TW201707976A - Layered body and method for manufacturing same - Google Patents

Abstract

To provide a layered body including a silicone resin layer and an organic polymer film, the layered body having excellent adhesion (peel strength) and good appearance quality. A layered body having a silane coupling agent layer on at least one surface of an organic polymer film, in which a silicone resin layer having polydimethylsiloxane (PDMS) as a main component thereof is layered via the silane coupling agent layer, the organic polymer film/silicone resin layered body being characterized in that the peel strength of the silicone resin layer and the polymer film is 0.3 N/cm to 15 N/cm.

Description

Laminate and method of manufacturing same

The present invention relates to a laminate comprising an organic polymer film and a polyoxyxylene resin layer, and more particularly to a laminate comprising a flexible, elastic, heat-resistant polyoxyxene resin, It is composed of an organic polymer film having a relatively high elastic modulus and excellent dimensional stability and excellent workability, and utilizes the advantages of each other.

Polyoxymethylene resin is a general term for a polymer compound having a main skeleton formed of a decane bond. It is known that various polyfluorene resins are used depending on the molecular weight, the degree of crosslinking, the substituent, and the like, but the physical properties are adjusted so as to have excellent heat resistance, water resistance, chemical resistance, and electrical properties, and particularly moderate. The elastic polyoxyxylene resin is called polyoxyxene rubber or polyoxyxene elastomer, and is widely used in gaskets, sealing materials, separators, laminating rolls, and electrophotographic carbons which are required to achieve both flexibility and heat resistance. Powder fixing roller and protective member for various purposes such as medical use and cosmetic molding. Moreover, since it lacks adhesiveness, it is also considered as a release sheet, a cushioning material, etc..

Although it is a polyoxyl resin having excellent properties, it is rarely used in electronic substrates. The reason is that the lack of adhesion is difficult to combine with various materials such as copper foil. Moreover, due to the soft material, it is difficult to view from the viewpoint of dimensional stability.

Polyoxymethylene resins have the disadvantage of being less mechanically strong due to softness. The use of a polysiloxane resin such as heat resistance, elasticity, and mold release property can be exemplified as a cushion sheet used in press working. In this application, in the case of a polyoxyxene resin sheet, if the pressure is too strong, there may be a case where the sheet is extended in the direction of the sheet, and the polyoxyacetin sheet itself is cracked or broken. Further, there is a case where the polyacetal resin sheet is entangled with the pressed object and broken together when it is broken. In order to solve these problems, attempts have been made to incorporate a reinforcing material into a polysiloxane sheet. It is known that a polyacetal resin sheet is added to a reinforcing material such as a glass cloth. The mechanical strength can be improved by inserting the cloth-like reinforcing material into the sheet, but the cloth-like reinforcing material is inhomogeneous, and there is a disadvantage that the flexibility of the sheet is impaired by the reinforcing. A reinforcing effect can be obtained in the same manner as in the case of bonding a polyoxyxylene resin sheet to a hard substrate such as a metal foil, a metal plate, a metal plate, a glass plate, a ceramic plate, or the like, or a hard substrate such as a glass epoxy board. However, it is often affected by the physical properties of the other material, and most of the results will impair the softness. An organic polymer film or an organic polymer sheet can be used as the reinforcing material for the flexibility of the polyoxynoxy resin. However, since the adhesion between the polyoxymethylene resin and the organic polymer material is insufficient, there are many problems such as peeling during use. .

For example, Patent Document 1 discloses an example in which a polyfluorene resin is provided on the surface of a polyimide film processed into a seamless belt to obtain an endless belt, and the endless belt is used in an electrophotographic type. The intermediate transfer belt of the printer. For example, Patent Document 2 discloses an example in which a polyimide material is used as a material, and an adhesive sheet of a polyoxyxylene resin is used as an adhesive. Further, Patent Document 3 discloses an example in which a laminate composed of a polyimide film and a polyoxymethylene resin film is used for a fixing film of an electrophotographic printer. [Prior Technical Literature] [Patent Literature]

Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

[Problems to be Solved by the Invention] As described above, the polyoxyxene resin has excellent properties such as heat resistance and flexibility, but it is considered to be due to its high chemical resistance and peelability. One of the materials that are difficult to combine with other material stacks. In order to solve such a problem, the present invention has been made in an effort to provide a laminate comprising a polyoxyxylene resin layer and an organic polymer film, which are excellent in adhesion (peel strength) and good in appearance quality. [Means for solving the problem]

In order to solve such problems by the surface treatment on the side of the organic polymer film, the inventors of the present invention conducted diligent research and found that the application of a decane coupling agent for a polyoxyxylene resin in a gas phase can be provided in a polymer film and A laminate having no foreign matter intervening and good adhesion between the polyoxyalkylene resin layers can produce a high-definition flexible electronic device in a good yield, and can improve the recyclability of the polyoxynoxy resin. The invention has been made.

That is, the present invention consists of the following constitution. A laminate having a decane coupling agent layer on at least one side of an organic polymer film and having a polyoxyxylene resin layer interposed therebetween, characterized in that the polyoxyalkylene resin The peel strength between the layer and the polymer film is 0.3 N/cm or more and 15 N/cm or less. 2. The laminate according to 1, wherein the number of the foreign substances containing ruthenium having a major axis of 10 μm or more in the decane coupling agent layer is 2,000/m ² or less. 3. The laminate according to any one of 1 to 2, wherein the decane coupling agent layer has a thickness of from 1 to 500 nm. 4. The laminate according to any one of 1 to 3, wherein the laminate has an area of 1000 cm ² or more. 5. The laminate according to any one of 1 to 4, wherein the organic polymer film is a polyimide film. A method of producing a laminate according to any one of items 1 to 5, which comprises exposing an organic polymer film to a gasified decane coupling agent to form a decane coupling. The step of the tie layer, and no vacuum is used in this step. 7. The method for producing a laminate according to 6, comprising the step of exposing the organic polymer film to a decane coupling agent vaporized by bubbling to form a decane coupling agent layer. 8. The method for producing a laminate according to 7, wherein in the step of exposing the organic polymer film to the vaporized decane coupling agent to form a decane coupling agent layer, drying using a dew point of 0 ° C or less is used. The gas acts as a carrier gas. 9. The method for producing a laminate according to any one of 6 to 8, wherein, in the step of exposing the organic polymer film to a gasified decane coupling agent to form a decane coupling agent layer, Gases with a dew point above 5 °C coexist. 10. The method for producing a laminate according to any one of 6 to 8, wherein, in the step of exposing the organic polymer film to the vaporized decane coupling agent to form a decane coupling agent layer, An electric field is applied to the organic polymer film. The method for producing a laminate according to any one of the items 6 to 9, which comprises the step of performing an activation treatment on the surface of the formation of the decane coupling agent layer of the organic polymer film before the formation of the silane coupling agent layer. 12. The method for producing a laminate according to any one of 6 to 11, wherein the step of exposing the organic polymer film to the vaporized decane coupling agent to form a decane coupling agent layer is formed. The three-dimensional surface roughness (Sa) of the surface of the decane coupling agent layer was 5.0 nm or less. [Effects of the Invention]

According to the present invention, a good laminate in which no foreign matter is interposed between the organic polymer film and the polyoxynized resin can be obtained, and as a result, the bonding strength between the organic polymer film and the polyoxymethylene resin is uniformized. In the present invention, when an organic polymer film having high heat resistance is more preferably used, it can be bonded without using an adhesive having a poor heat resistance and an adhesive, and a laminate can be used in a higher temperature range. For use in a high temperature range of 180 ° C or higher, preferably 230 ° C or higher, and more preferably 260 ° C or higher, it is desirable to use a cushioning material used for pressing at high temperature, laminating, electronic parts with soldering, and high temperature. Uses such as conveying members used in the environment.

The laminate system of the present invention comprises at least a laminate of a polyoxyxylene resin layer, an organic polymer film, and a decane coupling agent layer.

