JP2009226658A - Laminated film, surface-treated polyimide film used in laminated film, and method of treating surface of polyimide film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide film whose adhesiveness to an adhesive layer is improved by using a surface-treating agent safer than sodium and potassium hydroxides extremely stimulative to the skin, and a method of treating the surface of the polyimide film. <P>SOLUTION: A laminated film is composed of the polyimide film and the adhesive layer which are laminated on each other. The surface of the polyimide film on which the adhesive layer is laminated is treated by a solution containing a silicate compound. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is a laminated film obtained by laminating a polyimide film surface-treated with a silicate solution and an adhesive layer, the laminated film having good adhesion strength between the polyimide film and the adhesive layer, and these laminated films. The present invention relates to a polyimide film surface-treated with a silicate solution and a surface treatment method for a polyimide film excellent in adhesiveness with an adhesive layer.

Polyimide films are excellent in heat resistance and insulation, and are used as substrate materials for various wiring boards.
A laminated film obtained by laminating an adhesive layer on a polyimide film is used as a lead frame fixing tape, an interlayer adhesive sheet for a multilayer board, and an insulating cover material for a wiring board.
A copper foil laminated polyimide film in which a polyimide film and a copper foil are laminated via an adhesive layer is used as a wiring substrate or base substrate such as TAB, FPC, or COF.

For the purpose of modifying the adhesiveness of the polyimide film surface, a method using a high-concentration alkaline aqueous solution or a hydrazine solution, a method of etching using a gas, and the like are disclosed.
Patent Document 1 discloses a first aromatic polyamic acid solution obtained from an aromatic tetracarboxylic acid component having two benzene rings and an aromatic diamine component, and an aromatic tetracarboxylic acid component having one benzene ring. The second aromatic polyamic acid solution obtained from the diamine component and the aromatic diamine component is mixed at a ratio of 9: 1 to 6: 4 by weight ratio of the aromatic polyamic acid to form a cast / thin film imide. A method for producing a roughened polyimide film is disclosed, wherein the roughened film is treated with an alkaline solution.
Patent Document 2 discloses a polyimide film that is bonded with a polyimide-based adhesive and that is surface-treated with an alkaline aqueous solution containing a permanganate.
In Patent Document 3, as a pretreatment for performing electroless plating on an object to be plated having a polyimide resin, the object to be plated is added to an aqueous solution containing one or more alkali metal compounds and one or more primary amino alcohols. An electroless plating method characterized by performing electroless plating including a dipping process, a degreasing process, a catalyst applying process, and a catalyst activation process is disclosed, and a silicate compound is described as an alkali metal compound .
JP-A-6-313055 JP 2007-9186 A JP-A-2005-120407

Conventionally, surface modification of a polyimide film that improves the adhesion to an adhesive layer has been performed using a strong alkaline aqueous solution of sodium hydroxide or potassium hydroxide. Therefore, the present invention provides a polyimide film with improved adhesion to an adhesive layer using a surface treatment agent that is safer than sodium hydroxide or potassium hydroxide, which is highly irritating to the skin, and a surface treatment method thereof. With the goal.
In particular, a thin polyimide film continuously manufactured by a casting method is difficult to obtain a film having high adhesiveness with an adhesive layer, and improvement in adhesiveness is required. An object of the present invention is to provide a thin polyimide film with improved adhesion to an adhesive layer using a safe surface treating agent and a surface treating method thereof.
It aims at providing the laminated | multilayer film which laminated | stacked the polyimide film and adhesive layer which improved the adhesiveness with the adhesive layer surface-treated by the surface treatment method.

The first of the present invention is a laminated film in which a polyimide film and an adhesive layer are laminated,
The present invention relates to a laminated film characterized in that a polyimide film on the side of laminating an adhesive layer is surface-treated with a silicate compound-containing solution.
2nd of this invention is related with the polyimide film surface-treated with the silicate compound containing solution used for the 1st laminated film of this invention.
3rd of this invention is related with the laminated film characterized by further laminating | stacking the metal layer or the resin layer on the adhesive bond layer of the 1st laminated film of this invention.
Furthermore, the fourth of the present invention is a surface treatment method of a polyimide film used for lamination with an adhesive layer,
The polyimide film surface on the side where the adhesive layer is laminated is immersed in a silicate-containing solution, and the silicate-containing solution is applied, sprayed or sprayed on the surface of the polyimide film on which the adhesive layer is laminated. The present invention relates to a surface treatment method for a polyimide film.

The first to fourth preferred embodiments of the present invention will be described below. A plurality of these aspects can be arbitrarily combined.
1) The silicate is metasilicate.
2) The adhesive layer contains an epoxy resin or an acrylic resin.
3) The polyimide film is a polyimide film obtained from an acid component containing a biphenyltetracarboxylic acid component and a diamine component containing p-phenylenediamine.
4) The thickness of the polyimide film is 3 to 30 μm, and the polyimide film is continuously formed with a thickness of 3 to 30 μm.

