TWI645966B - Polyimide release film, laminated board equipped with polyimide release film with adhesive layer, laminated board, single-layer or multilayer circuit board equipped with polyimide release film with adhesive layer And manufacturing method of multilayer wiring board - Google Patents

Abstract

The invention provides a polyimide release film, which is used as a material. The material does not need to be etched after the hot-pressing step, an insulating layer having a surface roughness suitable for the semi-additive method can be obtained, and further, good flatness can be manufactured. Single-layer or multilayer circuit boards. Specifically, the present invention provides a polyimide release film having a release layer on at least one side of the polyimide film, the release layer containing an alkyd resin (A) and an amine-based resin (B). In addition, the present invention provides a method for manufacturing a multilayer wiring board. The method includes the steps of demolding a polyimide having an adhesive layer on a surface of the release layer that is not provided with a polyimide film. The film is laminated on a single-layer or multi-layer circuit board to produce a single-layer or multi-layer circuit board provided with a polyimide release film with an adhesive layer; the polyimide is provided with an adhesive layer and is released from the mold A step of removing a polyimide release film from a single-layer or multi-layer circuit board of the film; and a step of performing circuit processing.

Description

Polyimide release film, laminated board equipped with polyimide release film with adhesive layer, laminated board, single-layer or multilayer circuit board equipped with polyimide release film with adhesive layer And manufacturing method of multilayer wiring board

The invention relates to a polyimide mold release film, a laminated board configured with a polyimide release film with an adhesive layer, a laminated board, and a single sheet equipped with a polyimide release film with an adhesive layer. A multilayer or multilayer wiring board, and a method for manufacturing a multilayer wiring board.

Conventionally, a multilayer wiring board is manufactured through a hot pressing step. This hot-pressing step is performed by laminating a prepreg or a resin film and a copper foil on a single or double-sided circuit board having an inner layer circuit. The prepreg is impregnated with a resin composition, It is obtained by coating on a fiber substrate, and the resin film does not include a fiber substrate. The hot pressing step is widely used because of its high productivity.

In addition, in recent years, with the miniaturization and high integration of electronic equipment, fine wiring of multilayer wiring board materials is also required. As a method for forming a fine circuit, a semi-additive method is suitably used. After electroless copper plating is performed on the surface where a circuit is to be formed, electrolytic copper plating is performed only on a required portion, and by Etching removes the copper plating layer of the unnecessary part and forms a circuit. In this way, by making the copper layer to be removed by etching The thinner the thickness, that is, the thinner the copper plating layer is formed on the surface where the surface roughness is to be formed, and the thinner the copper plating layer is removed, the finer the wiring can be.

However, in the manufacture of a multilayer wiring board using a hot-pressing step, copper foil is required to be etched in order to perform a semi-additive method because a copper foil is laminated between a circuit-forming surface and a pressure plate during the hot-pressing step. Procedure (see, for example, Patent Document 1). In addition, since the surface roughness of the copper foil is transferred to the surface on which the multilayer circuit is to be formed, the surface roughness of the surface on which the circuit is to be formed is large and is about 0.3 μm.

In order to solve this problem, the use of thin film materials such as polyethylene terephthalate (PET) with a small surface roughness in place of copper foil is also being studied (see, for example, Patent Document 2). Low heat resistance or thermal deformation, so there is still room for further improvement.

Moreover, as a mold release agent of such a film material, the silicone release agent which is excellent in peelability is widely used.

[Prior technical literature] (Patent Literature)

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

Patent Document 2: Japanese Patent No. 5212578

However, in the case of using a polysiloxane-based release agent, there is a problem that a low-molecular-weight component in the polysiloxane composition is transferred to an insulating layer and the reliability is lowered.

In view of this situation, an object of the present invention is to provide a polyimide release film as a material that does not require etching after the hot pressing step previously required in the case of using copper foil, and can obtain a surface The roughness is suitable for the semi-additive insulation layer, and the release agent component is less transferred to the insulation layer, and further, a multilayer circuit board with good flatness can be manufactured.

The inventors have repeatedly researched in order to achieve the foregoing object, and found that the polyimide film having a release layer shown below, which is also a polyimide release film, can meet the above-mentioned purpose to complete the present invention.

That is, the present invention provides the following materials.

[1] A polyimide release film having a release layer on at least one side of the polyimide film, the release layer containing an alkyd resin (A) and an amine resin (B). to make.

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

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

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

[5] The polyimide release film according to any one of [1] to [4], wherein an adhesive layer is provided on a surface of the release layer on which the polyimide film is not provided.

[6] The polyimide release film according to [5], wherein the adhesive The landing layer is made of a resin composition containing an epoxy resin and an epoxy resin hardener.

[7] A laminated board in which a polyimide release film with an adhesive layer is arranged, wherein the polyimide release film according to [5] or [6] is laminated on the adhesive layer side and formed on the It is formed on at least one surface of a prepreg or an insulating layer.

[8] A laminated sheet obtained by peeling the polyimide release film of the laminated sheet according to [7].

[9] A single-layer or multilayer circuit board provided with a polyimide release film with an adhesive layer, which is an adhesive layer side of the polyimide release film according to [5] or [6], It is laminated on one side of the prepreg or insulation layer, and the other side of the prepreg or insulation layer is laminated on a single-layer or multilayer circuit board to be processed by a circuit.

[10] A method for manufacturing a multilayer wiring board, the method comprising the steps of manufacturing by laminating the polyimide release film described in [5] or [6] on a single-layer or multilayer wiring board A step of disposing a single-layer or multilayer circuit board with a polyimide release film with an adhesive layer; and removing a poly-imide film by a single-layer or multilayer circuit board with a polyimide release film with an adhesive layer A step of releasing the amine film; and a step of performing circuit processing.

According to the present invention, it is possible to provide a polyimide release film and a method for manufacturing a multilayer wiring board using the same. The polyimide release film is subjected to, for example, pressing using a hot plate, a roll laminator, and When forming a multilayer wiring board by a molding method such as a double press, it has excellent peelability from the insulating layer, and furthermore, it also has a film that will not be used even at high temperatures such as 200 ° C or higher. The heat resistance of fusing, the release agent component is less transferred to 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.

FIG. 1 shows the results of observing the surface state of the insulating layer after the polyfluorene imide release film was peeled off under pressure using a high-precision three-dimensional surface shape roughness measurement system in Example 1. FIG.

FIG. 2 shows the results of observing the surface state of the insulating layer after removing the surface of the electrolytic copper foil by etching using a high-precision three-dimensional surface shape roughness measurement system in Comparative Example 3. FIG.