<Polyoxygenated Resin> The polyoxyxylene resin forming the polyoxyxylene resin layer in the present invention means a substance which is solid at room temperature in the fluorene-based polymer compound having a main skeleton formed of a decane bond. . The polyoxynoxy resin which is preferably used in the present invention is preferably a polyoxyalkylene resin which has a polydialkylsiloxane as a basic skeleton and which has a molecular weight, a degree of crosslinking, a substituent, and the like adjusted in accordance with the purpose. In the polyoxyxene resin, by selecting a substituent to be introduced, the skeleton is further formed into a cyclic or branched structure, and various functions such as heat resistance, chemical resistance, hydrophilicity, or hydrophobicity can be enhanced or imparted. The substituent introduced into the polyoxymethylene resin of the present invention may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a substituted phenyl group, a polyether group, an epoxy group or an amine group. A substituent containing an amino group, a carboxyl group, an aralkyl group or the like, which may be introduced to a side chain or a molecular terminal. In the present invention, a polyfluorene oxide resin containing polydimethyl siloxane or polydiphenyl siloxane as a main skeleton, and a polyoxy siloxane resin containing both a methyl group and a phenyl group are preferred. The polydecane resin of the present invention may be a one-liquid or two-liquid type polyoxynoxy resin. The two-component polyoxynoxy resin separates the main material from a crosslinking agent, a reaction accelerator, and the like as a curing agent, and mixes the two before use. A preferred method and/or catalyst used for crosslinking the polyoxyxylene resin of the present invention is a condensation catalyst. Other catalysts and initiators can be used by preparing a polyoxyxene resin having a suitable reactive group. For example, a decane-olefin addition (hydrazine hydrogenation) catalyst, a free radical catalyst such as a peroxide catalyst can be used. , heat, and exposure to ultraviolet radiation. In the case of a free radical catalyst such as a peroxide catalyst, when the polyoxyxylene resin contains a vinyl group, it can be used as a blended hardener or catalyst. When the polyoxyxylene resin has a Si-H group at the terminal position, or when the resin has a terminal double bond, a decane-olefin addition catalyst is useful. Polyoxyxides having a hydroxyl group in the above-described sterol-terminated polydiorganotoxime containing a sterol-terminated (terminalized) polydimethyl siloxane can also be catalyzed by heat. A preferred curing system comprises a condensation reaction. For example, a phthalic acid ester of tetraethyl phthalate is reacted with a hydroxyl terminal group of a diorganooxyalkylene of the composition of the present invention by a condensation reaction. In the reaction, an alcohol is evolved, and the reaction is carried out using a metal soap such as, for example, dibutyltin dilaurate as a catalyst. Further, a more preferred catalyst is an organozinc compound such as zinc hexanoate. It is believed that a condensation catalyst such as zinc hexanoate promotes the sterol end group present in the sterol-terminated polydiorganotoxime, and is believed to be present in the polydimethylsiloxane polymer with methyl phenyl times A condensation reaction of a residual hydroxyl group (sterol) in a hemidecane.

<Organic polymer film> The organic polymer film of the present invention may be polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate or polyethylene naphthalate. All aromatic polyesters, other copolyesters, polymethyl methacrylate, other copolyacrylates, polycarbonates, polyamines, polybenzazoles, polyether oximes, polyether ketones, polyamidoximines, poly Ether quinone imine, aromatic polyimine, alicyclic polyimide, fluorinated polyimine, cellulose acetate, nitrocellulose, aromatic polyamine, polyvinyl chloride, polyphenol, polyaryl Membranes, polyphenylene sulfide, polyphenylene ether, polystyrene and other films. The effect of the present invention is particularly remarkable. The useful one is a polymer having a heat resistance of 100 ° C or higher, and a film of an engineering plastic. Here, heat resistance means a glass transition temperature or a heat distortion temperature.

The organic polymer film of the present invention can be obtained by subjecting a thermoplastic polymer material in the above polymer material to a melt-stretching method.

The thickness of the organic polymer film of the present invention is preferably 3 μm or more, more preferably 11 μm or more. The upper limit of the thickness of the organic polymer film is not particularly limited, and the thickness of the flexible electronic device is preferably 250 μm or less, more preferably 150 μm or less, and particularly preferably 90 μm or less. The area of the organic polymer film of the present invention (that is, the area of the laminate) is preferably a large area from the viewpoint of production efficiency and cost of the laminate or the flexible electronic device. More preferably, it is 1000 cm ² or more, more preferably 1500 cm ² or more, and more preferably 2000 cm ² or more.

The organic polymer film particularly suitable for use in the present invention is a polyimine film, and an aromatic polyimine, an alicyclic polyimine, a polyamidimide, a polyether quinone, or the like can be used. In particular, in the case of manufacturing a flexible display device, it is preferable to use a polyimide film having colorless transparency, and it is preferable to form a back surface element of a reflective or self-luminous type display. .

Generally, a polyimine film is coated on a support for producing a polyimide film by a solution of a polyaminic acid (polyimine precursor) obtained by reacting a diamine with a tetracarboxylic acid in a solvent. Drying to form a green film (also known as a "precursor film" or "polyglycolic acid film"), further on the support for the production of the polyimide film, or having peeled off from the support In the state, the green film is subjected to a high-temperature heat treatment to obtain a dehydration ring-closure reaction.

The diamine constituting the polyamic acid is not particularly limited, and an aromatic diamine, an aliphatic diamine or an alicyclic diamine which are generally used can be synthesized by using polyimine. From the viewpoint of heat resistance, it is preferred that the aromatic diamine is preferred, and the aromatic diamine has benzoic acid. The aromatic diamines of the azole structure are more preferred. Use with benzo The aromatic diamines of the azole structure exhibit high heat resistance and exhibit high modulus of elasticity, low heat shrinkage, and low coefficient of linear expansion. The diamines may be used singly or in combination of two or more.

With benzo The aromatic diamine of the azole structure is not particularly limited, and examples thereof include 5-amino-2-(p-aminophenyl)benzo. Azole, 6-amino-2-(p-aminophenyl)benzo Azole, 5-amino-2-(m-aminophenyl)benzo Azole, 6-amino-2-(m-aminophenyl)benzo Azole, 2,2'-p-phenylene bis(5-aminobenzo) Oxazole), 2,2'-p-phenylene bis(6-aminobenzo) Oxazole), 1-(5-aminobenzophenone Oxazo)-4-(6-aminobenzophenone Azolo)benzene, 2,6-(4,4'-diaminodiphenyl)benzo[1,2-d:5,4-d'] Azole, 2,6-(4,4'-diaminodiphenyl)benzo[1,2-d:4,5-d'] Azole, 2,6-(3,4'-diaminodiphenyl)benzo[1,2-d:5,4-d'] Azole, 2,6-(3,4'-diaminodiphenyl)benzo[1,2-d:4,5-d'] Azole, 2,6-(3,3'-diaminodiphenyl)benzo[1,2-d:5,4-d'] Azole, 2,6-(3,3'-diaminodiphenyl)benzo[1,2-d:4,5-d'] Oxazole and the like.

Benzene Examples of the aromatic diamines other than the aromatic diamines of the azole structure include 2,2'-dimethyl-4,4'-diaminobiphenyl and 1,4-bis[2-(4). -aminophenyl)-2-propyl]benzene (diphenylamine), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, 2,2'-di(trifluoro Methyl)-4,4'-diaminobiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl , bis[4-(3-aminophenoxy)phenyl]one, bis[4-(3-aminophenoxy)phenyl] sulfide, bis[4-(3-aminophenoxy) Phenyl]anthracene, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1 1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine, p-aminobenzylamine, 3,3'-diamino Diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3'-diamine Diphenylarylene, 3,4'-diaminodiphenylarylene, 4,4'-diaminodiphenylarylene, 3,3'-diaminodiphenyl hydrazine, 3,4' -diaminodiphenyl hydrazine, 4,4'-diaminodiphenyl hydrazine, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4' -diaminodiyl Benzophenone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(4- Aminophenoxy)phenyl]methane, 1,1-bis[4-(4-aminophenoxy)phenyl]ethane, 1,2-bis[4-(4-aminophenoxy) Phenyl]ethane, 1,1-bis[4-(4-aminophenoxy)phenyl]propane, 1,2-bis[4-(4-aminophenoxy)phenyl]propane , 1,3-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 1,1-double [4-(4-Aminophenoxy)phenyl]butane, 1,3-bis[4-(4-aminophenoxy)phenyl]butane, 1,4-bis[4-( 4-aminophenoxy)phenyl]butane, 2,2-bis[4-(4-aminophenoxy)phenyl]butane, 2,3-bis[4-(4-amino) Phenoxy)phenyl]butane, 2-[4-(4-aminophenoxy)phenyl]-2-[4-(4-aminophenoxy)-3-methylphenyl] Propane, 2,2-bis[4-(4-aminophenoxy)-3-methylphenyl]propane, 2-[4-(4-aminophenoxy)phenyl]-2-[ 4-(4-Aminophenoxy)-3,5-dimethylphenyl]propane, 2,2-bis[4-(4-aminophenoxy)-3,5-dimethylbenzene Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,4-bis(3- Phenoxy group) benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-amino group Phenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]one, bis[4-(4-aminophenoxy)phenyl]thioether, bis[4-(4 -aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, bis[4-(3-aminophenoxy)phenyl]ether, double [4-(4-Aminophenoxy)phenyl]ether, 1,3-bis[4-(4-aminophenoxy)benzylidene]benzene, 1,3-bis[4-( 3-aminophenoxy)benzhydryl]benzene, 1,4-bis[4-(3-aminophenoxy)benzylidene]benzene, 4,4'-bis[(3-amine) Phenyloxy)benzhydryl]benzene, 1,1-bis[4-(3-aminophenoxy)phenyl]propane, 1,3-bis[4-(3-aminophenoxy) Phenyl]propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3 , 3-hexafluoropropane, bis[4-(3-aminophenoxy)phenyl]methane, 1,1-bis[4-(3-aminophenoxy)phenyl]ethane, 1, 2-bis[4-(3-aminophenoxy)phenyl]ethane, bis[4-(3-aminophenoxy)phenyl]anthracene, 4,4'-bis[3-( 4-aminophenoxy)benzhydryl]diphenyl ether, 4,4'-bis[3-(3-aminophenoxy)benzylidene Diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4 -amino-α,α-dimethylbenzyl)phenoxy]diphenyl hydrazine, bis[4-{4-(4-aminophenoxy)phenoxy}phenyl]anthracene, 1,4 - bis[4-(4-aminophenoxy)phenoxy-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)phenoxy -α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-fluorophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-) Methylphenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-amino-6-cyanophenoxy)-α,α-dimethylbenzyl Benzo, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxybenzophenone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 4,4'-diamine 5-5-phenoxybenzophenone, 3,4'-diamino-4-phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 4,4'-diamino-5,5'-diphenoxydiphenyl Ketone, 3,4'-diamino-4,5'-diphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4' -diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-biphenoxybenzophenone, 3,4'-diamino-5'-biphenyl Oxybenzophenone, 1,3-bis(3-amino-4-phenoxybenzylidene)benzene, 1,4-bis(3-amino-4-phenoxybenzylidene) Benzene, 1,3-bis(4-amino-5-phenoxybenzylidene)benzene, 1,4-bis(4-amino-5-phenoxybenzylidene)benzene, 1 , 3-bis(3-amino-4-biphenoxybenzhydryl)benzene, 1,4-bis(3-amino-4-biphenoxybenzyl)benzene, 1,3 - bis(4-amino-5-biphenoxy benzhydryl)benzene, 1,4-bis(4-amino-5-biphenoxybenzylidene)benzene, 2,6-double [4-(4-Amino-α,α-dimethylbenzyl)phenoxy]benzonitrile, and a part or all of a hydrogen atom on the aromatic ring of the above aromatic diamine is substituted into a halogen atom or a carbon a group of 1 to 3 alkyl or alkoxy, cyano, or a hydrogen atom of an alkyl or alkoxy group which is partially or wholly substituted with a halogenated alkyl or alkoxy group having 1 to 3 carbon atoms of a halogen atom. Substituted aromatic diamines and the like.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane. 1,8-diaminooctane and the like. Examples of the alicyclic diamines include 1,4-diaminocyclohexane and 4,4'-methylenebis(2,6-dimethylcyclohexylamine). The total amount of the diamines (aliphatic diamines and alicyclic diamines) other than the aromatic diamines is preferably 20% by mass or less, more preferably 10% by mass or less, and 5% by mass based on the total of the diamines. The following is especially good. In other words, the aromatic diamine is preferably 80% by mass or more of all diamines, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