According to the present invention, a polyimide film surface can be modified by a safe and simple method to obtain a polyimide film having excellent adhesiveness with an adhesive layer, and a laminate having excellent adhesion between the polyimide film and the adhesive layer. A film can be obtained.
The laminated film of the present invention can be produced using a thin polyimide film such as a continuously produced thin polyimide film.
The polyimide film surface treatment method of the present invention can modify the polyimide film surface to obtain a polyimide film excellent in adhesiveness with an adhesive layer, and can also be applied to a thin polyimide film.

The laminated film of the present invention is a laminated film in which a polyimide film and an adhesive layer are directly laminated,
The polyimide film on the side on which the adhesive layer is laminated is surface-treated with a silicate compound-containing solution.

The polyimide film can be produced by a known method from a tetracarboxylic acid component and a diamine through a polyimide or a polyimide precursor.
As an example of the manufacturing method of polyimide film,
1) A method of producing a polyimide solution from a tetracarboxylic acid component and a diamine, casting it, and removing the solvent;
2) A method of producing a polyimide solution from a tetracarboxylic acid component and a diamine, casting it, and removing the solvent and heating simultaneously or sequentially,
3) A method of producing a polyimide precursor solution such as polyamic acid, casting it, and then removing the solvent and chemically or thermally imidizing,
4) A polyimide precursor solution such as polyamic acid can be produced, cast, and then the solvent is removed and chemically or thermally imidized simultaneously or sequentially.

（但し、一般式（１）において、Ｙは一般式（２）で示す群から選択された２価の基を示す。）

（但し、一般式（２）において、Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、単結合、−Ｏ−，−Ｓ−，−ＣＯ−，−ＳＯ_２−，−ＣＨ_２−，−Ｃ（ＣＨ_３）_２−及び−Ｃ（ＣＦ_３）_２−から選ばれる２価の基を示し、
Ｍ_１〜Ｍ_４、Ｍ’_１〜Ｍ’_４、Ｌ_１〜Ｌ_４、Ｌ’_１〜Ｌ’_４及びＬ”_１〜Ｌ”_４は、−Ｈ，−Ｆ，−Ｃｌ，−Ｂｒ，−Ｉ，−ＣＮ，−ＯＣＨ_３，−ＯＨ，−ＣＯＯＨ，−ＣＨ_３，−Ｃ_２Ｈ_５または−ＣＦ_３を示す。
Ｒ_２、Ｒ_３、Ｒ_４及びＲ_５は、それぞれ独立して、同一であっても、異なっていてもよく、
Ｍ_１〜Ｍ_４、Ｍ’_１〜Ｍ’_４、Ｌ_１〜Ｌ_４、Ｌ’_１〜Ｌ’_４及びＬ”_１〜Ｌ”_４は、それぞれ独立して、同一であっても、異なっていてもよい。）
中でも、好ましいジアミンとしては、下記一般式（１’）で表されるものが挙げられ、さらに好ましいジアミンとしては、下記一般式（１”）で表されるものが挙げられる。

（但し、一般式（１’）において、Ｙは一般式（２’）で示す群から選択された２価の基を示す。）

（但し、一般式（２’）において、Ｒ_２は、単結合、−Ｏ−、−Ｓ−、−ＣＨ_２−及び−Ｃ（ＣＨ_３）_２−から選ばれる２価の基を示し、
Ｒ_３は、−Ｏ−または−Ｓ−を示し、
Ｍ_１〜Ｍ_４、Ｍ’_１〜Ｍ’_４、Ｌ_１〜Ｌ_４、Ｌ’_１〜Ｌ’_４及びＬ”_１〜Ｌ”_４は、−Ｈまたは−ＣＨ_３を示す。
Ｒ_２及びＲ_３は、それぞれ独立して、同一であっても、異なっていてもよく、
Ｍ_１〜Ｍ_４、Ｍ’_１〜Ｍ’_４、Ｌ_１〜Ｌ_４、Ｌ’_１〜Ｌ’_４及びＬ”_１〜Ｌ”_４は、それぞれ独立して、同一であっても、異なっていてもよい。）

（但し、一般式（１”）において、Ｙは一般式（２”）で示す群から選択された２価の基を示す。）

（但し、一般式（２”）において、Ｒ_２は、単結合、−Ｏ−、−Ｓ−、−ＣＨ_２−及び−Ｃ（ＣＨ_３）_２−から選ばれる２価の基を示し、
Ｍ_１〜Ｍ_４及びＭ’_１〜Ｍ’_４は、−Ｈ、−ＯＣＨ_３、−ＣＨ_３または−Ｃｌを示す。
Ｍ_１〜Ｍ_４及びＭ’_１〜Ｍ’_４は、それぞれ独立して、同一であっても、異なっていてもよい。）
ジアミンは、一般式（１）に示すジアミン、好ましくは一般式（１’）に示すジアミン、さらに好ましくは一般式（１”）に示すジアミンが主成分として用いられ、一般式（１）に示すジアミン、好ましくは一般式（１’）に示すジアミン、さらに好ましくは一般式（１”）に示すジアミンを５０モル％以上、さらに好ましくは７０モル％以上、より好ましくは８０モル％以上、特に好ましくは９０モル％以上含むものを用いることが好ましい。 The diamine is preferably an aromatic diamine, preferably an aromatic diamine having 1 to 3 benzene rings, and more preferably an aromatic diamine having 1 to 2 benzene rings.
Examples of the diamine include those represented by the following general formula (1).