[Polyimide release film]

First, the polyimide release film of the present invention will be described. The polyimide release film of the present invention has a release layer on at least one side of the polyimide film, and the release layer is formed by containing an alkyd resin (A) and an amine-based resin (B). .

In addition, in the present specification, the meaning of "contained to" means any of the following states: the contained substance is contained in a state where it is not reacted, and the contained substance is A part is contained in a state where the reaction proceeds.

As the polyimide film used as the base material of the polyimide release film of the present invention, a film having an appropriate strength without causing cracks or the like when peeled is suitable. For example, from the viewpoint of film strength, an aromatic polyfluorene imide in which an aromatic compound is directly bonded by a fluorene imine bond is preferable, and it is more preferable to have Aromatic polyfluorene imine having a structural unit represented by the following formula (I).

(In formula (I), Z ¹ is a tetravalent aromatic hydrocarbon group having 6 to 18 carbon atoms, and 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.

As the divalent aromatic hydrocarbon group having 6 to 18 carbon atoms represented by Z ² , the following aromatic hydrocarbon group is preferred, for example.

As a commercially available polyimide film, for example, Ube Kosan 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; trade names manufactured by Zhong Yuan Chemical Industry Co., Ltd. Apical AH, Apical NPI, etc. In order to improve the adhesion with the release layer, the surface of these commercially available films may be subjected to, for example, a plasma treatment or a corona discharge treatment.

The thickness of the polyimide film used as the base material of the polyimide release film of the present invention can be selected according to the purpose and application. From the viewpoint of the followability and peelability of the polyimide film, the thickness of the polyimide film is, for example, preferably from 10 to 100 μm, more preferably from 20 to 50 μm, and even more preferably from 25 to 50 μm.

The surface roughness (Ra) of the polyimide film used as the base material of the polyimide release film of the present invention is preferably, for example, from the viewpoint of making the flatness of the insulating layer after peeling good. 0.2 μm or less, more preferably 0.1 μm or less, and 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 which at least one side of a mold release layer is to be formed.

The polyimide film of the present invention has a strength that will not be melted in a high-temperature region, so it is preferably used at 150 to 300 ° C, and more preferably, it does not show a significant glass transition temperature in this range, and it stores the elastic mold. The number (10Hz) exceeds 1GPa.

(Release layer)

A resin composition (hereinafter also referred to as a resin composition for a release layer) for forming a release layer of a polyimide release film of the present invention, which contains an alkyd resin (A) And amine-based resin (B). In the solid content of the resin composition for a release layer, the total content of the alkyd resin (A) and the amine resin (B) (however, the total content of the solid content when an organic solvent is contained) is preferably 50% by mass. Above, more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more.

By setting the release layer as a layer containing an alkyd resin (A) and an amine resin (B), a crosslinked structure can be obtained in the release layer, as compared with a polysiloxane release agent. In addition, the resin composition component for the release layer can be suppressed from being transferred to the insulating layer, and more favorable peelability can be 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 and the like of the insulating layer.

The thickness of the release layer is preferably, for example, 0.01 to 10 μm, more preferably 0.05 to 5 μm, and still more preferably 0.05 to 2 μm. When the thickness of the release layer is 0.01 to 10 μm, the peelability tends to be improved.

The ratio (A / B) of the component (A) to the component (B) is preferably 95/5 to 10/90, and more preferably 90/10 to 40/60, based on the solid content ratio.

When the ratio of the alkyd resin (A) is 95% by mass or less (that is, the ratio of the amine-based resin (B) is 5% by mass or more), a sufficient crosslinked structure can be obtained in the release layer, and peelability can be suppressed. Reduced tendency. When the ratio of the alkyd resin (A) is 10% by mass or more (that is, the ratio of the amine-based resin (B) is 90% by mass or less), the mold release layer does not become too hard and good peeling can be obtained. Sexual orientation.

In the present invention, the alkyd resin (A) refers to a synthetic resin obtained by a condensation reaction between a polyhydric alcohol and a polybasic acid. As the alkyd resin (A), Use any of the following: a condensate of a dibasic acid and a diol or a non-converting alkyd modified with a non-drying oil fatty acid; and a condensate of a dibasic acid and a trihydric or higher alcohol that is a converting alcohol acid.

In addition, the alkyd resin (A) used in the present invention may be various commercially available products, or may be synthesized according to a known method.

As a method of synthesizing the alkyd resin (A), for example, a method of heating and condensing a polyhydric alcohol and a polybasic acid, or adding a modifier to these, can be mentioned.

As the polyhydric alcohol, for example, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and neopentyl glycol; Glycerol, trimethylolethane, trimethylolpropane and other triols; diglycerol, triglycerol, pentaerythritol, monopentaerythritol, dipentaerythritol, mannitol, sorbitol and other polyols.

As the polybasic acid, for example, saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, and sebacic acid; maleic acid, maleic anhydride, and fumaric acid can be used. Unsaturated polybasic acids such as diacid, itaconic acid, methyl maleic anhydride, isophthalic acid, trimellitic anhydride; cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride Diacid anhydride adducts, rosin-maleic anhydride adducts, and the like are polybasic acids produced by the Diels-Alder reaction. Also, benzoic acid may be used in combination.

As the modifier, for example, coconut oil, linseed oil, tung oil, castor oil, dehydrated castor oil, and the like, fatty acids, caprylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, sub- Oleic acid, linolenic acid, paulownic acid, ricinoleic acid, dehydrated ricinoleic acid, etc.

Oil length (content ratio of fatty acid) of alkyd resin (A), It is preferably, for example, 0 to 60%, and more preferably 20 to 40%.

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

The hydroxyl value of the alkyd resin (A) is preferably, for example, 50 to 300 mgKOH / g, and more preferably 100 to 250 mgKOH / g.

Among these alkyd resins (A), for example, acrylic resins, polyester resins, epoxy resins, phenol resins, etc. can be modified or used in combination.

The amine-based resin (B) of the present invention is a resin obtained by a condensation reaction of an amine-containing compound and an aldehyde, and examples thereof include a melamine resin, an aniline resin, a urea formaldehyde resin, and a benzoguanamine resin.

As the amine-based resin used in the present invention, various commercially available amine-based resins can be used, or they can be synthesized according to a known method.

As the synthesis method, for example, various amine-based resins synthesized using a prepolymer as a raw resin can be used, and the prepolymer contains a prepolymer of methylol or an ether thereof.

