JP2006088581A - Method for producing laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a laminate which can obtain enough adhesive strength. <P>SOLUTION: The method for producing the laminate includes a process in which two or more resin films of the same kind or different kinds and at least one heat generation layer generating heat by an external factor are laminated and a process for making the heat generation layer generate heat by the external factor. For example, when the resin films in the shape of a sheet or a belt are laminated, at least one heat generation layer is laminated (lamination process), and in the production process, the heat generation layer is made to generate heat by the external factor. For example, a heat generation layer (1) containing a photothermal conversion material which generates heat by absorbing light of at least a part of a range from an ultraviolet domain to an infrared domain, a heat generation layer (2) comprising a metal which generates heat by electromagnetic induction, or a heat generation layer (3) holding water which generates heat by microwaves is used preferably as the heat generation layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a laminate of resin films.

  Conventionally, a laminate of resin films has been used in various fields. For example, a laminate in which a thin plate made of a heat-resistant resin or a thin plate obtained by impregnating a heat-resistant resin into a core material and a thin film of a conductive metal such as copper or aluminum is laminated has been widely used as a printed wiring board. Yes. Also, in an image forming apparatus using a dry toner such as an electrophotographic system or an electrostatic recording system, a film in which a heat-resistant resin and a metal thin film are laminated is used as an intermediate transfer body for temporarily supporting a toner image. Sometimes used. In this intermediate transfer member, a toner image formed by adhering toner to an electrostatic latent image is transferred, and this toner image is heated by electromagnetic induction to simultaneously transfer and fix it on a recording medium.

  For example, the intermediate transfer member is, for example, a film-like member made of a heat-resistant resin such as thermosetting polyimide, aromatic polyamide (aramid), or liquid crystal polymer having a thickness of 50 to 200 μm and copper having a thickness of about 1 to 50 μm. These are laminated to form an endless belt. The liquid crystal polymer is a polymer that exhibits liquid crystallinity in a solution state or a molten state, but a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state is particularly high strength, high heat resistance, low linear expansion coefficient, high insulation, low Excellent properties such as moisture absorption and high gas barrier properties. For this reason, the use as a mechanical part and a fiber is increasing as well as what utilizes liquid crystallinity.

  As described above, the production of a film-like member in which a heat-resistant resin layer and a metal thin film are laminated includes a method of bonding a heat-resistant resin film and a metal foil with an adhesive, etc., and electrolysis on a heat-resistant resin film. A method of forming a metal thin film by plating, electroless plating, vapor deposition, or the like is known.

  However, in the method of bonding with an adhesive or the like as described above, the adhesive strength when the metal thin film is repeatedly heated by electromagnetic induction is not reliable.

  Further, even in a method of forming a metal thin film on a heat resistant resin, it is generally difficult to firmly attach a heat resistant resin such as polyimide or aromatic polyamide (aramid) and a metal thin film such as copper. For this reason, a technique for improving adhesion is disclosed. For example, in Japanese Patent Laid-Open No. 5-299820, a metal vapor deposition film is formed on polyimide, and then an electron beam heating vapor deposition copper layer and an electrolytic plating copper layer are formed. A technique for sequentially stacking layers has been proposed.

  In Japanese Patent Laid-Open No. 6-316768, fluorine is contained in polyimide, and in order to use this fluorine as an adhesion site, first, a first-stage etching process is performed using an aqueous solution containing hydrazine, and then A technique is disclosed in which copper is easily deposited by performing a second-stage etching process with naphthalene-1-sodium. Japanese Patent Application Laid-Open No. 7-216225 discloses a technique for improving the adhesion with a metal film by plating by mixing a metal powder with a polyimide precursor.

  Further, even when the heat resistant resin is an aromatic polyamide (aramid), JP-A-6-256960 discloses an etching treatment with an aqueous solution containing hydrazine and an alkali metal hydroxide, and then for electroless plating. Techniques for performing catalyst application treatment have been proposed.