As the tetracarboxylic acid constituting the polyglycolic acid, polytetraimine can be used to synthesize commonly used aromatic tetracarboxylic acids (including acid anhydrides thereof), aliphatic tetracarboxylic acids (including acid anhydrides thereof), and alicyclic tetracarboxylic acids ( Including its anhydride). Among them, aromatic tetracarboxylic anhydrides and alicyclic tetracarboxylic anhydrides are preferred, and from the viewpoint of heat resistance, aromatic tetracarboxylic anhydrides are more preferable, and from the viewpoint of light transmittance, alicyclic four Carboxylic acids are preferred. When these are acid anhydrides, they may have one or two acid anhydride structures in the molecule, and preferably have two acid anhydride structures (dianhydrides). The tetracarboxylic acids may be used singly or in combination of two or more.

Examples of the alicyclic tetracarboxylic acid include alicyclic groups such as cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 3,3',4,4'-dicyclohexyltetracarboxylic acid. Group of tetracarboxylic acids, and such anhydrides. Among these, a dianhydride having two acid anhydride structures (for example, cyclobutane tetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3', 4,4' - Bicyclohexyltetracarboxylic dianhydride or the like) is preferred. Further, the alicyclic tetracarboxylic acid may be used singly or in combination of two or more. When the alicyclic tetracarboxylic acid is important in transparency, for example, it is preferably 80% by mass or more of all tetracarboxylic acids, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

The aromatic tetracarboxylic acid is not particularly limited, and is preferably a pyromellitic acid residue (that is, a structure having a structure derived from pyromellitic acid), and an acid anhydride is more preferable. Examples of such aromatic tetracarboxylic acids include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 4,4'-oxydiphthalic dianhydride. , 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylfluorene tetracarboxylic dianhydride, 2,2-bis[4-(3 , 4-dicarboxyphenoxy)phenyl]propionic anhydride, and the like. When the aromatic tetracarboxylic acid is important in heat resistance, for example, it is preferably 80% by mass or more of all the tetracarboxylic acids, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

In the organic polymer film of the present invention, the glass transition temperature is preferably 250 ° C or more, more preferably 300 ° C or more, more preferably 350 ° C or more, or preferably no glass transition point is observed in the range of 500 ° C or less. good. The glass transition temperature in the present invention is determined by differential thermal analysis (DSC).

The organic polymer film of the present invention preferably has a linear expansion coefficient (CTE) of -5 ppm/K to +20 ppm/K, more preferably -5 ppm/K to +15 ppm/K, and particularly preferably 1 ppm/K to +10 ppm/K. When the CTE is within the above range, the effective linear expansion coefficient of the entire laminate can be kept small, and the dimensional stability of the laminate can be improved. The coefficient of linear expansion in the present invention uses an average enthalpy between 30 and 200 ° C, but depending on the application, the temperature range is emphasized, and the treatment at a high temperature is sometimes adjusted to a range of 30 ° C to 400 ° C, and adjustment is made. In the range of 100 ° C to 400 ° C, when welding, it may be adjusted to a range of 50 ° C to 280 ° C. When used in automotive parts, the temperature range may be in the range of -50 ° C to 150 ° C.

The breaking strength of the organic polymer film in the present invention is preferably 60 MPa or more, more preferably 120 MP or more, and particularly preferably 240 MPa or more. There is no limit to the upper limit of the breaking strength, and in fact it is less than about 1000 MPa. In addition, the breaking strength of the organic polymer film here means the average enthalpy of the longitudinal direction and the width direction of the organic polymer film. The adhesive strength of the organic polymer film and the polyoxyxylene resin in the present invention is preferably 1/2 or less of the breaking strength of the organic polymer film. It is assumed that in the laminate of the present invention using a film having a thickness of 10 μm, the film has a bonding strength of 0.5 N/cm. The breaking force applied to the film having a width of 10 mm was: 0.5 N / (10 μm × 10 mm) = 0.5 N / 0.1 mm ² = 5 MPa. In such a case, if the film has about 10 times, that is, a breaking strength of 50 MPa or more, the peeling operation can be performed without any problem when the film is peeled off. The bonding strength is preferably 1/3 or less of the breaking strength of the organic polymer film, and more preferably 1/4 or less.

The thickness of the organic polymer film in the present invention is preferably 20% or less, more preferably 12% or less, still more preferably 7% or less, and particularly preferably 4% or less. If the thickness unevenness exceeds 20%, it tends to be difficult to apply to a narrow portion. Further, the thickness of the film is not uniform. For example, a film thickness can be measured by randomly measuring a film at a position of about 10 o'clock from the film to be measured by a contact film thickness meter, and the film thickness can be obtained by the following formula. Uneven thickness of film (%) = 100 × (maximum film thickness - minimum film thickness) ÷ average film thickness

In the production of the organic polymer film of the present invention, it is preferable to form a long film having a width of 300 mm or more and a length of 10 m or more, and it is preferably wound around a roll-shaped film of a winding core. The shape is better.

In the organic polymer film, in order to ensure operability and productivity, it is preferable to add and contain a sliding material (particles) to the film, and to impart fine unevenness to the organic polymer film to ensure slidability. The sliding material (particles) is preferably a fine particle composed of an inorganic material, and may be made of a metal, a metal oxide, a metal nitride, a metal carbide, a metal salt, a phosphate, a carbonate, a talc, a mica, a clay, or the like. Particles composed of clay minerals, etc. Metal oxides such as cerium oxide, calcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium pyrophosphate, hydroxyapatite, calcium carbonate, glass filler, phosphate, and carbonate are preferably used. There are only one type of sliding material, and two or more types may be used.

The volume average particle diameter of the sliding material (particles) is usually 0.001 to 10 μm, preferably 0.03 to 2.5 μm, more preferably 0.05 to 0.7 μm, and particularly preferably 0.05 to 0.3 μm. The volume average particle diameter is based on the measurement enthalpy obtained by the light scattering method. When the particle size is smaller than the lower limit, the industrial production of the organic polymer film becomes difficult. When the temperature exceeds the upper limit, the unevenness of the surface becomes excessively large, and the adhesion strength is weakened, and there is a problem in practical use.

The amount of the sliding material added is 0.02 to 50% by mass, preferably 0.04 to 3% by mass, and more preferably 0.08 to 1.2% by mass based on the amount of the polymer component in the organic polymer film. When the amount of the sliding material added is too small, the effect of adding the sliding material is difficult to be expected, and the slidability and the production of the organic polymer film are less likely to be ensured. If the amount of the sliding material is too large, the surface unevenness of the film may become too large, and even if it is ensured The slidability still causes a decrease in smoothness, a decrease in the breaking strength of the organic polymer film, a decrease in the elongation at break, or an increase in the CTE.

When the organic polymer film is added and the sliding material (particles) is contained, a single-layer organic polymer film in which the sliding material is uniformly dispersed may be used, and for example, one of the organic polymer films containing the sliding material may be used. A multilayer organic polymer film comprising an organic polymer film containing no sliding material or a sliding material but a small amount. In the film of the multilayer polymer, fine unevenness can be imparted to the surface of one layer (film), and slidability can be ensured in the layer (film), and good workability and productivity can be ensured.