More specifically, for example, methylated melamine resin, butylated melamine resin, methylated urea formaldehyde resin, butylated urea formaldehyde resin, methylated benzoguanamine resin, butylated benzoguanamine resin, and the like can be used. Various well-known. From the viewpoint of reusability, a methylated melamine resin is preferably used as a main component, and the methylated melamine resin is particularly preferably a methylated melamine resin containing one or more methylol groups per triazine core.

In the present invention, the methylated melamine resin that is particularly preferably used as an amine-based resin is generally obtained by starting an addition reaction between formalin and melamine in an alkaline environment, and further making methanol in an acidic environment. Ether 化 反应。 Reaction. Based on the difference in the amount of formalin addition or the etherification amount of methanol, the amount of fluorenimine, methylol, and methyl ether groups that are functional groups of the amine resin can be controlled.

The amount of methylol groups in each triazine nucleus can be calculated by titration analysis and machine analysis. For example, it can be calculated by measurement using a nuclear magnetic resonance device or an elemental analysis device.

Moreover, in this invention, within the range which suppresses the resin composition component for a release layer from being transferred to an insulating layer, from the standpoint of peelability, the resin composition for a release layer can be made to contain a silicone resin (C).

In this case, the content ratio of the silicone resin, that is, the content ratio of the silicone resin (C) to the total content of the alkyd resin (A) and the amine resin (B) (C / (A + B)), The mass ratio of solid content is preferably 20/100 or less, and more preferably 10/100 or less. With respect to 100 parts by mass of the total of the component (A) and the component (B), if the component (C) is 20 parts by mass or less, good hardenability can be obtained, and silicone resin (C) transfer is difficult to occur. tendency.

In addition, the silicone resin (C) of the present invention means an organic polysiloxane, a silicone rubber, and a silicone oil having a three-dimensional network structure using dimethylpolysiloxane as a main component. The polysiloxane resin (C) used in the present invention can be produced using various commercially available products or can be synthesized according to a known method.

As the polysiloxane resin (C), an organic polysiloxane is preferred. As long as a release layer having excellent heat resistance, gloss, peelability, and surface state can be obtained, any of linear and branched structures can be used. Yes, the resin composition for a release layer of the present invention is preferably one which has excellent compatibility with the alkyd resin (A) and the amine resin (B).

In addition, the organic polysiloxane can change the properties of the resin such as flexibility and elasticity by changing the molar ratio of the organic group to the silicon atom. Specific examples of such an organopolysiloxane include an organopolysiloxane represented by the following formula (1):

(In the formula, at least one of R ^{1 is} a substituent having reactivity with at least one of the alkyd resin and the amine-based resin (but including a reactant of the alkyd resin and the amine-based resin), and the rest are carbon numbers 1 to Unsubstituted or substituted alkyl of 12, X is 15 to 500, preferably 25 to 100, Y is 15 to 500, preferably 25 to 100, X + Y is 30 to 1000, preferably 50 to 200, And 0.15 ≦ Y / (X + Y) ≦ 0.5).

In one molecule of the organic polysiloxane, the organic group bonded to the silicon atom is preferably 15 to 50 mol% of phenyl group, and more preferably 15 to 40 mol%. When 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, if the amount of phenyl group is 50 mol% or less, there exists a tendency for suppressing a fall of peelability.

In order for the release layer to have sufficient release properties, it is preferred that at least one of the remaining organic groups other than the aforementioned phenyl group is a functional group that is reactive with at least one of the alkyd resin and the amine-based resin. Examples of the functional group reactive with at least one of the alkyd resin and the amine-based resin include an organic group substituted with a hydroxyl group, an organic group substituted with an amine group, an organic group substituted with a carboxyl group, and an organic group substituted with a carboxyl group. Glycidyl substituted organic groups and the like. Among these, a hydroxyl-substituted organic group is preferred from the viewpoint that the method for introducing the amino alkyd resin is easier.

When a hydroxy-substituted organic group is used, the hydroxy-substituted organic group preferably contains 1 to 20 polysiloxane resins per molecule, and more preferably contains 1 to 10 polysiloxane resins. Examples of the hydroxy-substituted organic group include a hydroxy-substituted organic group represented by the following formula (2) and a hydroxy-substituted organic group represented by the following formula (3): -CH ₂ CH ₂ CH _2- O (C ₂ H ₄ O) _n H (2)

(Where n is an average of 1 to 3); -R- (S) _a -R ² -OH (3)

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

By having such a substituent having reactivity with at least one of the alkyd resin and the amine-based resin, at least one of the alkyd resin and the amine-based resin reacts with the silicone resin to form a chemical bond in the release layer. The resulting structure can improve peelability and inhibit the transfer of polysilicon to the insulating layer.

Examples of the remaining unsubstituted or substituted alkyl group other than the above-mentioned organic group include a linear alkyl group or a branched alkyl group 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 an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, second butyl, third butyl, and octyl; or a carbon atom with such a group One or all of the hydrogen atoms of the bond are replaced by halogen atoms such as fluorine, chlorine, bromine and iodine, chloromethyl, trifluoropropyl, cyanoethyl, etc. Alkyl and the like. From the viewpoint of obtaining higher releasability, a methyl group is preferred.

The resin composition for a release layer used in the present invention can be formulated with a surfactant.

The surfactant in the present invention means a substance which is used to adjust an interface phenomenon and exhibits surface activity even at a low concentration. As the surfactant, an anionic anionic surfactant having a main agent as an anion, a cationic surfactant having a main body of a cation, an amphoteric amphoteric surfactant having a main body, and a nonionic non-dissociating agent The surfactant is preferably a cationic surfactant having antistatic properties from the viewpoint of efficacy.

Examples of the cationic surfactant include fourth-order ammonium salts, third-order ammonium salts, and ammonium quaternary ammonium salts. In order to further improve the antistatic effect, a grade 4 ammonium salt is preferred. Examples of the fourth-order ammonium salt include an alkyltrimethylammonium salt, a dialkyldimethylammonium salt, a tetraalkylammonium salt, an alkyldimethylbenzylammonium salt, an alkylpyridinium salt, and an alkane Morpholinium salt, alkylimidazolinium salt, ammonium ammonium salt, 5,5,7,7-tetramethyl-2-octenylmethylammonium chloride, quaternary ammonium of polyethyleneimine Salt, benzyltris (dimethylamino) phosphonium chloride, cetyltris (dimethylamino) phosphonium chloride.