(However, in General Formula (1), Y represents a divalent group selected from the group represented by General Formula (2).)

(However, in the general formula _{(2), R 2, R} 3, R 4 and _{R 5} is a single bond, -O -, - S -, - CO -, - SO 2 -, - CH 2 -, - C A divalent group selected from (CH ₃ ) ₂ — and —C (CF ₃ ) ₂ —;
M _{1 to} M ₄ , M ′ _{1 to} M ′ ₄ , L _{1 to} L ₄ , L ′ _{1 to} L ′ ₄ and L ″ _{1 to} L ″ ₄ are represented by —H, —F, —Cl, —Br, — shows _{I, -CN, -OCH 3, -OH} , -COOH, a -CH 3, _-C 2 _{H 5} or -CF _3.
R ₂ , R ₃ , R ₄ and R ₅ may each independently be the same or different,
M _{1 to} M ₄ , M ′ _{1 to} M ′ ₄ , L _{1 to} L ₄ , L ′ _{1 to} L ′ ₄ and L ″ _{1 to} L ″ ₄ are each independently the same or different. May be. )
Among them, preferred diamines include those represented by the following general formula (1 ′), and more preferred diamines include those represented by the following general formula (1 ″).

(However, in General Formula (1 ′), Y represents a divalent group selected from the group represented by General Formula (2 ′).)

(However, in General Formula (2 ′), R ₂ represents a divalent group selected from a single bond, —O—, —S—, —CH ₂ —, and —C (CH ₃ ) ₂ —;
R ₃ represents —O— or —S—,
M _{1 to} M ₄ , M ′ _{1 to} M ′ ₄ , L _{1 to} L ₄ , L ′ _{1 to} L ′ ₄ and L ″ _{1 to} L ″ ₄ represent —H or —CH ₃ .
R ₂ and R ₃ may each independently be the same or different,
M _{1 to} M ₄ , M ′ _{1 to} M ′ ₄ , L _{1 to} L ₄ , L ′ _{1 to} L ′ ₄ and L ″ _{1 to} L ″ ₄ are each independently the same or different. May be. )

(In the general formula (1 ″), Y represents a divalent group selected from the group represented by the general formula (2 ″).)

(In the general formula (2 ″), R ₂ represents a divalent group selected from a single bond, —O—, —S—, —CH ₂ —, and —C (CH ₃ ) ₂ —;
M _{1 to} M ₄ and M ′ _{1 to} M ′ ₄ represent —H, —OCH ₃ , —CH ₃ or —Cl.
M _{1 to} M ₄ and M ′ _{1 to} M ′ ₄ may independently be the same or different. )
As the diamine, a diamine represented by the general formula (1), preferably a diamine represented by the general formula (1 ′), more preferably a diamine represented by the general formula (1 ″) is used as a main component, which is represented by the general formula (1). A diamine, preferably a diamine represented by the general formula (1 ′), more preferably a diamine represented by the general formula (1 ″), is 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably. It is preferable to use those containing 90 mol% or more.

As a specific example of diamine,
1) One diamine nucleus diamine such as 1,4-diaminobenzene, 1,3-diaminobenzene, 2,4-diaminotoluene, 2,6-diaminotoluene,
2) 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-dimethyl-4, 4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4 , 4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, bis (4-aminophenyl) sulfide, 4,4′-diaminobenzanilide, 3,3 ′ -Dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2'-dimethoxybenzidine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,3′-diamino-4,4′-dichlorobenzophenone 3,3′-diamino-4,4′-dimethoxybenzophenone, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 2,2-bis (3-aminophenyl) ) Propane, 2,2-bis (4-aminophenyl) propane, , 2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl) -1,1,1,3,3,3 Two diamine diamines such as hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide,
3) 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-amino) Phenyl) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) -4-trifluoromethylbenzene, 3,3'-diamino-4- (4-phenyl) phenoxybenzophenone, 3,3'-diamino-4,4'-di (4-phenylphenoxy) benzophenone, 1,3-bis (3-aminophenyl sulfide) benzene, 1,3-bis (4-aminophenyl sulfide) benzene, 1,4-bis (4-aminophenyls) Fido) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4-aminophenylsulfone) benzene, 1,3- Bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) isopropyl] benzene, etc. The benzene core of three diamines,
4) 3,3′-bis (3-aminophenoxy) biphenyl, 3,3′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [3- (3-aminophenoxy) phenyl] ether, bis [3- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] ether, Bis [4- (4-aminophenoxy) phenyl] ether, bis [3- (3-aminophenoxy) phenyl] ketone, bis [3- (4-aminophenoxy) phenyl] ketone, bis [4- (3-amino Phenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [3- (3-aminophenoxy) phenyl] Sulfide, bis [3- (4-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [3- (3 -Aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, Bis [3- (3-aminophenoxy) phenyl] methane, bis [3- (4-aminophenoxy) phenyl] methane, bis [4- (3-aminophenoxy) phenyl] methane, bis [4- (4-amino Phenoxy) phenyl] methane, 2,2-bis [3- (3-aminophenoxy) phenyl] propane, , 2-bis [3- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [3- (4-aminophenoxy) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Four diamine diamines such as propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane,
And so on. These may be used alone or in combination of two or more. The diamine to be used can be appropriately selected according to desired characteristics.