When the multilayer organic polymer film is a film obtained by a melt-stretch film formation method, for example, first, an organic polymer film material containing no sliding material is used as a film, and in the middle of the step, at least one side of the film is coated with a sliding material. Obtained from the resin layer. Needless to say, the organic polymer film material containing the sliding material may be used as a film, and in the middle of the step or after the film formation is completed, the organic polymer film material containing no sliding material may be applied to obtain a film. In the case of using an organic polymer film obtained by a solution forming method of a polyimide film, for example, a sliding material (preferably having an average particle diameter of about 0.05 to 2.5 μm) can be used with respect to polyglycine. The polymer solid content in the solution is from 0.02% by mass to 50% by mass (preferably 0.04 to 3% by mass, more preferably 0.08 to 1.2% by mass) of the polyaminic acid solution, and the content of the sliding material or the content thereof is a small amount (preferably less than 0.02% by mass, more preferably less than 0.01% by mass relative to the solid content of the polymer in the polyaminic acid solution) as a poly-proline solution (polyamide) The imine precursor solution is produced.

The multilayer (lamination) method of the multilayer organic polymer film is not particularly limited as long as the adhesion between the two layers is not problematic, and it is only required to be bonded without interposing an adhesive layer or the like.

In the case of a polyimide film, for example, i) a method in which one of the polyimide films is formed, and another polyamine solution is continuously coated on the polyimide film and ruthenium imidized; Ii) a method in which a poly-proline solution is cast and a poly-proline film is formed, and another poly-proline solution is continuously coated on the poly-proline film to carry out hydrazine imidization; iii) use a method of co-extrusion; iv) spraying a polyamic acid solution containing a large amount of sliding material on a film formed of a polyamic acid solution containing no sliding material or a small amount of sliding material, spraying, T-coating, etc. A method of coating and ruthenium imidization or the like. Preferably, the method of the above i) or the above ii) is preferably used in the present invention.

The ratio of the thickness of each layer in the multilayer organic polymer film is not particularly limited, and the polymer layer containing a large amount of the sliding material is (a) layer, the sliding material is not contained, or the polymer layer having a small amount is (b) In the case of the layer, the layer (a)/(b) is preferably 0.05 to 0.95. When the layer (a) or layer (b) exceeds 0.95, the smoothness of the layer (b) tends to be lost. On the other hand, when it is less than 0.05, the effect of improving the surface characteristics is insufficient and the slipperiness is lost.

<Surface Activation Treatment of Organic Polymer Film> The organic polymer film used in the present invention is preferably subjected to surface activation treatment. By the surface activation treatment, the surface of the organic polymer film can be reformed to a state in which a functional group exists (so-called activated state), and the adhesion to the decane coupling agent can be improved. The surface activation treatment in the present invention is a dry or wet surface treatment. The dry treatment of the present invention may be carried out by treating the surface with an active energy ray such as ultraviolet rays, electron beams, X-rays, corona treatment, vacuum plasma treatment, normal piezoelectric slurry treatment, flame treatment, ITRO treatment, or the like. The wet treatment can be exemplified by a treatment in which the surface of the membrane is brought into contact with an acid or alkali solution. The surface activation treatment which can be desirably used in the present invention is a plasma treatment, which is a combination of a plasma treatment and a wet acid treatment.

The plasma treatment is not particularly limited, and includes RF plasma treatment, microwave plasma treatment, microwave ECR plasma treatment, atmospheric piezoelectric slurry treatment, corona treatment, etc. in a vacuum, and also includes fluorine gas treatment, using an ion source. The ion implantation treatment, the treatment using the PBII method, the flame treatment exposed to the hot plasma, the ITRO treatment, and the like. Among these, RF plasma treatment, microwave plasma treatment, and atmospheric piezoelectric slurry treatment in a vacuum are preferred.

For the appropriate conditions of the plasma treatment, it is preferable to use a plasma having a high chemical etching effect such as oxygen plasma, a fluorine-containing plasma such as CF ₄ or C ₂ F ₆ , or a plasma such as Ne, Ar, Kr or Xe. A plasma-like treatment in which a physical energy is supplied to a polymer surface and a physical etching effect is high is preferable. Further, a plasma such as CO ₂ , CO, H ₂ , N ₂ , NH ₄ or CH ₄ , and such a mixed gas or further water vapor are also preferred. Further, the preparation needs to be made to be selected from, for example, OH, N ₂ , N, CO, CO ₂ , H, H ₂ , O ₂ , NH, NH ₂ , NH ₃ , COOH, NO, NO ₂ , He, Ne, Ar. , Kr, Xe, CH ₂ O, Si(OCH ₃ ) ₄ , Si(OC ₂ H ₅ ) ₄ , C ₃ H ₇ Si(OCH ₃ ) ₃ , C ₃ H ₇ Si(OC ₂ H ₅ ) ₃ At least one or more components in the group are used as a gas or as a plasma of a decomposition product in the plasma. When the target is for a short period of time, it is preferable that the plasma has a high energy density, a high kinetic energy of ions in the plasma, and a high density of the active material, but the surface smoothness is required. Therefore, there is a limit to the improvement of energy density. When oxygen plasma is used, although surface oxidation is performed and OH groups are generated, it is easy to produce a surface which is insufficiently bonded to the film itself, and the surface roughness (roughness) becomes large, so the adhesion is also good. Getting worse. Further, when a plasma of Ar gas is used, a pure physical collision occurs on the surface, and in this case, the surface roughness is also increased. In consideration of these, microwave plasma treatment, microwave ECR plasma treatment, plasma irradiation using an ion source that is easy to implant high-energy ions, PBII method, and the like are also preferable.

The surface activation treatment cleans the surface of the polymer and further generates a reactive functional group. The generated functional group and the coupling agent layer are linked by hydrogen bonding or chemical reaction, and the organic polymer film layer and the coupling agent layer can be firmly adhered. The effect of etching the surface of the organic polymer film can also be obtained in the plasma treatment. In particular, in the organic polymer film containing a relatively large amount of the sliding material particles, there is a case where the protrusion due to the sliding material interferes with the film and the polyoxymethylene resin. At this time, the surface of the organic polymer film is etched thin by the plasma treatment, and after the sliding material particles are partially exposed, and then treated with hydrofluoric acid, the sliding material particles in the vicinity of the surface of the film can be removed.

The surface activation treatment may be carried out only on one side of the organic polymer film, or may be carried out on both sides. When the plasma treatment is performed on one side, the organic polymer film may be placed on the one-side electrode and placed on the surface of the organic polymer film that is not in contact with the electrode. Perform plasma treatment. Further, when the organic polymer film is placed in a state of being electrically floating in a space between the two electrodes, the plasma treatment can be performed on both surfaces. Further, a plasma treatment may be performed in a state in which a protective film is attached to one surface of the organic polymer film to perform one-side treatment. Further, as the protective film, a PET film to which an adhesive is attached, an olefin film, or the like can be used.

<Hydrane coupling agent> The decane coupling agent in the present invention means physically or chemically interposed between the polyoxynoxy resin and the organic polymer film, and has an adhesion between the two. The compound of action. Preferred examples of the decane coupling agent include N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane and N-2-(aminoethyl)-3. -Aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyl Triethoxy decane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, Vinyltrichloro Decane, vinyltrimethoxydecane, vinyltriethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropyl Methyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methyl Propylene oxypropyl triethoxy decane, 3-propenyl methoxypropyl trimethoxy decane, N-phenyl-3-aminopropyl trimethoxy decane, N-(vinyl benzyl)-2 -Aminoethyl-3-aminopropyltrimethoxydecane hydrochloride, 3-ureidopropyltriethoxydecane, 3-chloropropyltrimethoxydecane, 3-mercaptopropylmethyldi Methoxydecane, 3-mercaptopropyltrimethoxydecane, bis(triethoxymethylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxydecane, gins-(3-trimethoxyfluorene) Isopropyl)isocyanurate, chloromethylphenethyltrimethoxydecane, chloromethyltrimethoxydecane, aminophenyltrimethoxydecane, aminophenethyltrimethoxydecane, amine Phenylaminomethylphenethyltrimethoxydecane, hexamethyldioxane, and the like.

The decane coupling agent which can be used in the present invention may be used, in addition to the above, n-propyltrimethoxydecane, butyltrichlorodecane, 2-cyanoethyltriethoxydecane, cyclohexyltrichlorodecane or decyl group. Trichlorodecane, diethyl methoxy dimethyl decane, diethoxy dimethyl decane, dimethoxy dimethyl decane, dimethoxy diphenyl decane, dimethoxymethyl phenyl decane , dodecyltrichlorodecane, dodecyltrimethoxydecane, ethyltrichlorodecane, hexyltrimethoxydecane,octadecyltriethoxydecane,octadecyltrimethoxydecane, n-octyltrichloro Decane, n-octyltriethoxydecane, n-octyltrimethoxydecane, triethoxyethyldecane, triethoxymethyldecane, trimethoxymethylnonane, trimethoxyphenylnonane, pentane Triethoxy decane, pentyl trichloro decane, triethoxy methoxymethyl decane, trichlorohexyl decane, trichloromethyl decane, trichlorooctadecyl decane, trichloropropyl decane, trichlorotetradecane Base decane, trimethoxy propyl decane, allyl trichloro decane, allyl triethoxy decane, allyl trimethoxy fluorene , diethoxymethyl vinyl decane, dimethoxymethyl vinyl decane, trichlorovinyl decane, triethoxy vinyl decane, vinyl ginseng (2-methoxyethoxy) decane, Trichloro-2-cyanoethyl decane, diethoxy (3-glycidoxypropyl) methyl decane, 3-glycidoxypropyl (dimethoxy) methyl decane, 3 - glycidoxypropyltrimethoxydecane, and the like.