The amount of the cationic surfactant is 0.05 to 10 parts by mass based on 100 parts by mass of the composition composed of the alkyd resin (A), the amine resin (B), and the polysiloxane resin (C). It is preferably 0.1 to 5 parts by mass. When the addition amount is 0.05 parts by mass or more, there is a tendency that good antistatic performance is obtained. Moreover, when the addition amount is 10 parts by mass, good coating film hardenability can be obtained, and there is a tendency that the decrease in peelability is suppressed. In addition, in the present invention, in addition to the cationic surfactant within the range exhibiting the effects of the present invention, anions can also be used in combination. Ionic surfactants, non-ionic surfactants, amphoteric surfactants. Examples of the anionic surfactant include alkyl phosphates, alkyl sulfonates, and alkylbenzene sulfonates. Examples of the nonionic surfactant include glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene alkylamine fatty acid ester, and N-hydroxyethyl-N-2. -Hydroxyalkylamine, alkyldiethanolamine and the like. Examples of the amphoteric surfactant include alkyl betaine, alkyl imidazolinium salt betaine, and the like. Various commercially available products can be used as the cationic surfactant, nonionic surfactant, anionic surfactant, and amphoteric surfactant.

In the present invention, the resin composition for a release layer may contain an acid catalyst. This acidic catalyst functions as a catalyst which reacts the said alkyd resin (A) and an amine resin (B). By using an acidic catalyst, low-temperature coating is possible, and productivity is improved. Examples of the acidic catalyst include p-toluenesulfonic acid, oxalic acid, and phosphoric acid.

The purpose of introducing a silicone resin (C) containing a functional group reactive with at least one of the alkyd resin (A) and the amine resin (B) into the resin composition for a release layer is to adjust the releasability. . Moreover, when a silicone resin is not introduced, the coating property when forming an adhesive layer on a release layer is good.

Further, a resin composition containing a polysiloxane resin is commercially available, and the polysiloxane resin has a compound obtained by reacting the alkyd resin (A), the amine-based resin (B), and the alkyd resin with the amine-based resin. A reactive functional group (hereinafter, this resin composition is also referred to as a polysiloxane-containing amino alkyd resin). For example, trade names: Tesfine 319, TA31-209E, etc. manufactured by Hitachi Chemical Polymer Co., Ltd. may be mentioned.

In addition, a resin composition containing an alkyd resin and an amine-based resin (hereinafter also referred to as a non-polysiloxane-based amine-based alkyd resin) is also commercially available. For example, trade names of Tesfine 303 and Tesfine 305 manufactured by Hitachi Chemical Polymer Co., Ltd. may be mentioned.

The resin composition for a release layer is preferably in a state finally formed into a varnish (hereinafter also referred to as a resin varnish for a release layer) in which each component is dissolved or dispersed in an organic solvent.

Examples of the organic solvent used in the production of varnish include alcohol-based solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, and methyl isobutyl Ketones such as ketones and cyclohexanone; ester solvents such as butyl acetate, propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, mesitylene; dimethylformamidine Solvents containing nitrogen atoms, such as amines, N, N-dimethylformamidine, and N-methylpyrrolidone; Solvents containing sulfur atoms, such as dimethylsulfinium. These can be used alone or in combination of two or more.

Among these, for example, from the viewpoints of solubility and appearance at the time of coating, an aromatic solvent and a ketone solvent are preferred, and a mixed solvent of toluene and methyl ethyl ketone (MEK) is more preferred.

The content (solid content concentration) of the resin composition in the varnish finally obtained may be, for example, 1 to 40% by mass of the entire varnish, and 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, the film thickness at the time of coating can be easily controlled.

Moreover, a slip agent, an antistatic agent, etc. may be added to the mold release layer, that is, to the resin composition for a mold release layer as needed. Normally during the hot pressing step Static electricity is often generated, so it is preferable to add an antistatic agent. In addition, an antistatic layer can also be formed by coating on the surface on which the release layer is not formed.

Examples of a method for forming a release layer having a desired thickness on at least one side of the polyimide film include a method of using a reverse roll coater on the polyimide film. ), Gravure coater, rod coater, air doctor blade coater, etc., and then, for example, drying at 50 ° C to 200 ° C for 10 seconds to 600 seconds .

(Adhesive layer)

The polyimide release film of the present invention may have an adhesive layer on the side of the release layer on which the polyimide film is not provided.

The adhesive layer is preferably formed on a release layer by using a resin composition (hereinafter also referred to as a resin composition for an adhesive layer) containing an epoxy resin and an epoxy resin hardener. Epoxy resins are preferred because they are excellent in heat resistance and alkali resistance. The resin composition "containing epoxy resin and epoxy resin hardener" may contain epoxy resin and epoxy resin hardener in an unreacted state, and may also contain epoxy resin and ring in a reaction state. Oxygen resin hardener.

The thickness of the adhesive layer is preferably 0.01 to 10 μm, and more preferably 0.05 to 8 μm. By setting it as this range, a polyimide release film can be removed more easily at the interface of an adhesive layer and a release layer after a hot plate is pressurized.

Here, an "epoxy resin" is an epoxy resin which has two or more epoxy groups in a molecule. Examples of the resin having two epoxy groups in the molecule include a bisphenol A epoxy resin and a bisphenol F epoxy resin. In addition, a polyfunctional epoxy resin having an average of more than two epoxy groups in a molecule may be used.

Examples of the polyfunctional epoxy resin include a biphenylaralkyl epoxy resin, a phenol novolac epoxy resin, a cresol novolac epoxy resin, an aralkyl epoxy resin, and a naphthalene epoxy resin. Resin, naphthol novolak-type epoxy resin, etc. Among them, the polyfunctional epoxy resin is preferably, for example, an aralkyl novolac epoxy resin or a naphthol novolac epoxy resin. From the viewpoint of adhesion with the copper plating layer, the polyfunctional epoxy resin of the adhesive layer is preferably, for example, one having a biphenyl structure.

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

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

Examples of the epoxy resin hardener include polyfunctional phenolic compounds such as phenol novolac and cresol novolac; dicyandiamide, diaminodiphenylmethane, and diaminodiphenylphosphonium. Amine compounds; acid anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride, and maleic anhydride copolymers. These can be used individually by 1 type or in mixture of 2 or more types.

The resin composition for an adhesive layer may be made by containing a hardening accelerator. As the hardening accelerator, for example, various imidazoles, BF ₃ amine complexes, and phosphorus-based hardening accelerators that are latent thermal hardeners can be used.

The blending amount of the hardening accelerator is preferably 0.1 to 5% by mass relative to the blending amount of the epoxy resin.