（但し、一般式（３）において、Ｘは一般式（４）で示す群から選択された４価の基を示す。）

（但し、一般式（４）において、Ｒ_１は、一般式（５）から選ばれる２価の基を示す。）

中でも、好ましいテトラカルボン酸二無水物としては、下記一般式（３’）で表されるものが挙げられる。

（但し、一般式（３’）において、Ｘは一般式（４’）で示す群から選択された４価の基を示す。）

As the tetracarboxylic acid component, a tetracarboxylic dianhydride from which a polyamic acid that is a polyimide precursor is obtained and an ester compound thereof are preferable.
As tetracarboxylic dianhydride, what is represented by following General formula (3) is mentioned.

(In the general formula (3), X represents a tetravalent group selected from the group represented by the general formula (4).)

(However, in General Formula (4), R ₁ represents a divalent group selected from General Formula (5).)

Among these, preferred tetracarboxylic dianhydrides include those represented by the following general formula (3 ′).

(However, in General Formula (3 ′), X represents a tetravalent group selected from the group represented by General Formula (4 ′).)

The tetracarboxylic dianhydride includes a tetracarboxylic dianhydride represented by the general formula (3), preferably a tetracarboxylic dianhydride represented by the general formula (3 ′) as a main component. A known tetracarboxylic dianhydride other than the tetracarboxylic dianhydride represented by the general formula (3) can be used as long as it is not impaired.
As the tetracarboxylic dianhydride, the tetracarboxylic dianhydride represented by the general formula (3) is 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more. It is preferable to use what is included.

  Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA), 2,3,3 ′, 4 ′. -Biphenyltetracarboxylic dianhydride (a-BPDA), oxydiphthalic dianhydride, diphenylsulfone-3,4,3 ', 4'-tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) Sulfide dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,3 ′, 4′-benzophenone Tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4 Dicarboxyl Nyl) propane dianhydride, p-phenylenebis (trimellitic acid monoester acid anhydride), p-biphenylenebis (trimellitic acid monoester acid anhydride), m-terphenyl-3,4,3 ′, 4 '-Tetracarboxylic dianhydride, p-terphenyl-3,4,3', 4'-tetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) biphenyl dianhydride, 2,2-bis [(3,4-di Carboxyphenoxy) phenyl] propane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4 ′-(2, 2- And the like hexafluorobutene isopropylidene) diphthalic anhydride. It is also preferable to use an aromatic tetracarboxylic acid such as 2,3,3 ', 4'-diphenylsulfonetetracarboxylic acid. These may be used alone or in combination of two or more. The tetracarboxylic dianhydride to be used can be appropriately selected according to desired characteristics.

Above all, the polyimide film
1) 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes simply referred to as BPDA) and paraphenylenediamine (hereinafter sometimes simply referred to as PPD) and optionally. Further, a polyimide produced from a component containing 4,4′-diaminodiphenyl ether (hereinafter sometimes simply referred to as DADE) as a main component (provided that it is 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more of the acid component containing BPDA, 50 mol% or more, more preferably 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol% or more of PPD. A diamine component containing
2) pyromellitic dianhydride (hereinafter sometimes abbreviated simply as PMDA), or an aromatic tetracarboxylic dianhydride that is a combination of BPDA and PMDA, and an aromatic diamine such as benzenediamine or biphenyldiamine. And the main component of the polyimide (provided that the aromatic diamine is paraphenylene diamine, aromatic diamine having a PPD / DADE of 90/10 to 10/90, or tolidine (ortho, meta In this case, BPDA / PMDA is preferably 0/100 to 90/10),
3) A polyimide produced from a component containing pyromellitic dianhydride, paraphenylenediamine and 4,4′-diaminodiphenyl ether as main components (provided that DADE / PPD is 90/10 to 10/90). preferable),
Etc. are preferable.

  The present invention can be applied to commercially available polyimide films having various film thicknesses. Commercially available polyimide films include Ube Industries brand name Upilex (S, SN, R, etc.), Toray DuPont brand names Kapton (H, V, EN, etc.), Kaneka Corporation brand names Apical (HP, NPI, etc.) ).

The polyimide film can be produced by a known method. For example, 1) A polyimide precursor solution such as polyamic acid is cast into a thin film, dried by heating to produce a self-supporting film, and both ends of the self-supporting film. Is fixed using a tenter, etc., then heated, imidized to produce a polyimide film,
2) In the case of polyimide with excellent solvent solubility, a polyimide solution is cast into a thin film, heated and dried, and then fixed on both ends of the film using a tenter as necessary, and then dried by heating to produce a polyimide film. The method of doing, etc. can be mentioned.
If necessary, the polyimide precursor solution or the polyimide solution may contain an imidization catalyst, an organic phosphorus compound, or inorganic fine particles. The organophosphorus compound is useful for peeling from the support.

  The synthesis of the polyimide precursor is achieved by random polymerization or block polymerization of approximately equimolar aromatic tetracarboxylic dianhydride and aromatic diamine in an organic solvent. May also be mixed with the reaction conditions was keep two or more polyimide precursors in which either of these two components is excessive, the respective polyimide precursor solution together. The polyimide precursor solution thus obtained can be used for the production of a self-supporting film as it is or after removing or adding a solvent if necessary.