Further, other alkoxy decane such as tetramethoxy decane or tetraethoxy decane may be appropriately added to the decane coupling agent.

Further, when other alkoxy decane such as tetramethoxy decane or tetraethoxy decane is appropriately added to the decane coupling agent, or when it is not added, mixing, heating, and some reuse of the reaction may be applied.

Among the decane coupling agents, the decane coupling agent preferably used in the present invention is preferably a decane coupling agent having a chemical structure of a ruthenium atom per molecule coupling agent. In the present invention, a particularly preferred decane coupling agent is N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3- Aminopropyltrimethoxydecane, N-2-(aminoethyl)-3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltri Ethoxy decane, 3-triethoxyindolyl-N-(1,3-dimethyl-butylene)propylamine, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3 -glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, Aminophenyltrimethyl Oxydecane, aminophenethyltrimethoxydecane, aminophenylaminomethylphenethyltrimethoxydecane, and the like. When high heat resistance is required in the treatment, it is preferred that the Si and the amine group be bonded by an aromatic group. Further, the present invention may be used in combination with a phosphorus-based coupling agent, a titanate-based coupling agent, or the like as needed.

<Coating method of decane coupling agent> In the prior art, the coating of the decane coupling agent is carried out in a solution state in which a decane coupling agent is diluted with a solvent such as an alcohol. However, the present invention is characterized in that the decane coupling agent coating step is carried out through a gas phase. That is, in the present invention, the organic polymer film is exposed to a vaporized decane coupling agent to be applied. The decane coupling agent coating may also be referred to as a decane coupling agent treatment. The gasification means a vapor of a decane coupling agent, that is, a substantially gaseous decane coupling agent, or a state in which a silane coupling agent in a particulate state exists. Exposure means that the organic polymer film is in contact with a gas or vacuum state containing the aforementioned vaporized decane coupling agent.

The vapor of the decane coupling agent can be easily obtained by heating the liquid state decane coupling agent to a temperature of from 40 ° C to the boiling point of the decane coupling agent. The vapor of the decane coupling agent can also be formed below the boiling point. It is also possible to use a state in which the particles of the decane coupling agent coexist. Further, the operation of increasing the vapor density can be carried out by the operation of temperature and pressure. The boiling point of the decane coupling agent varies depending on the chemical structure, and is approximately in the range of 100 to 250 °C. However, heating at 200 ° C or higher may cause a side reaction of the organic side of the decane coupling agent, which is not preferable.

The environment in which the decane coupling agent is heated may be any one under pressure, under normal pressure and under reduced pressure. In order to promote gasification of the decane coupling agent, it is preferably under normal pressure or under reduced pressure. good. Since the decane coupling agent is mostly classified as a flammable liquid, it is preferably contained in a closed container, and it is preferred to carry out the gasification operation after replacing the inside of the container with a passive gas. On the other hand, in order to improve production efficiency and reduce the price of production equipment, it is preferable to coat the decane coupling agent in an environment where no vacuum is used. For example, the organic polymer film may be placed in a chamber under normal pressure, and a carrier gas containing a gasification decane coupling agent at a normal pressure may be filled in the chamber, from the deposition of the decane coupling agent to The state of returning to the state in which the vaporized decane coupling agent was not returned was carried out at about atmospheric pressure.

The time during which the organic polymer film is exposed to the vaporized decane coupling agent is not particularly limited, and is preferably within 20 hours, preferably within 60 minutes, more preferably within 15 minutes, and even more preferably within 1 minute. The temperature of the organic polymer film during exposure of the organic polymer film to the vaporized decane coupling agent depends on the type of the decane coupling agent and the thickness of the obtained decane coupling agent layer, and is preferably controlled at -50. A suitable temperature between ° C and 200 ° C is preferred.

The organic polymer film exposed to the vaporized decane coupling agent is preferably heated at 70 ° C to 200 ° C, more preferably 75 ° C to 150 ° C after exposure. By this heating, the hydroxyl group or the like on the surface of the organic polymer film is reacted with the alkoxy group or the decyl group of the decane coupling agent, and the decane coupling agent treatment is completed. The time required for heating is 10 seconds or more and 10 minutes or less. When the temperature is too high or the time is too long, the coupling agent is deteriorated. Also, if the time is too short, the processing effect cannot be obtained. Further, when the substrate temperature during the exposure to the decane coupling agent is 80 ° C or more, the subsequent heating may be omitted. Further, the heating temperature or time depends on the heat resistance of the organic polymer film. It is preferable to use an organic polymer film having high heat resistance in terms of improving the degree of freedom of the conditions of the treatment.

In the present invention, it is preferred that the decane coupling agent of the organic polymer film is coated with the coating surface facing downward to be exposed to the decane coupling agent vapor. In the conventional method of coating a solution of a decane coupling agent, the coated surface of the organic polymer film is inevitably faced upward during and after the coating process, so that it is impossible to deny that the floating foreign matter in the working environment is deposited on the polyoxyn resin. The possibility of the surface. However, in the present invention, since the organic polymer film is held downward, the adhesion of foreign matter in the environment can be greatly reduced.

In addition, when a gas containing a gasified decane coupling agent is introduced into a room where the polymer substrate is exposed, when two or more kinds of gases are temporarily separated and introduced, two or more kinds of gases collide in the room to cause disorder. The flow is also effective for the operation of homogenizing the distribution of the decane coupling agent. As a method of vaporizing the decane coupling agent, in addition to vaporization by heating, it is also preferable to introduce a gas into the decane coupling agent liquid to generate bubbles. This mode is hereinafter referred to as bubbling. In the case of bubbling, it is also effective to place a gas-containing pipe in a decane coupling agent liquid, to attach a porous body to the tip of the pipe, and to generate a large number of fine bubbles, and to superimpose the ultrasonic wave and promote vaporization. Moreover, the vaporized decane coupling agent is often charged, and when an electric field is applied to the organic polymer film during exposure, more decane coupling agent can be deposited in a short time, and the decane coupling agent has kinetic energy, so that it can be suppressed. The deposited film becomes an island film. Further, regarding the carrier gas to be used, it is known that when moisture is contained, the moisture and the decane coupling agent start to react. Therefore, the low dew point is effective. The dew point is preferably 15 ° C or less, more preferably 10 ° C or less, and more preferably 5 ° C or less.

Further, in the present invention, when the dew point of the carrier gas is 0° C. or lower and the reaction between the water and the decane coupling agent is highly suppressed, the reaction of the decane coupling agent in a state in which the film thickness of the deposited film is not uniform at the initial stage of deposition is suppressed. As a result, the film thickness of the deposited film is sufficiently uniform and then uniformly reacts, so that extremely fine unevenness of the surface can be suppressed, and an extremely smooth surface state can be achieved.

The number of the ruthenium-containing foreign matter having a long diameter of 10 μm or more in the decane coupling agent layer of the organic polymer film/polyoxymethylene resin laminate is 2,000/m ² or less, preferably 1,000/m ² or less. A preferred embodiment of the present invention is preferably 500/m ² or less. Further, by combining the above operations, the number of foreign substances containing impurities can be achieved.

Regarding the coating amount and thickness of the coupling agent, it is theoretically sufficient that one molecule layer is sufficient, and the thickness can be neglected at a mechanical design level. In general, it is preferably less than 200 nm (less than 0.2 μm), preferably 150 nm or less (0.15 μm or less), and more preferably 100 nm or less (0.1 μm or less), more preferably 50 nm or less, and even more preferably 10 nm or less. However, when it is calculated to be in the range of 5 nm or less, it is presumed that the coupling agent does not become a uniform coating film but exists in a cluster form, which is not preferable. The bonding of the decane coupling agent layer to the polyoxynoxy resin needs to be carried out. Since the liquid is not in contact with the soft, soft layer, but the solid is in contact with the solid, it cannot be followed without first contacting it. Although the film has flexibility, it cannot follow a fine surface roughness, and the surface roughness needs to be 5.0 nm or less, preferably 3.0 nm or less, and more preferably 1.0 nm or less. The film thickness of the coupling agent layer can be calculated from the concentration of the coupling agent solution and the coating amount at the time of ashing analysis or coating by the ellipsometry method, the fluorescent X-ray method, or the ICP method.

