core) and the surface of the circuit-processed core, and A wiring board made by processing a circuit on a prepreg or an insulating layer.

The manufacturing method of the multilayer wiring board of the present invention includes: by laminating the above-mentioned release polyimide film with the adhesive layer on the single-layer or multilayer wiring board, thereby manufacturing the release polyimide film with the adhesive layer. A process of single-layer or multi-layer wiring board of imide film; a process of removing the release polyimide film from the single-layer or multi-layer wiring board with the release polyimide film with adhesive layer; and carrying out The process of circuit processing. Here, as the manufacturing method of the release polyimide film having an adhesive layer, it is preferable to include: coating a release agent containing an alkyd resin (A) and an amino resin (B) on one side of the polyimide film. A step of forming a mold release layer with an agent composition (release polyimide film manufacturing process); and forming an adhesive layer on the surface of the above mold release layer on which the polyimide film is not provided to manufacture a film with an adhesive layer. Process of releasing polyimide film (production process of release polyimide film with adhesive layer).

Among the above steps, the mold release polyimide film production process and the release polyimide film production process with an adhesive layer are as described above.

Hereinafter, the manufacturing process of the single-layer or multilayer wiring board with the release polyimide film with an adhesive layer, and the removal process of the release polyimide film are demonstrated.

It should be noted that after the release polyimide film is removed from the single-layer or multilayer wiring board with the release polyimide film with the adhesive layer, the adhesive layer is used as the insulating layer of the multilayer wiring board. function.

In the manufacturing process of a single-layer or multilayer wiring board with a release polyimide film with an adhesive layer, for example, first, the release polyimide film of the present invention having an adhesive layer is formed according to The adhesive layer is superimposed on the prepreg or the insulating layer so as to be inside, and this is superposed on one side or both sides of the wiring board to be circuit-processed. The panels are further laminated on the outside and press-molded. By removing the panel, a single-layer or multilayer wiring board in which the release polyimide film of the present invention is arranged on one or both surfaces 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 step of performing circuit processing.

The heating temperature (temperature of the hot plate) of the above-mentioned press molding is, for example, preferably 180 to 300°C, more preferably 200 to 250°C. The pressure at the time of pressurization is preferably 1 to 4 MPa.

In addition, before peeling (release polyimide film removal process), you may perform drilling process and laser processing from the upper surface of a polyimide film as needed, and you may remove a release polyimide film after that. By performing hole processing from the upper surface of the polyimide film, resin scattering during processing can be prevented, and the yield rate can be significantly improved.

Here, the materials of the prepreg and the insulating layer used in the method of manufacturing the multilayer wiring board of the present invention are not particularly limited, and commonly used materials can be applied. For example, a material mixed with a multifunctional epoxy resin, an epoxy resin curing agent, a curing accelerator, a solvent, and if necessary, an inorganic filler can be used as the material of the insulating layer, and the material can be further impregnated or coated on the laminate. Plates are prepregs derived from glass cloth. A commercial item may be used as a prepreg, and as a commercial item, GEA-67N, GEA-679F, GEA-679GT, GEA-700G etc. by Hitachi Chemical Co., Ltd. are mentioned, for example.

The inner layer circuit board in the single-layer wiring board or multi-layer wiring board processed by the circuit is, for example, the inner layer substrate with the first circuit layer (inner layer wiring) formed on the surface. As the inner layer substrate, it can be used in common Known laminated boards used in wiring boards, such as glass cloth-epoxy resin, paper-phenolic resin, paper-epoxy resin, glass cloth, or cellophane-epoxy resin, are not particularly limited. In addition, 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.

There is no particular limitation on the method of forming the circuit. For example, known circuit forming methods such as a semi-additive method of forming a circuit using a plating process and an additive method of forming a circuit on a desired portion of an insulating substrate by electroless plating can be used.

When performing circuit processing by a plating process on the adhesive layer of the laminated board or the single-layer or multi-layer wiring board of the present invention, first, roughening treatment is performed. As the roughening liquid at this time, for example, oxidizing roughening liquids such as chromium/sulfuric acid roughening liquid, alkaline permanganic acid roughening liquid, sodium fluoride/chromium/sulfuric acid roughening liquid, and fluoboric acid roughening liquid can be used. As the roughening treatment, for example, the following method can be cited: First, heat an aqueous solution of diethylene glycol monobutyl ether and NaOH as a swelling liquid to 70°C, and perform 5 minutes on a laminated board or a single-layer or multi-layer wiring board. Dipping treatment. Next, an aqueous solution of KMnO ₄ and NaOH as a roughening solution was heated to 80° C. and dipped for 10 minutes. Next, immersion treatment is performed for 5 minutes in a neutralizing solution, for example, an aqueous hydrochloric acid solution of stannous chloride (SnCl ₂ ) at room temperature to perform neutralization.