  The synthesis of the polyimide is achieved by random polymerization or block polymerization of approximately equimolar aromatic tetracarboxylic dianhydride and aromatic diamine in an organic solvent. May also be mixed with the reaction conditions was keep two or more polyimide solution is excessive advance either component, the respective polyimide solution together. The polyimide solution thus obtained can be used in the production of a polyimide film as it is or after removing or adding a solvent if necessary.

  Examples of the organic solvent for the polyimide precursor solution or polyimide solution include amide solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, phenol, o Examples thereof include phenol solvents such as -cresol, m-cresol, p-cresol, and p-chlorophenol. These organic solvents may be used alone or in combination of two or more.

If necessary, an imidization catalyst, a dehydration aid, an organic phosphorus-containing compound, inorganic fine particles, organic fine particles, and the like may be added to the polyimide precursor solution.
If necessary, an organic phosphorus-containing compound, inorganic fine particles, organic fine particles, and the like may be added to the polyimide solution.

  Examples of the imidization catalyst include a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound of the nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, an aromatic hydrocarbon compound having a hydroxyl group, or an aromatic heterocyclic compound. Cyclic compounds such as 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl-4-imidazole, 5-methylbenzimidazole and the like. Imidazole, benzimidazole such as N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-dimethylpyridine, 2,4-dimethylpyridine, 4-n-propyl Suitable use of substituted pyridines such as pyridine It can be. The amount of the imidization catalyst used is preferably about 0.01-2 times equivalent, particularly about 0.02-1 times equivalent to the amic acid unit of the polyamic acid. It is preferable to use an imidization catalyst because the properties of the resulting polyimide film, particularly elongation and end tear resistance, are improved.

  Examples of the organic phosphorus-containing compound include monocaproyl phosphate, monooctyl phosphate, monolauryl phosphate, monomyristyl phosphate, monocetyl phosphate, monostearyl phosphate, triethylene glycol monotridecyl Monophosphate of ether, monophosphate of tetraethylene glycol monolauryl ether, monophosphate of diethylene glycol monostearyl ether, dicaproyl phosphate, dioctyl phosphate, dicapryl phosphate, dilauryl phosphate, dimyristyl phosphate, Dicetyl phosphate, distearyl phosphate, diethylene phosphate of tetraethylene glycol mononeopentyl ether, triethyl Diphosphate of glycol mono tridecyl ether, diphosphate of tetraethyleneglycol monolauryl ether, and phosphoric acid esters such as diphosphate esters of diethylene glycol monostearyl ether, amine salts of these phosphates. As amine, ammonia, monomethylamine, monoethylamine, monopropylamine, monobutylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, monoethanolamine, diethanolamine, triethanolamine Etc.

  Any dehydrating aid may be used as long as it aids dehydration for converting a known polyimide precursor into an imide. For example, pyridine, α-picoline, β-picoline, isoquinoline and the like can be used.

  Inorganic fine particles include fine particle titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, inorganic oxide powder such as zinc oxide powder, fine particle silicon nitride powder, and titanium nitride powder. Inorganic nitride powder such as silicon carbide powder, inorganic carbide powder such as silicon carbide powder, and inorganic salt powder such as particulate calcium carbonate powder, calcium sulfate powder, and barium sulfate powder. These inorganic fine particles may be used in combination of two or more. In order to uniformly disperse these inorganic fine particles, a means known per se can be applied.

The polyimide precursor solution self-supporting film is composed of the polyimide precursor organic solvent solution as described above, or a polyimide precursor solution composition in which an imidization catalyst, a dehydrating aid, an organic phosphorus-containing compound, inorganic fine particles, and the like are added. An object is cast-coated on a support and becomes self-supporting (meaning a stage before a normal curing step), for example, it can be peeled off from the support at a temperature of 100 to 180 ° C., It is preferably produced by heating at 100 to 160 ° C., more preferably 100 to 140 ° C. for 2 to 60 minutes, preferably 2 to 30 minutes, more preferably 2 to 10 minutes, further preferably about 2 to 5 minutes.
The polyimide precursor solution preferably contains about 8 to 30% by mass and about 8 to 25% by mass of the polyimide precursor.

  As the support, it is preferable to use a smooth base material, for example, a stainless steel substrate, a stainless steel belt, or the like.

また、上記の自己支持性フィルムのイミド化率は、ＩＲ（ＡＴＲ）で測定し、フィルムとフルキュア品との振動帯ピーク面積の比を利用して、イミド化率を算出することができる。振動帯ピークとしては、イミドカルボニル基の対称伸縮振動帯やベンゼン環骨格伸縮振動帯などを利用する。またイミド化率測定に関し、特開平９−３１６１９９号公報に記載のカールフィッシャー水分計を用いる手法もある。 The self-supporting film preferably has a loss on heating in the range of 20 to 40% by mass, and further has a loss on heating in the range of 20 to 40% by mass and an imidization rate in the range of 8 to 40%.
The loss on heating of the self-supporting film is a value calculated according to Equation 1 from the weight W1 before drying and the weight W2 after drying after drying the film to be measured at 420 ° C. for 20 minutes.