<Method for Producing Laminates> In the present invention, a laminate of an organic polymer film and a polyoxyxene resin can be obtained by the following method: a decane couple of an organic polymer film having a decane coupling agent layer formed thereon On the side of the binder layer, a liquid dimethyl sulfoxane resin is applied, and then it is hardened and solidified by a chemical reaction. The hardening of the polyoxyxylene resin is mainly carried out by dehydration reaction or dealcoholization reaction of a hydroxyl group (-OH) with a methoxy group (-OCH ₃ ) or a hydroxyl group by high molecular weight and crosslinking. Usually, the reaction occurs at 200 ° C to 250 ° C, but can be reduced by the use of a curing catalyst or modification of a polyoxyxylene resin. The coating of the liquid polyoxyl resin can be carried out by spin coating, dip coating, bar coating, applicator, die coater, comma coater, screen printing, gravure printing, capillary coating, spray coating, and the like. Coating method. The thickness of the polyoxyxene resin in the present invention is preferably from 0.5 μm to 10 mm, more preferably from 2 μm to 3 mm, still more preferably from 5 μm to 500 μm. Further, in the present invention, the surface of the film or sheet of the polyoxyxylene resin is activated, and the organic polymer film is coated with the decane coupling agent, and heated and pressurized to obtain a laminate. In this case, it is preferred that the polyoxyphthalocene resin has an unreacted group remaining. In other words, by using the polyoxymethylene resin in the B-stage state, the laminate can be obtained with good efficiency. As a method of heating and pressurizing, a roll grinding method, a pressing method, or the like can be used, and in order to obtain a compact laminate having no foaming or the like, a vacuum pressing device is preferably used. In the present invention, the peeling strength of the polyoxyxene resin layer and the polymer film is 0.3 N/cm or more and 15 N/cm or less. The peeling strength is preferably 0.4 N/cm or more and 12 N/cm or less, more preferably 0.7 N/cm or more and 10 N/cm or less, and more preferably 1.5 N/cm or more and 8 N/cm or less. The peeling strength of the polyoxyxene resin layer and the polymer film can be controlled by the surface treatment of the polymer film, the coating conditions of the decane coupling agent, the coating amount, the coating film thickness, and the lamination conditions. A particularly important parameter is the thickness of the decane coupling agent. By setting the thickness of the decane coupling agent layer to about 40 nm or less, the peel strength can be made within the specified range.

<Application Field of Laminates> The laminate of the present invention exhibits excellent properties of flexibility, heat resistance, electrical properties, chemical durability, and rigidity of an organic polymer film which are possessed by the silicone resin. A laminate obtained by disposing a polyoxymethylene resin on both surfaces of an organic polymer film having excellent heat resistance and dimensional stability can be used as a high-frequency circuit substrate because of good electrical properties and good dimensional stability. High frequency antenna substrate. The organic polymer film is formed into a seamless tube or a seamless strip, and a seamless tube or a seamless belt having a polyoxyxylene resin layer formed on the surface thereof is used as a toner image of a laser printer or the like. A fixing belt for heat fixing, a conveying belt for conveying and superimposing an electrostatic image are useful. When the laminate of the present invention is used as a cushioning material for pressing, both the cushioning property in the thickness direction and the rigidity in the plane direction can be achieved, and the unevenness of the surface direction of the fiber reinforcing body is not obtained, so that it is very Exquisite and good compaction. [Examples]

Hereinafter, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples. Further, the physical property evaluation methods in the following examples are as follows. 1. The reduced viscosity (ηsp/C) of polylysine will be dissolved in N-methyl-2-pyrrolidone (or N,N-dimethylacetone in such a way that the polymer concentration becomes 0.2 g/dl). The solution obtained from the amine was measured at 30 ° C using a Ubbelohde viscosity tube. (When the solvent used for the preparation of the polyaminic acid solution is N,N-dimethylacetamide, the polymer is dissolved and measured using N,N-dimethylacetamide.) 2. Polymer The thickness of the film or the like was measured using a micrometer (manufactured by Feinpruf Co., Ltd., Millitron 1245D). 3. Tensile modulus, tensile breaking strength and tensile elongation at break of the polymer film The polyimine film of the measurement object was cut into 100 mm in the flow direction (MD direction) and the width direction (TD direction), respectively. Short strip of 10mm, used as a test piece, using a tensile tester (made by Shimadzu Corporation, Autograph(R) model name AG-5000A), with a tensile speed of 50mm/min and a distance of 40mm between the chucks, MD The tensile modulus, the tensile strength at break, and the tensile elongation at break were measured in the direction and the TD direction, respectively. 4.90-degree peeling strength The peeling strength of the polyfluorene-oxygen resin layer and the polymer film was determined in accordance with the 90-degree peeling method of JIS K6854-1. Device name: manufactured by Shimadzu Corporation Autograph AG-IS Measurement temperature: room temperature Peeling speed: 50 mm/min Environment: Atmosphere Measuring sample width: 1 cm

5. Linear expansion coefficient (CTE) The polymer film to be measured is measured for the expansion ratio in the flow direction (MD direction) and the width direction (TD direction) under the following conditions, and is measured at 30 ° C to 45 ° C, 45 ° C to 60 ° C, The expansion ratio/temperature of the 15°C interval was measured, and the measurement was carried out up to 300° C., and the average of all the measured values was calculated as the CTE. Equipment name: MMA4000S made by MAC Science Sample length: 20mm Sample width: 2mm Temperature rise temperature: 25°C Temperature rise temperature: 400°C Temperature increase rate: 5°C/min Environment: Argon initial load: 34.5g/mm ² 6 In the average particle diameter of the inorganic particles, the inorganic particles to be measured are dispersed in a solvent as described later, and the particle size distribution is determined by a laser scattering type particle size distribution meter LB-500 manufactured by Horiba, Ltd., and the weight (volume) average is calculated. Particle size and CV 値. 7. Measurement of Thickness of Coupling Agent Layer The thickness of the coupling layer was measured by measuring the film thickness of the Si wafer. The film thickness measurement method was performed using an ellipsometric thickness gauge, and the measuring apparatus used FE-5000 manufactured by Photal Corporation. The hardware specifications of the tester are as follows. The reflection angle range is 45 to 80°, the wavelength range is 250 to 800 nm, the wavelength resolution is 1.25 nm, the spot diameter is 1 mm, the tan Ψ measurement accuracy is ±0.01, and the cos Δ measurement accuracy is ±0.01. The measurement was carried out at 0 to 360° and 250 to 800 nm under the conditions of a deflection angle of 45°, an incident angle of 70°, and a scale of the analyzer of 11.25°. The film thickness was determined by fitting using a nonlinear least squares method. At this time, the model is a model of Air/film/Si, and the wavelength dependence C1 to C6 is obtained by the following equation. n=C3/λ4+C2/λ2+C1 k=C6/λ4+C5/λ2+C4 8. Evaluation of polymer film: roll winding property of a strip-shaped multilayer polyimide film at 2 m/min When the speed was wound around the winding roller (the outer diameter of the mandrel: 15 cm), it was evaluated as ○ when the winding was smoothly wound without wrinkles, and when the wrinkles were partially generated, it was evaluated as Δ, wrinkles were generated, and when it was attached to the roll and could not be smoothly wound. The evaluation is ×. 9. Dry Nitrogen In the present example, it is described that nitrogen gas having a dew point of -10 ° C or less is used in the case of drying nitrogen gas. Further, the nitrogen purity was 99.9% or more. 10. Surface roughness of polymer film The surface roughness of the organic polymer film in the table of the present embodiment refers to the three-dimensional surface roughness Sa after the application of the decane coupling agent to the organic polymer film. 11. The three-dimensional arithmetic mean roughness (Sa) of the SC layer was obtained by using a non-contact surface/layer cross-sectional shape measurement system (VertScan R2.0, manufactured by Ryo Chemical Co., Ltd.). The measurement was carried out under the following conditions. Measurement mode: Phase mode Field of view size: 640 × 480 Filter: 520 nm filter object lens magnification: × 5 Zoom lens magnification: × 1 Measurement range per measurement: 1.4 mm × 1.8 mm Cumulative number: 1 time for the above The raw data obtained by the condition was subjected to only 4 times of surface correction without interpolation, and was used as measurement data. From the measurement data, the following formula is calculated and obtained.

[Math 1] (l _x , l _y are the range of the x direction and the y direction, respectively, and Z (x, y) is the height from the average plane)

<Foreign Density> The range of 100 mm × 100 mm is sampled, and the sampling range is observed by a microscope with a length measurement function of 100 times magnification. For the foreign matter confirmed by 100 times observation, the magnification is further set to 400 times, and the length of the long diameter is measured. Calculate the number of foreign matter of 10 μm or more and divide it by the observed area as the foreign matter density. The unit of foreign matter density is (pieces/m ² ).

<Appearance quality> The appearance of the roll was visually observed and the range from the outer circumference of the roll was about 2 m. When no defects such as scratches, wrinkles, and flatness (undulation) were observed, it was evaluated as ◎, and the defect was partially confirmed, but it was cut into 300 mm width. When the defect portion was avoided, it was evaluated as ○, and when it was cut into 150 mm, the defect portion was evaluated as Δ, and when the defect was unavoidable, it was evaluated as ×.

[Production Examples 1 and 2] (Preparation of Polyamide Acid Solution A1 to A2) After a nitrogen gas replacement was carried out in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 5-amino-2-(amine) was added. Phenyl) benzo After 223 parts by mass of azole and 4416 parts by mass of N,N-dimethylacetamide, and completely dissolved, 217 parts by mass of pyromellitic dianhydride was added to make cerium oxide into the colloidal amount of the amount shown in Table 1. Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industries, Ltd.) in which cerium oxide was dispersed in dimethylacetamide was stirred at a reaction temperature of 25 ° C for 24 hours to obtain a brown and viscous polyamine solution A1 to A2.