After the roughening treatment, a plating catalyst imparting treatment for attaching palladium is performed. The plating catalyst treatment is performed by immersing in a palladium chloride-based plating catalyst solution. Next, the electroless plating process deposits the electroless-plating layer (conductor layer) with a thickness of 0.3-1.5 micrometers on the whole surface of the primer layer for plating processes by immersing in an electroless-plating liquid.

Next, after the plating resist is formed, a plating process is performed to form a circuit with a desired thickness at a desired location. As the electroless plating solution used in the electroless plating treatment, known electroless plating solutions can be used without any particular limitation. As the anti-plating film, a known anti-plating film can also be used, and it is not particularly limited. In addition, known methods can also be used for electroplating treatment, and are not particularly limited. These platings are preferably copper plating. Furthermore, the electroless plating at unnecessary parts can be etched away to form an outer layer circuit.

In addition, the method of surface-treating the surface of the circuit layer to a state suitable for adhesiveness is not particularly limited. For example, known production methods such as forming needle-shaped crystals of copper oxide on the surface of the circuit layer 1 with an aqueous alkali solution of sodium hypochlorite, and reducing the formed needle-shaped crystals of copper oxide by immersing them in an aqueous solution of dimethylamine borane can be used. .

Thereafter, a multilayer wiring board having a large number of layers can be produced by further repeating the same steps.

Example

Next, the present invention will be described using examples, but the scope of the present invention is not limited by these examples.

[Preparation of resin varnish for adhesive layer]

(preparation example 1)

Phenol aralkyl resin (manufactured by Mitsui Chemicals, Inc., trade name: XLC- LL) 22.5g, add pimelinketone 850g, carry out stirring and kneading. To this was added 100 g of acrylic rubber (manufactured by Nagase Chemtex Co., Ltd., trade name: HTR-860P-3, weight average molecular weight: 800,000, glass transition temperature: 13° C.), and 1-cyanoethyl- 0.25 g of 2-phenylimidazole (manufactured by Shikoku Chemical Industry Co., Ltd., trade name: Curezol 2PZ-CN) was stirred to obtain a resin varnish A for an adhesive layer (solid content concentration: about 15% by mass).

(preparation example 2)

After blending 159 g of N,N-dimethylacetamide (DMAc) into 18 g of polyamide (manufactured by Nippon Kayaku Co., Ltd., trade name: BPAM-155), biphenyl aralkyl type epoxy resin (Japan Kayaku Co., Ltd., trade name: NC3000H) 50 g, bisphenol A novolak type phenolic resin (Mitsubishi Chemical Co., Ltd., trade name: YLH129) 20 g, and 2-phenylimidazole (Shikoku 0.5 g of Kasei Kogyo Co., Ltd., trade name: 2PZ) was diluted with a mixed solvent containing DMAc and methyl ethyl ketone, and 5 g of alumina filler (CI Kasei Co., Ltd., trade name: NanoTek) was added. Kogyo Co., Ltd. product, brand name: Nanomizer), and resin varnish B for an adhesive layer (solid content concentration: about 25 mass %) was obtained.

[Preparation of resin varnish for release layer]

(preparation example 3)

31.5 g of non-silicone-based amino alkyd resin [Tesfine 303, manufactured by Hitachi Kasei Polymer Co., Ltd., solid content 48.7%] was mixed with p-toluenesulfonic acid [Dryer 900, manufactured by Hitachi Kasei Polymer Co., Ltd., solid content 50%] as an acidic catalyst %] 1.5 g, and then diluted with 1050 g of toluene and 450 g of MEK to obtain a resin varnish A for a release layer.

(preparation example 4)

To 31.5 g of non-silicone-based amino alkyd resin [Tesfine 305, manufactured by Hitachi Kasei Polymer Co., Ltd., trade name, solid content 48.7%], p-toluenesulfonic acid [Dryer900, manufactured by Hitachi Kasei Polymer Co., Ltd., commercial product] was added as an acidic catalyst. name, solid content 50%] 1.5 g, and then diluted with 1050 g of toluene and 450 g of MEK to obtain a resin varnish B for a release layer.

(preparation example 5)

To 31.5 g of silicone-containing amino alkyd resin [Tesfine 319, manufactured by Hitachi Kasei Polymer Co., Ltd., solid content 48.7%], p-toluenesulfonic acid [Dryer900, manufactured by Hitachi Kasei Polymer Co., Ltd., product name, solid] was blended as an acidic catalyst. Component 50%] 1.5 g, and then diluted with 1050 g of toluene and 450 g of MEK to obtain a resin varnish C for a release layer.