Moreover, the imidation rate of said self-supporting film can be measured by IR (ATR), and an imidation rate can be calculated using the ratio of the vibration band peak area of a film and a full cure product. As the vibration band peak, a symmetric stretching vibration band of an imidecarbonyl group, a benzene ring skeleton stretching vibration band, or the like is used. Further, regarding the imidization rate measurement, there is also a method using a Karl Fischer moisture meter described in JP-A-9-316199.

  In the present invention, the self-supporting film of the polyimide precursor solution is manufactured by a method using chemical imidization or a combination of thermal imidization and chemical imidization in addition to the thermal imidization described above. Can be used.

In the present invention, a polyimide film can be obtained by heat-treating a self-supporting film or a cast thin film of a polyimide solution.
In the heat treatment, it is appropriate to first gradually perform imidization of the polymer and evaporation / removal of the solvent at a temperature of about 100 to 400 ° C. for about 0.05 to 5 hours, particularly 0.1 to 3 hours. In particular, this heat treatment is a stepwise primary heat treatment at a relatively low temperature of about 100-170 ° C. for about 0.5-30 minutes, and then at a temperature of 170-220 ° C. for about 0.5-30 minutes. It is preferable to perform the second heat treatment, and then the third heat treatment at a high temperature of 220 to 400 ° C. for about 0.5 to 30 minutes. If necessary, the fourth high-temperature heat treatment may be performed at a high temperature of 400 to 550 ° C. Further, in the continuous heat treatment at 250 ° C. or higher, it is preferable to perform the heat treatment with pin tenters, clips, frames, etc., at least fixing both end edges in the direction perpendicular to the longitudinal direction of the long solidified film. The heat treatment can be performed using various known devices such as a hot stove and an infrared heating furnace.

In the present invention, the thickness of the polyimide film is not particularly limited, but the thickness can be 150 μm or less, preferably 3 to 120 μm, particularly 30 μm or less, further 15 μm or less, and further 5 When the present invention is applied to the production of a 10 μm polyimide film, the effects of the present invention can be obtained more remarkably.
In the present invention, the polyimide film can be used after being subjected to a surface treatment such as corona discharge treatment, low-temperature plasma discharge treatment or atmospheric pressure plasma discharge treatment, or chemical etching.

The adhesive layer is not particularly limited as long as it is provided on one or both sides of the polyimide film in an uncured or semi-cured state and can be laminated with a metal foil such as a copper foil to obtain a laminate. Thereafter, those having a chemical structure that is cured (including cross-linking) by a method such as heating, pressing, or ultraviolet rays can be appropriately selected and used.
The adhesive layer is used when mounting a known semiconductor integrated circuit, a tape-like substrate such as TAB or COF, a substrate for connecting a semiconductor member such as an IC, a lead frame fixing tape, an interlayer adhesive sheet of a multilayer substrate, etc. A known adhesive for further laminating a copper foil can be mentioned.
Examples of the adhesive layer include those containing at least one kind of thermosetting resin component selected from epoxy resin, acrylic resin, phenol resin, polyimide resin, maleimide resin, polyamide resin and the like. .
As the adhesive layer, the thickness of the adhesive layer after curing may be appropriately selected depending on the intended use, and is preferably in the range of 5 to 100 μm, more preferably 5 to 50 μm.

The adhesive layer is usually uncured on one or both sides of the polyimide film after coating or spraying the adhesive or adhesive-containing solution on the polyimide film, then removing the solvent, heating or drying, etc. It can be formed in a state or semi-cured state.
In addition, the adhesive layer is usually uncoated on one side of the film after coating or spraying on the protective film from which the adhesive or adhesive-containing solution can be peeled, and then removing the solvent and heating or drying. It can be formed in a cured state or a semi-cured state. Furthermore, the adhesive layer of this protective film and a polyimide film can be laminated | stacked, and the polyimide film with an adhesive layer with a protective film can be obtained.
The protective film only needs to be a film that can be easily peeled off from the adhesive layer, for example, a polyester film subjected to a peeling treatment such as silicone or a fluorine compound, a resin film such as a polyolefin such as polyethylene or polypropylene, a paper that has been further peeled, Nonwoven fabrics can be mentioned.

The epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule.
As the epoxy resin, bisphenol A, bisphenol F, bisphenol S, epoxidized phenol novolak, epoxidized cresol novolak, alicyclic epoxy resin, and the like can be used.

  As acrylic resins, acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, acrylonitrile, acrylic acid, etc. An acrylic resin copolymerized with can be used. An acrylic resin epoxy-modified with an epoxy group-containing acrylate or methacrylate such as glycidyl acrylate or glycidyl methacrylate can be used.

The adhesive layer can be added with a known thermosetting resin curing agent or curing accelerator, if necessary.
A known thermosetting resin curing inhibitor can be added to the adhesive layer as necessary.
To the adhesive layer, organic components such as antioxidants and thermoplastic resins and inorganic components can be added as long as the characteristics of the present invention are not impaired.