【Table 1】

[Production Examples 3 to 4] (Production of Polyamide Acid Solution B1 to B2) After a nitrogen gas substitution in a reaction vessel equipped with a nitrogen gas introduction tube, a thermometer, and a stir bar, 3, 3 of tetracarboxylic dianhydride was used. 398 parts by mass of '4,4'-biphenyltetracarboxylic dianhydride and 147 parts by mass of p-phenylenediamine were dissolved in 4,600 parts by mass of N,N-dimethylacetamide, and added to make cerium oxide a watch 2, the amount of colloidal cerium oxide dispersed in dimethylacetamide, which is made of Snowtex (DMAC-ST30, manufactured by Nissan Chemical Industry Co., Ltd.), and stirred at a reaction temperature of 25 ° C for 24 hours to obtain a brown and viscous poly Proline solution B1 to B2.

【Table 2】

"Film Preparation Example 1" Polyacrylic acid solution A1 was applied to a non-sliding material surface of polyethylene terephthalate film A-4100 (manufactured by Toyobo Co., Ltd.) using a comma-type coater. After drying at 110 ° C for 5 minutes, the polyamic acid film was wound without being peeled off from the support. The obtained polyaminic acid film is mounted on the winding portion of the film forming machine, and the polyamic acid solution A2 is applied to the surface of the polyaminic acid film by using a comma coater to make the polyaminic acid solution A1. The coating amount was a thickness ratio shown in Table 3, and it was dried at 110 ° C for 20 minutes to obtain a two-layered polylysine film. The coating thickness was adjusted so that the thickness of the entire two layers became the thickness shown in Table 3 after the heat treatment. The multilayer poly-proline membrane was subjected to heat treatment in the first stage of 150 ° C × 2 minutes, the second stage of 220 ° C × 2 minutes, and the third stage of 475 ° C × 4 minutes by a pin comber having three heat treatment zones. , cut into a width of 500 mm to obtain a multilayer polyimide film. At this time, the film (film A) having the microadhesive layer attached to the PET film is laminated on the side of the polyaminic acid solution A1 as a non-polyimine protective film which can be peeled off after the heat treatment, and then rolled. Wrap around. The obtained polyimide film was film 1. The properties of the polyimide film are shown in Table 3.

Film Production Example 2 Film 2 was obtained in the same manner as in Production Example 1 except that the coating thicknesses of the polyaminic acid solutions A1 and A2 were set to those shown in Table 3. The contents thereof are also shown in Table 3 in the same manner as in Production Example 1.

Film Production Example 3 A film 3 was obtained in the same manner as in Production Example 1 except that the coating thicknesses of the polyamic acid solutions B1 and B2 were set to those shown in Table 3. The contents thereof are also shown in Table 3 in the same manner as in Production Example 1.

As the film 4, a polyethylene terephthalate film A4100 (manufactured by Toyobo Co., Ltd.) having a thickness of 100 μm was used.

【table 3】

<Coupling Agent Layer Formed in Organic Polymer Film><Coating Example 1 Using a vacuum chamber having a hot plate, a decane coupling agent was applied to the organic polymer film under the following conditions. 100 parts by mass of a decane coupling agent (KBM-903: 3-aminopropyltrimethoxydecane) manufactured by Shin-Etsu Chemical Co., Ltd. was filled in a shallow pan and placed on a hot plate. At this time, the temperature of the hot plate was 25 °C. Then, the organic polymer film of 350 mm × 490 mm was fixed to the frame of SUS and kept vertical in a place separated from the liquid surface of the decane coupling agent by 100 mm or more in the horizontal direction, and the vacuum chamber was closed, and evacuation and nitrogen were performed several times. The introduction is repeated until the oxygen concentration at atmospheric pressure becomes 0.1% or less, and then the pressure in the chamber is reduced to 3 × 10 ^-1 Pa, and the temperature of the hot plate is raised to 60 ° C, and the temperature is kept for 10 minutes, and the vaporization of the decane coupling agent is carried out. After exposure, the temperature of the hot plate is lowered, and the clean dry nitrogen gas is gently introduced into the vacuum chamber from four places and returned to atmospheric pressure, and the organic polymer film fixed to the frame is taken out and placed in a clean environment together with the frame of SUS. 100 ° C heating plate. Due to the thickness of the SUS frame, the organic polymer film is not directly heated in contact with the heating plate. The heat treatment was performed for about 3 minutes to obtain an organic polymer film S1 having a decane coupling agent layer formed on both surfaces of the organic polymer film.

<Coating Example 2> Using a vacuum chamber in which an organic polymer film was placed and a device for volatilizing a decane coupling agent, a decane coupling agent layer was formed on the organic polymer film under the following conditions. The organic polymer film is attached with a protective film on one side in advance. Further, a 350 mm × 490 mm organic polymer film to which a protective film was attached was fixed to a frame of SUS, and was placed vertically in a vacuum chamber. Thereafter, the vacuum chamber was closed, and the vacuum chamber was depressurized to -0.099 MPa. Thereafter, nitrogen gas introduction and evacuation were carried out several times, and evacuation and nitrogen gas introduction were repeated until the oxygen concentration at atmospheric pressure became 0.1% or less. After vacuuming the inside of the vacuum chamber, the state of the silane coupling agent liquid was controlled while the carrier gas was blown to the liquid surface of the decane coupling agent, and the decane coupling agent (KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) was used. : 3-Aminopropyltrimethoxydecane) is added to a device for generating a vapor of a decane coupling agent, and after passing through a temperature adjustment to 30 ° C, a nitrogen gas having a purity of 99.9% or more is passed. The nitrogen gas containing the produced decane coupling agent was introduced into the vacuum chamber through a pipe adjusted to 25 ° C until it reached atmospheric pressure (the degree of vacuum was -0.009 MPa), and it was kept for 20 minutes. After that, the vacuum chamber was evacuated again, and after introducing nitrogen gas and returning to atmospheric pressure, the organic polymer film was taken out from the vacuum chamber, the protective film was peeled off, and heat treatment was performed on a hot plate at 100 ° C for about 3 minutes to obtain an organic system. An organic polymer film S2 having a decane coupling agent is laminated on one side of the polymer film. The vacuum chamber was placed in a room that was tempered to a room temperature of 25 ° C.

<Coating Example 3> Using a vacuum chamber in which an organic polymer film was placed and a device for volatilizing a decane coupling agent, a decane coupling agent layer was formed on the organic polymer film under the following conditions. A protective film is attached to one side of the organic polymer film in advance. Further, a 350 mm × 490 mm organic polymer film to which a protective film was attached was fixed to a frame of SUS, and was placed vertically in a vacuum chamber. Thereafter, the vacuum chamber was closed, and the vacuum chamber was depressurized to -0.099 MPa. Thereafter, nitrogen gas introduction and evacuation were carried out several times, and evacuation and nitrogen gas introduction were repeated until the oxygen concentration at atmospheric pressure became 0.1% or less. After evacuating the vacuum chamber, while controlling the temperature of the decane coupling agent liquid, it is easy to generate bubbles in the porous ceramic and blow the carrier gas by arranging the gas introduction tube to be disposed at the tip end in the decane coupling agent liquid. A decane coupling agent ("KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd.: 3-aminopropyltrimethoxydecane) was added to the apparatus to generate a decane coupling agent vapor, and the temperature was adjusted to 20 ° C. Nitrogen gas having a purity of 99.9% or more is passed. The nitrogen gas containing the produced decane coupling agent was introduced into the vacuum chamber through a pipe adjusted to 25 ° C until the degree of vacuum became +0.009 MPa, and the exhaust port was opened once and then closed, and was brought to about atmospheric pressure for 20 minutes. After that, the vacuum chamber was evacuated again, and then nitrogen gas was introduced. After returning to atmospheric pressure, the organic polymer film was taken out from the vacuum chamber, the protective film was peeled off, and heat treatment was performed on a hot plate at 100 ° C for about 3 minutes to obtain an organic polymer. An organic polymer film S3 having a decane coupling agent is laminated on one side of the film. The vacuum chamber was placed in a room that was tempered to a room temperature of 25 ° C.

<Coating Example 4> Using a vacuum chamber in which an organic polymer film was placed and a device for volatilizing a decane coupling agent, a decane coupling agent layer was formed on the organic polymer film under the following conditions. A protective film is attached to one side of the organic polymer film in advance. Further, a 350 mm × 490 mm organic polymer film to which a protective film was attached was fixed to a frame of SUS, and was placed vertically in a vacuum chamber. Thereafter, the vacuum chamber was closed, and the vacuum chamber was depressurized to -0.099 MPa. Thereafter, nitrogen gas introduction and evacuation were performed several times, and evacuation and nitrogen gas introduction were repeated until the oxygen concentration at atmospheric pressure became 0.1% or less. After evacuating the vacuum chamber, while controlling the temperature of the decane coupling agent liquid, it is easy to generate bubbles in the porous ceramic and blow the carrier gas by arranging the gas introduction tube to be disposed at the tip end in the decane coupling agent liquid. A decane coupling agent ("KBM-903" manufactured by Shin-Etsu Chemical Co., Ltd.: 3-aminopropyltrimethoxydecane) was added to the apparatus to generate a decane coupling agent vapor, and the temperature was adjusted to 20 ° C. Nitrogen gas having a purity of 99.9% or more is passed. Nitrogen containing the produced decane coupling agent was introduced into the vacuum chamber through a pipe adjusted to 25 ° C until the degree of vacuum became -0.09 MPa and held for 5 minutes. Thereafter, the vacuum chamber was again evacuated, and then nitrogen gas containing a decane coupling agent was introduced until the degree of vacuum became -0.09 MPa and held for 5 minutes. This operation was repeated four times, and coating was carried out for 40 minutes. After introducing nitrogen gas and returning to atmospheric pressure, the organic polymer film was taken out from the vacuum chamber, the protective film was peeled off, and heat treatment was performed on a hot plate at 100 ° C for about 3 minutes to obtain a heat treatment. An organic polymer film S4 having a decane coupling agent is laminated on one surface of the organic polymer film. The vacuum chamber was placed in a room that was tempered to a room temperature of 25 °C.