From the viewpoints of storage stability of the resin composition for an adhesive layer or the handleability and soldering heat resistance of the resin composition for an B-stage (semi-hardened) adhesive layer In particular, imidazoles and phosphorus-based hardening accelerators are preferred.

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-methyl 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-tri Addition reactants of the aforementioned imidazole compounds and trimellitic acid; Addition reactants of the aforementioned imidazole compounds and isotricyanic acid; Addition of the aforementioned imidazole compounds and hydrobromic acid The reaction was; the addition reaction of an imidazole compound with an epoxy resin; the imidazole compound and an addition reaction of the cyanate resin and the like. Among these, 2-phenylimidazole and 2-ethyl-4-methylimidazole are preferable.

The phosphorus-based hardening accelerator is preferably a hardening accelerator that contains a phosphorus atom and can accelerate the hardening reaction of the epoxy resin. For example, a phosphorus-based hardening accelerator may be used alone, or one or two or more other hardening accelerators may be used in combination. Examples of the phosphorus-based hardening accelerator include triphenylphosphine, diphenyl (alkylphenyl) phosphine, gins (alkylphenyl) phosphine, gins (alkoxyphenyl) phosphine, and gins (alkyl- (Alkoxyphenyl) phosphine, gins (dialkylphenyl) phosphine, gins (trialkylphenyl) phosphine, gins (tetraalkylphenyl) phosphine, gins (dialkoxyphenyl) phosphine, ginseng (Trialkoxyphenyl) phosphines, gins (tetraalkoxyphenyl) phosphines, trialkylphosphines, dialkylarylphosphines, alkyldiarylphosphines and other organic phosphines; these organic phosphines Organic boron complexes; tertiary phosphine and quinone adducts.

Furthermore, the resin composition for an adhesive layer of the present invention can be used in accordance with the purpose to use any known inorganic filler, organic filler, thermoplastic resin, flame retardant, ultraviolet absorber, antioxidant, photopolymerization initiator, fluorescent Light whitening agents and adhesion promoters.

Examples of the inorganic filler include silicon dioxide, alumina, talc, mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, nitrogen Boron, calcium carbonate, barium sulfate, aluminum borate, potassium titanate; and glass powder or hollow glass beads of E glass, T glass, D glass, etc. These can be used individually or in mixture of 2 or more types.

The content of the inorganic filler is preferably 10% by mass or less in the resin composition for an adhesive layer. When the blending amount is 10% by mass or less, a good surface shape can be maintained after the roughening treatment, and reduction in plating characteristics and insulation reliability between layers can be prevented.

As the organic filling material, for example: resin particles of a uniform structure, which are composed of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, polysiloxane resin, tetrafluoroethylene resin, etc .; Resin particles having a core layer in a rubber state and a shell layer in a glass state. The core layer is composed of an acrylate resin, a methacrylate resin, a conjugated diene resin, and the like. The shell layer is made of an acrylate resin, a methacrylate resin, an aromatic vinyl resin, a vinyl cyanide resin, or the like.

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 of the resin components.

Examples of the thermoplastic resin include polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, polyimide resin, xylene resin, and petroleum resin. And polysiloxane resin.

Examples of the flame retardant include halogen-containing flame retardants containing bromine or chlorine; triphenyl phosphate, tricresyl phosphate, ginseng (dichloropropyl) phosphate, phosphate compounds, and red phosphorus Combustion agents; nitrogen-based flame retardants such as guanidine sulfamate, melamine sulfate, melamine polyphosphate, and melamine melamine; flame retardants such as cyclophosphazene and polyphosphazene Agent; inorganic flame retardants such as antimony trioxide.

As another ultraviolet absorber, a benzotriazole-type ultraviolet absorber etc. are mentioned, for example. Examples of the antioxidant include hindered phenol-based or hindered amine-based antioxidants. Examples of the photopolymerization initiator include benzophenones, benzyl ketals, and anthracene-based photopolymerization initiators. Examples of the fluorescent whitening agent include stilbene derivatives. Examples of the adhesiveness-improving agent include urea compounds such as urea-silane; coupling agents such as silane-based, titanate-based, and aluminate-based compounds.

The resin composition for an adhesive layer is preferably in a state finally formed into a varnish (hereinafter also referred to as a resin varnish for an adhesive layer) in which each component is dissolved or dispersed in an organic solvent.

Examples of the organic solvent used in the production of varnish include alcohol-based solvents such as methanol, ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, and methyl isobutyl Ketone solvents such as ketones and cyclohexanone; ester solvents such as butyl acetate, propylene glycol monomethyl ether acetate; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, and mesitylene; dimethylformamide Nitrogen, N, N-dimethylacetamide, N-methylpyrrolidone and other nitrogen atom-containing solvents; dimethylsulfinium and other sulfur atom-containing solvents, etc., can be used alone or in combination of two or more Mixed use.

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

Among these, 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 are preferred; dimethylformamide, N , N-dimethylacetamide, N-methylpyrrolidone and other nitrogen atom-containing solvents; ketone solvents and nitrogen atom-containing solvents are mixed solvents.

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

The adhesive layer of the present invention is a resin composition (or a varnish containing the same) for the adhesive layer using a reverse roll coater, a gravure coater, an air blade coater, a die coater, and a lip. A coating device such as a lip coater is applied to the release layer of the polyimide release film, and is obtained by, for example, drying at 80 to 230 ° C. for 30 seconds to 600 seconds.

In the present invention, the polyimide release film is not provided with a release layer. There may be an adhesive layer on the surface, or it may be used in the hot plate pressing step in this state.

By using the polyimide release film of the present invention, the surface flatness of the insulating layer after the hot pressing step can be improved. This surface flatness is the result of observing the surface state of the insulating layer using a high-precision 3-dimensional surface shape roughness measurement system as shown in Figs. 1 and 2 when the copper foil shown in Fig. 2 is used. There are undulations on the surface, but when using the polyfluorene imide release film of the present invention, as shown in FIG. 1, there is almost no undulation. This fluctuation is presumably caused by the difference in thermal expansion rate between the insulating layer with a lower thermal expansion rate and the copper foil with a higher thermal expansion rate during the hot pressing step.

[Laminated boards with polyimide release film with adhesive layer, laminated boards with polyimide release film from laminated board peeled, and polyimide with release layer Thin film single-layer or multilayer wiring board, and manufacturing method of multilayer wiring board]

In the present invention, a laminated board provided with a polyimide release film with an adhesive layer is formed by laminating and forming the polyimide release film with an adhesive layer on the prepreg or insulation layer. Formed on at least one of the faces.