(preparation example 6)

P-toluenesulfonic acid (Dryer900, manufactured by Hitachi Kasei Polymer Co., Ltd., manufactured by Hitachi Kasei Polymer Co., Ltd.) Brand name, solid content 50%] 1.5 g, and then diluted with 1050 g of toluene and 450 g of MEK to obtain a resin varnish D for a release layer.

(Example 1)

Release polyimide film with adhesive layer:

As the polyimide film, Upilex 25SGA (trade name) manufactured by Ube Industries, Ltd. having a thickness of 25 μm and a surface roughness Ra of less than 0.05 μm was used. The release layer resin varnish A prepared in Production Example 3 was coated on this polyimide film using a die coater, and dried at 160° C. for 40 seconds to obtain a release layer with a thickness of 0.2 μm.

The resin varnish A for an adhesive layer prepared in Preparation Example 1 was coated on the release surface of the obtained release polyimide film, and dried at 140° C. for 5 minutes to form an adhesive layer with a thickness of 5 μm to obtain a tape. Release polyimide film for adhesive layer.

· Laminates:

Four sheets of prepreg (manufactured by Hitachi Chemical Co., Ltd., trade name: GEA-700G, 0.10 mm thick) are stacked, and the polyimide film surface of the above-mentioned release polyimide film with an adhesive layer becomes The mold release polyimide film with an adhesive layer was superimposed on the outside, and then the panel and cushion paper were superimposed, and heat-cured at 3.0 MPa and 240° C. for 1 hour using a press machine to obtain a laminated board.

(Example 2)

As the polyimide film, Kapton 100H (trade name) manufactured by Toray Dupont Co., Ltd. with a thickness of 25 μm and a surface roughness Ra of less than 0.05 μm was used, except that, in the same manner as in Example 1, a mold release with an adhesive layer was obtained. Polyimide films and laminates.

(Example 3)

As the release layer, the release layer resin varnish B prepared in Preparation Example 4 was used, and the adhesive layer varnish B prepared in Preparation Example 2 was used as the adhesive layer. Similarly, a release polyimide film with an adhesive layer and a laminated board were obtained.

(Example 4)

As the release layer, the release layer resin varnish C prepared in Preparation Example 5 was used, and the adhesive layer varnish B prepared in Preparation Example 2 was used as the adhesive layer. Similarly, a release polyimide film with an adhesive layer and a laminated board were obtained.

(Example 5)

The release layer resin varnish D prepared in Preparation Example 6 was used as the release layer, and the adhesive layer varnish B prepared in Preparation Example 2 was used as the adhesive layer. Similarly, a release polyimide film with an adhesive layer and a laminated board were obtained.

(comparative example 1)

Instead of a polyimide film with a release layer, a polyethylene terephthalate film with a release layer (Unipeel TR1, manufactured by Unitika Co., Ltd., trade name, thickness 38 μm), in addition, In the same manner as in Example 1, a release film with an adhesive layer and a laminate were obtained.

(comparative example 2)

Except not forming a mold release layer on the polyimide film, operate in the same manner as in Example 1, coat and form an adhesive layer on the polyimide film surface, and obtain a release film with an adhesive layer and a laminate. plate.

(comparative example 3)

Instead of the mold release polyimide film, an adhesive layer was coated on the glossy surface of an electrolytic copper foil (manufactured by Furukaw Circuit Foil Co., Ltd., GTS-18, thickness 18 μm), and a laminate was obtained in the same manner as in Example 1.

(comparative example 4)

A laminated board was obtained in the same manner as in Example 1 except that a silicone-based release agent (Shin-Etsu Chemical Co., Ltd. make, KS-774, brand name) was used instead of the resin varnish A for a release layer.

For the laminated board produced in the above manner, the measurement of film peelability after pressing was carried out in the following manner, and for the laminated board after peeling which could be easily peeled off, the insulating layer (adhesion after thermosetting) was implemented in the following manner Determination of surface roughness, non-transferability and surface flatness of layer). The results are shown in Table 1 and Table 2 below.

[Peelability after pressing]

After pressing, it was confirmed whether the film could be peeled off independently without deformation, welding, or cracking of the release film. Moreover, when the release film was peeled from the laminated sample after pressing, it was confirmed visually whether peeling was possible at the interface with the release layer.

A: It can be easily peeled off at the interface.

C: It cannot be easily peeled off at the interface.

"It cannot be easily peeled at the interface" means the case where the film cannot be peeled alone, or the case where the resin composition of the adhesive layer adheres to the release film after peeling.

[Surface roughness]

The surface roughness of the insulating layer after pressing and peeling off the film was measured under the following measurement conditions using a surface shape measuring device (manufactured by Veeco, trade name: WykoNT9100).