Examples of the silicate compound-containing solution include a solution in which a silicate compound is dissolved, an alkali solution, an aqueous solution, or an alkaline aqueous solution.
Examples of the silicic acid compounds include orthosilicic acid and these compounds, metasilicic acid and these compounds or metadisilicic acid and these compounds, or compounds containing two or more of these components, such as water, alkaline aqueous solution, A compound that can be dissolved in an alkali solution or the like in which these are heated can be used, and it is particularly preferable to include a metasilicate compound such as an alkali silicate such as metasilicate, sodium metasilicate, or potassium metasilicate. The silicate compound used may be a hydrate.
The concentration of the silicic acid compound contained in the silicic acid compound-containing solution can be appropriately selected depending on the use. Preferably, the silicic acid compound is 0.5 to 50 parts by mass, more preferably 1 with respect to 100 parts by mass of the solution. -30 mass parts, It is preferable that 1-20 mass parts is contained especially preferably.

As a surface treatment method using a silicate compound-containing solution on the surface of the polyimide film, known means can be used, and there is no particular limitation.
As a surface treatment method,
1) A method of immersing a polyimide film in a silicate compound-containing solution placed in a batch tank,
2) A method of spraying or spraying a solution containing a silicate compound on a polyimide film by spraying or showering,
3) The method etc. which apply | coat a silicate compound containing solution to the polyimide film surface are mentioned. Moreover, it may process continuously by the roll-to-roll system which can be conveyed, and an individual piece may be batch-processed.

When the surface of the polyimide film is treated with the silicate compound-containing solution, the concentration of the silicate compound contained in the silicate compound-containing solution, the temperature of the solution, and the treatment time may be appropriately selected depending on the purpose of use.
When the surface of the polyimide film is treated using the silicate compound-containing solution, the temperature of the silicate compound-containing solution is more preferably in the range of 5 ° C to 80 ° C, and more preferably in the range of 10 ° C to 60 ° C.
What is necessary is just to select processing time suitably according to the objective, for example, about 0.1 to 20 minutes, Preferably it is about 0.2 to 15 minutes, More preferably, it is about 0.3 to 10 minutes. By increasing the temperature of the silicate compound-containing solution or the concentration of the silicate compound, the treatment capability can be improved and the treatment time can be shortened.

The laminated film can be produced by laminating a metal layer or a resin layer on the adhesive layer of the laminated film to produce a laminated film having three or more layers.
For the laminated film, a known method can be used as a method of further laminating a metal layer or a resin layer on the adhesive layer of the laminated film, and the laminated film can be laminated by pressurization, heating, pressure heating, or the like.

The metal layer is not particularly limited in the type of metal, but includes copper, copper alloy such as rolling or electrolysis, wiring members such as stainless steel, iron, titanium, aluminum, nickel, silicon, and chip members such as IC chips. Further, a combination of two or more layers can be used.
Although the thickness of a metal layer is not specifically limited, What is necessary is just the thickness which can be utilized as metal foil or a board, Preferably it is 2 micrometers-5000 micrometers, More preferably, it is the range of 3 micrometers-2000 micrometers, More preferably, it is the range of 5 micrometers-100 micrometers. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

(Evaluation methods)
1) Measurement of adhesive strength: In accordance with JIS C6471-8.1, a 90 ° peel was measured at a peeling rate of 50 mm / min to obtain an adhesive strength. The value of the adhesive strength was an average value of 5 or 6 measurements. When the polyimide precursor solution was cast on the metal support during film production, the air side surface was designated as A surface, and the metal support side surface was designated as B surface. Table 1 shows the results of adhesive strength measurement.

(Comparative Example 1)
A cover side CVA0525KA manufactured by Arisawa Manufacturing Co., Ltd. was pressed at 180 ° C. and 3 MPa for 30 minutes on the A-side of Ube Industries, Ltd. product name Upilex SN (thickness 7.5 μm) as a polyimide film. A laminate was obtained.
A coverlay CVA0525KA manufactured by Arisawa Seisakusho Co., Ltd. was pressed at 180 ° C. and 30 MPa for 30 minutes on the B side of the product name Upilex SN (thickness 7.5 μm) manufactured by Ube Industries, Ltd. as a polyimide film. A laminate was obtained.
The adhesive strength of the two types of laminates obtained was measured, and the results are shown in Table 1.

Example 1
Dissolve 50 g of sodium metasilicate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 950 g of pure water to prepare a 5 mass% sodium metasilicate nonahydrate aqueous solution, dilute 100 mL of 2N sulfuric acid to 1 L with pure water Thus, 0.2N sulfuric acid was prepared.
Ube Industries, Ltd. product name Upilex SN (thickness 7.5 μm) was immersed in a 5 mass% sodium metasilicate nonahydrate aqueous solution at 23 ° C. for 5 minutes, and then washed with pure water. Further, the treated film was immersed in 0.2N sulfuric acid at 23 ° C. for 2 minutes and then washed with pure water. The obtained film was dried in an environment of 23 ° C. and a relative humidity of 50%. Seven days after the sodium metasilicate treatment, a coverlay was bonded to the A-side or B-side in the same manner as in Comparative Example 1 to obtain two types of laminates, an A-side laminate and a B-side laminate. The adhesive strength of these laminates was measured. The results are shown in Table 1.