The laminated board provided with a polyimide release film with an adhesive layer according to the present invention can superimpose the polyimide release film with an adhesive layer on the prepreg or insulation so that the adhesive layer becomes the inner side One or both sides of the layer are manufactured by laminating an end plate on the outside and press molding.

In addition, in the laminated board provided with a polyimide release film with an adhesive layer, for example, the polyimide release film with an adhesive layer can be superimposed on the prepreg so that the adhesive layer becomes the inner side. One or both sides of the body or insulation layer are laminated by heating and pressing with a laminator equipped with a heat-resistant rubber sheet, and It is manufactured by heating and hardening the layer.

The heating temperature (temperature of the hot plate) of the pressure molding is preferably set to 150 to 260 ° C. The pressure during pressurization is preferably 0.5 to 10 MPa. The heating temperature of the laminator provided with the heat-resistant rubber sheet is preferably set to 80 to 150 ° C. The pressure during pressurization is preferably 0.3 to 10 MPa.

Either method, after laminating and forming, the polyimide release film can be appropriately peeled to obtain a laminated board.

The aforementioned single-layer or multi-layer circuit board configured with a polyimide release film (polyimide release film with an adhesive layer) is a polyimide release film with an adhesive layer. Adhesive layer side, laminated on one side of the prepreg or insulation layer, and laminated on the other side of the prepreg or insulation layer on the single-layer or multilayer circuit board to be processed by the circuit . The prepreg may be a prepreg before hardening, or may be at least a part of the prepreg after hardening.

Here, "to be processed by a circuit" means a case where a process that can normally be performed when a circuit board is manufactured after circuit processing is performed, and specifically includes a case where a plating process is performed after circuit processing and the like. In addition, a single-layer circuit board refers to a circuit board having one circuit layer when a prepreg or an insulating layer is laminated on only one side, and a case where a prepreg or an insulating layer is laminated on both sides. The surface of the circuit board has one circuit layer (that is, a total of two circuit layers). On the other hand, a multilayer wiring board refers to the following: at least one side of which is processed by a core; and at least one layer of prepreg or insulation layer is laminated on the surface of the core which has been processed by the circuit. Circuit board for circuit processing on prepreg or insulation.

The method for manufacturing a multilayer wiring board of the present invention includes the following steps: By laminating the aforementioned polyfluorene imide release film with an adhesive layer on a single-layer or multi-layer circuit board, a single-layer or multi-layer circuit board equipped with the polyfluorine-imide release film with an adhesive layer is manufactured. A step of removing the polyimide release film from a single-layer or multi-layer circuit board provided with a polyimide release film with an adhesive layer; and a step of performing circuit processing. Here, as a method for producing a polyimide release film with an adhesive layer, it is preferable to include the step of applying an alkyd resin (A) and an amine to one surface of the polyimide film. A step of forming a release layer (polyimide release film manufacturing step) of the release agent composition of the base resin (B); forming an adhesive layer on the surface of the release layer that is not provided with a polyimide film To produce a polyimide release film with an adhesive layer (step of producing a polyimide release film with an adhesive layer).

In the above steps, the manufacturing process of the polyimide release film and the manufacturing process of the polyimide release film with an adhesive layer are as described above.

The following describes the manufacturing steps of a single-layer or multi-layer circuit board equipped with a polyimide release film with an adhesive layer and a polyimide release film removal step.

In addition, after the polyimide release film is removed from a single-layer or multilayer wiring board provided with a polyimide release film with an adhesive layer, the adhesive layer functions as an insulating layer of the multilayer circuit board.

In the manufacturing process of a single-layer or multi-layer circuit board equipped with a polyimide release film with an adhesive layer, for example, first, a polyimide release film of the present invention with an adhesive layer formed is used to The adhesive layer is superposed on the prepreg or the insulating layer in such a way that it becomes the inner side, and then this is superposed on one or both sides of the circuit board to be processed by the circuit. An end plate is further stacked on the outside and press-molded. By removing the end plate, one side or both sides are provided with the polyimide removal of the present invention. Single-layer or multi-layer circuit board of mold film. After that, the polyimide release film of the present invention is peeled and removed (polyimide release film removal step), and a multilayer circuit board is obtained through a step of performing circuit processing.

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

In addition, if necessary, the polyimide release film may be removed by performing a drilling process and laser processing from the upper surface of the polyimide film before peeling (polyimide release film removal step). By performing a hole-cutting process from the top surface of the polyimide film, the resin scattering during processing can be prevented, and the yield can be significantly improved.

Here, the materials for the prepreg and the insulating layer used in the method for manufacturing the multilayer wiring board of the present invention are not particularly limited, and generally used materials can be applied. For example, a mixture of a polyfunctional epoxy resin, an epoxy resin hardener, a hardening accelerator, a solvent, and an inorganic filler as required may be used as a material for the insulating layer, and the material may be further impregnated or coated with the material. A prepreg obtained by laminating glass cloth. As the prepreg, a commercially available product may be used. As the commercially available product, for example, trade names manufactured by Hitachi Chemical Co., Ltd .: GEA-67N, GEA-679F, GEA-679GT, GEA-700G, and the like.

The inner-layer circuit board in the single-layer circuit board or the multilayer circuit board to be processed by the circuit is, for example, an inner-layer substrate having a first circuit layer (inner-layer circuit) formed on the surface. As the inner-layer substrate, a general circuit can be used. There are no particular restrictions on the known laminated boards used for the board, such as glass cloth-epoxy, paper-phenol resin, paper-epoxy, glass cloth, or cellophane-epoxy. also, Can also be used: BT substrates impregnated with bis-cis- butene diimide-triazine resin; and polyimide film substrates obtained using polyimide films as substrates.

The method of forming the circuit is not particularly limited. For example, a known circuit formation method such as a semi-additive method for forming a circuit by a plating process, and an additive method for forming a circuit by electroless plating at a desired portion of an insulating substrate can be adopted.

In the case of using the plating process to perform circuit processing on the laminated layer of the present invention or the adhesive layer of a single-layer or multi-layer circuit board, roughening treatment is performed first. As the roughening solution in this case, for example, an oxidizing roughening solution such as a chromium / sulfuric acid roughening solution, an alkaline permanganic acid roughening solution, a sodium fluoride / chromium / sulfuric acid roughening solution, or a fluoroboric acid roughening solution can be used. As the roughening treatment, for example, there are the following methods: First, an aqueous solution of diethylene glycol monobutyl ether and NaOH as a swelling liquid is heated to 70 ° C, and then the laminated board or a single-layer or multilayer wiring board is impregnated. Process for 5 minutes. Next, an aqueous solution of KMnO ₄ and NaOH as a roughening solution was heated to 80 ° C., and then subjected to an immersion treatment for 10 minutes. Next, in a neutralizing solution, for example, in a hydrochloric acid aqueous solution of stannous chloride (SnCl ₂ ), immersion treatment is performed at room temperature for 5 minutes to neutralize.