(Coating Example 5) The SUS plate was placed on the side opposite to the side on which the organic polymer film was attached, and the potential was set to +3 kV, and the operation of the coating example 3 was carried out to obtain a single-sided stack of the organic polymer film. The layer is an organic polymer film S5 having a decane coupling agent. (Coating Example 6) The operation of the coating example 3 was carried out except that the gas to be used was changed from a nitrogen gas having a purity of 99.9% or more to a clean dry air, and a decane coupling was obtained on one side of the organic polymer film. The organic polymer film S6 of the agent. <Coating Example 7> The vacuum chamber in which the organic polymer film was placed was repeatedly evacuated and introduced into the nitrogen gas until the oxygen concentration at atmospheric pressure became 0.1% or less, and then clean dry air adjusted to 25° C. and 60% RH was introduced. After -0.19 MPa, the clean dry air containing the produced decane coupling agent was introduced into the vacuum chamber through a pipe adjusted to 25 ° C until the degree of vacuum became +0.009 MPa, and the exhaust port was opened once and then closed. Atmospheric pressure for 20 minutes. In addition to the above, the operation of the coating example 3 was carried out to obtain an organic polymer film S7 having a decane coupling agent laminated on one surface of the organic polymer film.

<Coating Example 8> After the dry nitrogen gas was replaced in the glove box, a small amount of dry nitrogen gas was passed, and a decane coupling agent (KBM-903) manufactured by Shin-Etsu Chemical Co., Ltd.: 3-aminopropyltrimethoxy 0.5 parts by mass of decane) and 99.5 parts by mass of isopropyl alcohol were stirred and mixed in a clean glass vessel to prepare a decane coupling agent solution. On the other hand, a glass plate for liquid crystal of 370 mm × 470 mm and a thickness of 0.7 mm was placed in a spin coater manufactured by Japan Create Co., Ltd., first, 50 ml of isopropyl alcohol was added dropwise to the center of the glass, and the mixture was washed at 500 rpm, and then washed. Approximately 30 ml of the previously prepared decane coupling agent solution was added dropwise to the center of the glass plate, rotated at 500 rpm for 10 seconds, and then the rotation speed was increased to 1500 rpm and rotated for 20 seconds to remove the decane coupling agent solution. Then, the glass plate was taken out from the stopped spin coater, and the decane coupling agent was applied to the hot plate at 100 ° C in a clean environment, and heat treatment was performed for about 3 minutes to obtain a single side of the organic polymer film. An organic polymer film S8 having a decane coupling agent laminated thereon. (Coating Example 9) The operation of the coating example 2 was carried out except that the time for introducing the nitrogen gas containing the decane coupling agent into the vacuum chamber was set to 60 minutes, and the decane couple was laminated on one side of the organic polymer film. The organic polymer film S9 of the crosslinking agent.

In the coating example 10, the temperature of the hot plate on which the decane coupling agent was placed was set to 60 ° C, and the time was set to 60 minutes, and the operation of the coating example 1 was carried out to obtain a laminate on both sides of the organic polymer film. An organic polymer film S10 of a decane coupling agent. (Coating Example 11) The operation of the coating example 4 was carried out except that the time for introducing the nitrogen gas containing the decane coupling agent into the vacuum chamber was set to 60 minutes, and the decane couple was laminated on one side of the organic polymer film. The organic polymer film S11 of the crosslinking agent. (Coating Example 12) The operation of the coating example 3 was carried out except that the time for introducing the nitrogen gas containing the decane coupling agent into the vacuum chamber was set to 60 minutes, and the decane couple was laminated on one side of the organic polymer film. The organic polymer film S12 of the crosslinking agent.

<Coating Example 13> A Cu plate to which a water-cooled tube is welded is provided on the side opposite to the side on which the organic polymer film is attached, and the organic polymer film is cooled to 5° C., and the gas to be used is purged with nitrogen having a purity of 99.9% or more. The operation of the coating example 3 was carried out to obtain an organic polymer film, except that the time of introducing the clean dry air containing the decane coupling agent into the vacuum chamber was set to 60 minutes. An organic polymer film S13 having a decane coupling agent laminated on one side.

【Table 4】 In the table, SCA means a decane coupling agent, and CDA means clean dry air.

(Examples 1 to 18, and Comparative Examples 1 to 6) On the side of the decane coupling agent layer of the organic polymer film of the obtained decane coupling agent layer, the second manufactured by Shin-Etsu Chemical Co., Ltd. was applied by an applicator. The liquid-hardened polyoxyloxy resin SIM-260 was heat-treated at 150 ° C for 30 minutes to obtain a laminate as shown in Table 5. Further, the ratio of the main agent to the hardener was set to a mass ratio of 10/1. The thickness of the polyoxyalkylene resin layer was changed by the following coating conditions to obtain a laminate as shown in Table 5. Further, in Table 5, SC means a decane coupling agent.

【table 5】

<<Example of activation treatment of film>> Using the film Nos. 1 to 4, activation treatment was carried out by vacuum plasma treatment on the side of the film containing no sliding material (A2 layer or B2 layer) to obtain an activation treatment film. The vacuum plasma processing is performed by using the RIE mode RF plasma of the parallel plate type electrode, and the flow control is performed by the mass flow controller in the vacuum chamber so that the N ₂ gas and the Ar gas flow rate are 20 SCCM: 10 SCCM. Import. The process was performed for 2 minutes by introducing high frequency power of 13.56 MHz.

(Examples 19 to 36 and Comparative Examples 7 to 12) Operations were carried out in the same manner as in Examples 1 to 23 and Comparative Example 1, except that the activation treatment film obtained in accordance with the activation treatment example of the film was used. The results are shown in Table 6.

[Table 6] [Industrial use]

As described above, when the coating method of the present invention is used, a laminate of an organic polymer film and a polyoxymethylene resin having excellent appearance quality can be obtained. Such a laminate having a good appearance quality can be used as a support material for a cushion material for precision pressing, a substrate for an electronic component such as a high-frequency circuit substrate, a fixing machine for a heat-fixed image requiring high overlapping precision, and an image conveyance belt. In addition, in the field of information electronics and precision machining, the contribution to the industry is great.

1‧‧‧ polymer film
2‧‧‧ decane coupling agent

Fig. 1 is a conceptual diagram of an apparatus for applying a decane coupling agent to an organic polymer film by a vapor phase method.

no

Claims (12)

A laminate having a decane coupling agent layer on at least one side of an organic polymer film and having a polyoxyalkylene resin layer interposed therebetween, wherein the polyoxyalkylene resin layer is The peeling strength of the polymer film is 0.3 N/cm or more and 15 N/cm or less. The laminate of the first aspect of the invention, wherein the number of the foreign matter containing ruthenium having a long diameter of 10 μm or more in the decane coupling agent layer is 2,000/m ² or less. The laminate according to any one of claims 1 to 2, wherein the decane coupling agent layer has a thickness of from 1 to 500 nm. The laminate according to any one of claims 1 to 2, wherein the laminate has an area of 1000 cm ² or more. The laminate according to any one of claims 1 to 2, wherein the organic polymer film is a polyimide film. A method of manufacturing a laminate according to any one of claims 1 to 5, which comprises: exposing an organic polymer film to a gasified decane coupling agent; The step of forming a layer of a decane coupling agent, and no vacuum is used in this step. The method for producing a laminate according to claim 6, comprising the steps of: exposing the organic polymer film to a decane coupling agent vaporized by bubbling to form a decane coupling agent layer. The method for producing a laminate according to claim 7, wherein in the step of exposing the organic polymer film to the vaporized decane coupling agent to form a decane coupling agent layer, a dew point of 0 ° C is used. The following dry gas acts as a carrier gas. The method for producing a laminate according to any one of claims 6 to 8, wherein the step of exposing the organic polymer film to the vaporized decane coupling agent to form a decane coupling agent layer In the middle, a gas having a dew point of 5 ° C or more is allowed to coexist. The method for producing a laminate according to any one of claims 6 to 8, wherein the step of exposing the organic polymer film to the vaporized decane coupling agent to form a decane coupling agent layer An electric field is applied to the organic polymer film. The method for producing a laminate according to any one of claims 6 to 8, wherein the activation treatment is performed on the surface of the decane coupling agent layer of the organic polymer film before the formation of the decane coupling agent layer. The steps. The method for producing a laminate according to any one of claims 6 to 8, wherein the step of exposing the organic polymer film to the vaporized decane coupling agent to form a decane coupling agent layer The three-dimensional surface roughness (Sa) of the surface of the decane coupling agent layer formed was 5.0 nm or less.