(Examples 2 to 6)
The adhesive strength was evaluated in the same manner as in Example 1 except that the coverlay was bonded after 14 days, 19 days, 28 days, 61 days, and 94 days from the day of the sodium metasilicate treatment. The results are shown in Table 1.

(Example 7)
A polyimide film was treated in the same manner as in Example 1 except that 150 g of sodium metasilicate nonahydrate was dissolved in 850 g of pure water and used as a 15% by mass aqueous solution of sodium metasilicate nonahydrate. One day after the treatment with the sodium metasilicate nonahydrate solution, a coverlay was bonded in the same manner as in Example 1, and the adhesive strength was measured. The results are shown in Table 1.

(Comparative Example 2)
In the same manner as in Comparative Example 1, on the A side or B side of the trade name Upilex SN (thickness 7.5 μm) manufactured by Ube Industries, Ltd., an acrylic adhesive (trade name: PILARAX LF0100) manufactured by DuPont, Nikko Rolled copper foil (BHY-13H-T, 18 μm thickness) manufactured by Metal Co., Ltd. is overlaid, pressed with a press at 180 ° C. and 9 MPa for 5 minutes, and further heat treated at 180 ° C. for 60 minutes to Two types of laminates were obtained: a layer laminate and a three-layer laminate on the B-side. With respect to these two types of laminates, 90 ° peel was measured at a peeling rate of 50 mm / min in accordance with JIS C6471-8.1, and this was taken as the adhesive strength. The results are shown in Table 2.

(Example 8)
Ube Industries, Ltd. product name Upilex SN (thickness 7.5 μm) was immersed in a 5 mass% sodium metasilicate nonahydrate aqueous solution at 23 ° C. for 5 minutes, and then washed with pure water. Furthermore, this film was immersed in 0.2N sulfuric acid at 23 ° C. for 2 minutes and then washed with pure water. The obtained film was dried in an environment of 23 ° C. and a relative humidity of 50%. Seven days after the treatment with the sodium metasilicate solution, two types of three-layer laminates (A side and B side) were prepared in the same manner as in Comparative Example 2, and the adhesive strength was measured. The results are shown in Table 2.

(Examples 9 to 12)
Adhesive strength was evaluated in the same manner as in Example 8 except that the laminate was produced 14 days, 19 days, 28 days, and 61 days after the treatment with the sodium metasilicate solution. The results are shown in Table 2.

(Example 13)
A polyimide film treated with a sodium metasilicate nonahydrate solution was prepared in the same manner as in Example 8 except that 150 g of sodium metasilicate nonahydrate was dissolved in 850 g of pure water and used as a 15% by mass aqueous solution.
One day after the treatment with the sodium metasilicate solution, two types of three-layer laminates (A side and B side) were prepared in the same manner as in Example 8, and the adhesive strength was measured. The results are shown in Table 2.

  When Examples 1-7 and Comparative Example 1 or Examples 8-13 and Comparative Example 2 were compared, the polyimide film treated with the sodium metasilicate nonahydrate solution was more than untreated on both the A and B sides. Adhesive strength improved. In addition, the adhesiveness of the polyimide film treated with the sodium metasilicate nonahydrate solution does not change even after 93 days or 61 days, and the adhesiveness is maintained for a long time.

Claims (13)

It is a laminated film in which a polyimide film and an adhesive layer are laminated,
A laminated film, wherein the polyimide film on the side on which the adhesive layer is laminated is surface-treated with a silicate-containing solution.   The laminated film according to claim 1, wherein the silicate is metasilicate.   The laminated film according to claim 1 or 2, wherein the adhesive layer contains an epoxy resin or an acrylic resin.   The laminated film according to claim 1, wherein the polyimide film has a thickness of 3 to 30 μm.   The laminated film according to any one of claims 1 to 3, wherein the polyimide film is a polyimide film continuously formed with a thickness of 3 to 30 µm.   The laminate according to claim 1, wherein the polyimide film is a polyimide film obtained from an acid component containing a biphenyltetracarboxylic acid component and a diamine component containing p-phenylenediamine. the film.   The polyimide film surface-treated with the silicate containing solution used for the laminated | multilayer film in any one of Claims 1-6.   A laminated film in which a metal layer or a resin layer is further laminated on the adhesive layer of the laminated film according to claim 1. It is a surface treatment method of a polyimide film used for lamination with an adhesive layer,
The polyimide film surface on the side where the adhesive layer is laminated is immersed in a silicate-containing solution, and the silicate-containing solution is applied, sprayed or sprayed on the surface of the polyimide film on which the adhesive layer is laminated. A surface treatment method for a polyimide film.   The method for treating a surface of a polyimide film according to claim 9, wherein the adhesive layer contains an epoxy resin or an acrylic resin.   The thickness of a polyimide film is 3-30 micrometers, The surface treatment method of the polyimide film of Claim 9 or Claim 10 characterized by the above-mentioned.   The polyimide film surface treatment method according to claim 9, wherein the polyimide film is a polyimide film continuously formed with a thickness of 3 to 30 μm.   The polyimide film according to any one of claims 9 to 12, wherein the polyimide film is a polyimide film obtained from an acid component containing a biphenyltetracarboxylic acid component and a diamine component containing p-phenylenediamine. A film surface treatment method.