After the roughening treatment is performed, a plating catalyst supply treatment for attaching palladium is performed. The plating catalyst treatment is performed by immersion in a palladium chloride-based plating catalyst liquid. Next, it is immersed in an electroless plating solution to perform an electroless plating treatment, so that an electroless plated layer (conductor layer) having a thickness of 0.3 to 1.5 μm is deposited on the entire surface of the primer layer for the plating process.

Next, after forming an anti-plating layer, an electroplating process is performed to form a desired portion. The desired thickness of the circuit. The electroless plating solution used for the electroless plating treatment may be a known electroless plating solution, and is not particularly limited. The plating layer may be a known plating layer and is not particularly limited. Moreover, a well-known method can also be used for electroplating process, and there is no restriction | limiting in particular. These platings are preferably copper plating. The electroless plating layer at an unnecessary portion can be further removed by etching to form an outer layer circuit.

The surface of the circuit layer may be subjected to surface treatment to make it suitable for adhesiveness as required, and this method is not particularly limited. For example, a known manufacturing method can be used in which needle-shaped crystals of copper oxide are formed on the surface of the circuit layer 1 with an alkaline aqueous solution of sodium hypochlorite, and the needle-shaped crystals of the formed copper oxide are immersed in dimethylamine borane. In aqueous solution.

Hereinafter, the same steps can be repeated to produce a multilayer wiring board with a large number of layers.

[Example]

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

[Preparation of resin varnish for adhesive layer]

(Preparation Example 1)

Add 27.5 g of cresol novolac epoxy resin (manufactured by Shin Nippon Epoxy Co., Ltd., trade name: YDCN-700-10) to a phenol aralkyl resin (manufactured by Mitsui Chemicals Co., Ltd., trade name: XLC -LL) 22.5 g, and then 850 g of cyclohexanone was added and kneaded. Here, 100 g of acrylic rubber (manufactured by Nagase Chemtex Co., Ltd., trade name: HTR-860P-3, weight average molecular weight 800,000, glass transition point: 13 ° C.) was added, and 1-cyanoethyl- 2-phenylimidazole (Shikoku Chemical 0.25 g (trade name: Curezol 2PZ-CN) manufactured by Industrial Co., Ltd., and stirred to obtain a resin varnish A (solid content concentration of about 15% by mass) for the adhesive layer.

(Preparation Example 2)

To 18 g of polyammonium (manufactured by Nippon Kayaku Co., Ltd., trade name: BPAM-155), 159 g of N, N-dimethylacetamide (DMAc) was blended, and then a biphenylaralkyl-based epoxy was added. Resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000H) 50 g, bisphenol A novolac phenol resin (manufactured by Mitsubishi Chemical Corporation, trade name: YLH129) 20 g, and 2-benzene as a hardening accelerator is further added. 0.5 g of imidazole (manufactured by Shikoku Chemical Industry Co., Ltd., trade name: 2PZ), diluted with a mixed solvent composed of DMAc and methyl ethyl ketone, and then added an alumina filler (manufactured by CI Kasei Corporation, trade name: NanoTek ) 5 g, using a disperser (manufactured by Yoshida Machinery Industrial Co., Ltd., trade name: Nanomizer) to obtain a resin varnish B (solid content concentration of about 25% by mass) for the adhesive layer.

[Preparation of resin varnish for release layer]

(Preparation Example 3)

To 31.5 g of non-silicone amino alkyd resin [trade name Tesfine 303, manufactured by Hitachi Chemical Co., Ltd., solid content 48.7%], p-toluenesulfonic acid [trade name Dryer 900, Manufactured by Hitachi Chemical Polymer Co., Ltd., solid content 50%] 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)

In 31.5 g of non-silicone amino alkyd resin [trade name Tesfine 305, manufactured by Hitachi Chemical Co., Ltd., solid content 48.7%], 1.5 g of p-toluenesulfonic acid [trade name: Dryer 900, manufactured by Hitachi Chemical Co., Ltd., 50% solid content] was prepared as an acidic catalyst, 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 polysiloxane-containing amino alkyd resin [Tesfine 319, manufactured by Hitachi Chemical Co., Ltd., solid content 48.7%], p-toluenesulfonic acid [trade name: Dryer 900, Hitachi Chemical Co., Ltd.] was prepared as an acid catalyst. Polymer Co., Ltd., solid content 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)

Polyacrylic acid-containing amino alkyd resin [trade name TA31-209E, manufactured by Hitachi Chemical Co., Ltd., solid content 48.7%], 31.5 g of p-toluenesulfonic acid [trade name Dryer 900 as an acid catalyst] , Manufactured by Hitachi Chemical Co., Ltd., 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)

． Polyimide release film with adhesive layer:

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

Preparation example of coating on the release layer of the obtained polyimide release film 1. The prepared resin varnish A for the adhesive layer was dried at 140 ° C. for 5 minutes to form an adhesive layer having a thickness of 5 μm, to obtain a polyimide release film with an adhesive layer.

． Laminated boards:

Four pieces of prepreg (manufactured by Hitachi Chemical Co., Ltd. under the trade name of GEA-700G, 0.10 mm thick) were stacked, and the above polyimide release film with an adhesive layer was superposed on the top and bottom of the polyimide film. It turned to the outer side, and then an end plate and a buffer paper were superimposed, and heat-cured at 3.0 MPa and 240 ° C. for 1 hour using a press to obtain a laminated board.

(Example 2)

Except that Kapton 100H (trade name) manufactured by Toray DuPont Co., Ltd. having a thickness of 25 μm and a surface roughness Ra of less than 0.05 μm was used as the polyimide film, a polyfluorene with an adhesive layer was obtained in the same manner as in Example 1. Imine release film and laminated board.

(Example 3)

Except that the resin varnish B for the release layer prepared in Preparation Example 4 was used as the release layer and the resin varnish B for the adhesive layer prepared in Preparation Example 2 was used as the adhesive layer, the rest was obtained in the same manner as in Example 1. Polyimide release film and laminated board.