-Measurement conditions-

Internal lens: 1x

External lens: 50 times

Measuring range: 0.125×0.095mm

Measuring depth: 10μm

Measuring method: vertical scanning interference method (VSI method)

[non-metastatic]

After peeling off the polyimide film from the laminated board after pressing, Magic Ink (registered trademark) No. 500 (black) manufactured by Teranishi Chemical Industry Co., Ltd. was applied on the insulating layer, and the state of ink repellency (はじき) was observed. . The ink repelling phenomenon indicates the transfer of the release layer components to the insulating layer, so the case of repelling was evaluated as "C", and the case of not repelling was evaluated as "A".

[Surface Flatness]

The surface shape of the pressed insulating layer was observed using a high-precision three-dimensional surface roughness measuring system (WYKO NT9100, manufactured by Veeco). Fig. 1 and Fig. 2 show the results of surface observation of the X-axis: 125 μm, Y-axis: 95 μm shape range.

[Table 1]

project unit Example 1 Example 2 Example 3 Example 4 Example 5 Stripping - A A A A A Surface roughness μm <0.05 <0.05 <0.05 <0.05 <0.05 Non-metastatic - A A A A A

[Table 2]

project unit Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Stripping - C C C A Surface roughness μm - - - 0.05 Non-metastatic - - - - C

As can be seen from Table 1: the characteristics of the release polyimide film of the present invention and the laminated board with the adhesive layer are as shown in Examples 1 to 5, and can be easily peeled off after being pressed by a hot plate at a high temperature of 240°C. Molded polyimide film, and can get the insulating layer with flat surface.

On the other hand, as can be seen from Table 2: in Comparative Example 1 using films other than the polyimide film, the polyethylene terephthalate film was welded to the panel, and the release film could not be easily peeled off alone. And an insulating layer with a good surface state cannot be obtained. In addition, in Comparative Example 2, it was confirmed that the polyimide film was broken and the polyimide film could not be peeled off alone. In Comparative Example 3, it was confirmed that the copper foil was cracked and the copper foil could not be peeled off alone. In Comparative Example 4, it was confirmed that when Magic Ink was applied on the insulating layer, repelling of the ink was observed, and components of the release layer migrated to the insulating layer.

In addition, the observation results of the surface flatness of Example 1 are shown in FIG. 1, and the observation results of the surface flatness of Comparative Example 3 are shown in FIG. The surface of the insulating layer of the release polyimide film of the present invention is flat.

Industrial availability

The mold release polyimide film of this invention can be utilized effectively as a mold release film when manufacturing a multilayer wiring board by the shaping|molding method using a hot plate press, a roll laminator, a double press, etc.

Claims (10)

1. a demoulding polyimide film, it has containing alkyd resin (A) and amino at least one side of polyimide film The release layer of resin (B).

Demoulding polyimide film the most according to claim 1, wherein, the thickness of described release layer is 0.01～10 μm.

Demoulding polyimide film the most according to claim 1 and 2, wherein, the thickness of described polyimide film is 10～100 μm。

4. according to the demoulding polyimide film according to any one of claims 1 to 3, wherein, the formation of described polyimide film The surface roughness (Ra) in the face of described release layer side is below 0.2 μm.

5., according to the demoulding polyimide film according to any one of Claims 1 to 4, it is not provided with polyamides described release layer On the face of imines film, there is adhesive linkage.

Demoulding polyimide film the most according to claim 5, wherein, described adhesive linkage uses and comprises epoxy resin and epoxy The resin combination of resin curing agent forms.

7. having a plywood for the demoulding polyimide film of band adhesive linkage, it is by the demoulding polyamides described in claim 5 or 6 The adhesive linkage side at least one side in prepreg or insulating barrier cascading into shape of imines film forms.

8. a plywood, the demoulding polyimide film of the plywood described in claim 7 is peeled off and is formed by it.

9. having a single or multiple lift wiring plate for the demoulding polyimide film of band adhesive linkage, it is by described in claim 5 or 6 The adhesive linkage side of demoulding polyimide film be laminated in prepreg or the one side of insulating barrier and by another of prepreg or insulating barrier Surface layer is laminated on forming through the single or multiple lift wiring plate of circuit fabrication.

10. a manufacture method for multiwiring board, comprising:

By the demoulding polyimide film described in claim 5 or 6 being laminated in single or multiple lift wiring plate, thus manufacture and have The operation of the single or multiple lift wiring plate of the demoulding polyimide film with adhesive linkage；

The operation of demoulding polyimide film is removed from the single or multiple lift wiring plate of the demoulding polyimide film with band adhesive linkage； And

Carry out the operation of circuit fabrication.