(Example 4)

Except that the resin varnish C for the release layer prepared in Preparation Example 5 was used as the release layer, and the resin varnish B for the adhesive layer prepared in Preparation Example 2 was used as the adhesive layer, the rest was obtained in the same manner as in Example 1. Polyimide release film and laminated board.

(Example 5)

Except that the resin varnish D for the release layer prepared in Preparation Example 6 was used as the release layer, and the resin varnish B for the adhesive layer prepared in Preparation Example 2 was used as the adhesive layer, the rest was obtained in the same manner as in Example 1. Polyimide release film and laminated board.

(Comparative example 1)

Except for using a polyethylene terephthalate film with a release layer (trade name Unipeel TR1, manufactured by Unitika Co., Ltd., 38 μm thick) instead of the polyimide film with a release layer, the rest are the same as in the examples. 1 Similarly, a release film and a laminated board with an adhesive layer were obtained.

(Comparative example 2)

Except that no release layer was formed on the polyimide film, as in Example 1, an adhesive layer was formed on the surface of the polyimide film by coating to obtain a release film and a laminated board with the adhesive layer.

(Comparative example 3)

Except for using electrolytic copper foil (manufactured by Furukawa Circuit Foil Co., Ltd., trade name: GTS-18, thickness: 18 μm) instead of the polyimide release film, and applying an adhesive layer on the glossy surface, the procedure was the same as in Example 1. A laminated board was obtained.

(Comparative Example 4)

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

Regarding the laminated board produced as described above, the film peelability after pressurization And the peelable laminated board which can be easily peeled off, the surface roughness, non-transferability, and surface flatness of the insulating layer (adhesive layer after heat curing) were measured in the following manner. The results are shown in Tables 1 and 2 below.

[Peelability after pressing]

After pressing, it was confirmed whether the film can be peeled independently without deformation, welding, or cracking of the release film. Furthermore, it was visually confirmed whether the release film was peelable at the interface with the release layer after peeling the release film from the laminated sample after pressing.

A: It can be easily peeled at the interface.

C: It cannot be easily peeled at the interface.

"Easy peeling at the interface" refers to the case where the film cannot be peeled individually, or the resin composition of the adhesive layer after the peeling is attached to the release film.

〔Surface roughness〕

The surface roughness of the insulating layer after pressing and peeling the film was measured using a surface shape measuring device (manufactured by Veeco, trade name: Wyko NT9100) under the following measurement conditions.

-Measurement conditions-

Internal lens: 1x

External lens: 50 times

Measurement range: 0.125 × 0.095mm

Measurement depth: 10μm

Measurement method: vertical scanning type interference method (VSI method)

[No transferability]

After the polyimide film was peeled from the pressurized laminated board, Magic Ink (registered trademark) No. 500 (black) manufactured by Sisai Chemical Industry Co., Ltd. was coated on the insulating layer, and repellency of the ink was observed. )situation. The phenomenon of ink repulsion indicates that the components of the release layer are transferred to the insulating layer, so the repellent evaluated it as "C" and the non-repellent evaluated it as "A".

〔Surface flatness〕

A high-precision 3-dimensional surface shape and roughness measuring system (manufactured by Veeco, trade name WYKO NT9100) was used to observe the surface shape of the insulating layer after pressing. The first and second figures show the results of surface observation on a shape range of X-axis: 125 μm and Y-axis: 95 μm.

As can be seen from Table 1, the properties of the polyfluorene imide release film and the laminated board with an adhesive layer of the present invention are as shown in Examples 1 to 5, and it can be easily pressed at a high temperature of 240 ° C on a hot plate. The polyimide release film was peeled to obtain an insulating layer having a flat surface.

On the other hand, as can be seen from Table 2, in Comparative Example 1, since a film other than a polyimide film was used, the polyethylene terephthalate film was welded. In the end plate, it was confirmed that the release film could not be easily peeled individually, and an insulating layer having a good surface condition could not be obtained. Furthermore, in Comparative Example 2, the polyimide film was cracked, and it was confirmed that the polyimide film could not be separated alone. In Comparative Example 3, the copper foil was cracked, and it was confirmed that the copper foil could not be separated individually. In Comparative Example 4, when Magic Ink was applied to the insulating layer, ink repellency was observed, and it was confirmed that the release layer component was transferred 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. 2. From these drawings, it can be confirmed that the use of the first The insulating layer of the polyimide release film of the present invention has a flat surface.

[Industrial availability]

The polyimide release film of the present invention can be effectively used as a release film when a multilayer wiring board is manufactured by a forming method using a hot plate press, a roll laminator, a double press, or the like.

Claims (10)

A polyimide release film having a release layer on at least one side of the polyimide film, the release layer comprising an alkyd resin (A) and an amine-based resin (B), wherein An adhesive layer is provided on the surface of the release layer on which the polyimide film is not provided. The polyimide release film according to claim 1, wherein the thickness of the release layer is 0.01 to 10 μm. The polyimide release film according to claim 1 or 2, wherein the thickness of the polyimide film is 10 to 100 μm. The polyimide release film according to claim 1 or 2, wherein a surface roughness (Ra) of a surface of the polyimide film on one side of the release layer to be formed is 0.2 μm or less. The polyimide release film according to claim 1 or 2, wherein the ratio (A / B) of the alkyd resin (A) to the amine-based resin (B) is calculated as a solid content mass ratio. 95/5 ~ 10/90. The polyimide release film according to claim 1, wherein the adhesive layer is made of a resin composition containing an epoxy resin and an epoxy resin hardener. A laminated board provided with a polyimide release film with an adhesive layer is formed by laminating and forming the polyimide release film as described in claim 1 or 6 on a prepreg or The insulating layer is formed on at least one side. A laminated board is obtained by peeling a polyimide release film of the laminated board according to claim 7. A single-layer or multi-layer circuit board provided with a polyimide release film with an adhesive layer, which is a layer of a polyimide release film as described in claim 1 or 6 laminated on a pre-impregnated layer. One side of the body or insulating layer, and the other side of the prepreg or the insulating layer are laminated on a single-layer or multi-layer circuit board to be processed by a circuit. A method for manufacturing a multilayer wiring board, the method comprising the steps of: manufacturing and disposing a laminate by laminating a polyimide release film according to claim 1 or 6 on a single-layer or multilayer wiring board; Step of single-layer or multilayer circuit board of polyimide release film with adhesive layer; removal of polyimide release film by single-layer or multi-layer circuit board equipped with polyimide release film with adhesive layer Steps; and, steps for performing circuit processing.