  However, the method of forming a heat-resistant resin and then forming a metal thin film thereon after forming a heat-resistant resin as described above does not provide sufficient adhesion, or the manufacturing process is rationalized. difficult.

  On the other hand, when a liquid crystal polymer is used as the heat-resistant resin, the film-like material can be directly thermocompression bonded to the metal foil, but the liquid crystal polymer film-like member is generally remarkably oriented during molding and is unidirectional. It will be easy to tear. In order to prevent this, Japanese Patent Application Laid-Open No. 2002-248705 proposes manufacturing a belt while reinforcing the belt with a metal foil.

  On the other hand, in Japanese Patent Application Laid-Open No. 2004-4393, a method for producing a polyimide belt mainly composed of polyimide is proposed, and a belt in which silicone rubber or fluororesin is laminated is proposed.

In JP-A-2002-36441, while having excellent impact resistance and weather resistance, etc., the surface hardness is high, and in particular, a hard coat film suitable for application to an outer surface such as a window glass or a plastic board for windows is the same or It has been proposed to provide a silicone-based hard coat layer on one surface of a multilayer base material formed by laminating a plurality of different types of resin films.
JP-A-5-299820 JP-A-6-316768 JP 7-216225 A JP-A-6-256960 JP 2002-248705 A JP 2004-4393 A JP 2002-36441 A

  However, as in the above-described conventionally known techniques, in a laminated body, it is not possible to obtain a sufficient adhesion strength between layers by simply laminating a heat-resistant resin or providing a metal layer. When a force is applied, the phenomenon of a seat that breaks from a thin part with a weak film thickness may occur.

  Accordingly, it is an object of the present invention to solve the conventional problems and achieve the following object. That is, the objective of this invention is providing the manufacturing method of the laminated body from which sufficient adhesive strength is obtained.

The above problem is solved by the following means. That is,
The method for producing the laminate of the present invention comprises:
Laminating a plurality of the same or different resin films and at least one heat generating layer that generates heat due to external factors;
Heating the heat generating layer due to external factors;
It is characterized by having.

  In the method for producing a laminate of the present invention, a resin film is laminated together with a heat generation layer, and the heat generation layer generates heat, whereby the laminate is efficiently heated from the inside of the laminate, and a different resin or metal or resin and metal contact surface Therefore, even if different resin films or functional layers such as metal layers are present, sufficient adhesive strength can be obtained between the respective layers. In addition, the adhesive strength can be more effectively obtained by heating in advance and releasing released gas such as moisture and unreacted monomers present in the material. In the case of dissimilar films, lubricating oil may be applied for protection, and it is costly to use it by wiping it with an organic solvent. This can be removed and the cleaned surface can be provided for bonding.

  The heat generating layer may be laminated in a state where it is formed on the surface of the laminated body, or may be laminated so as to be interposed between the resin films.

  In the manufacturing method of the laminated body of this invention, the following three types are mentioned suitably as said heat generating layer. 1) A heat generating layer containing a photothermal conversion material that generates heat by absorbing at least part of light from the ultraviolet region to the infrared region. 2) A heat generating layer made of a metal that generates heat by electromagnetic induction. 3) A heating layer that retains moisture generated by microwaves.

  In the method for producing a laminate of the present invention, the plurality of resin films may be the same resin film or different resin films. Further, the plurality of resin films may include a heat resistant resin film and an impact resistant resin film.

  In the method for producing a laminate of the present invention, a functional layer may be further laminated together with the plurality of resin films. Examples of the functional layer include a metal layer for electromagnetic induction heating and a silicone hard coat layer for protecting the surface so that the laminate can generate heat when used as a fixing member or an intermediate transfer member of an electrophotographic apparatus. It is done. Moreover, a functional layer may be laminated | stacked in the state formed in the surface of a laminated body, and may be laminated | stacked so that it may interpose between resin films.

  In the manufacturing method of the laminated body of this invention, a laminated body can be formed in a sheet form or a belt form.

  In the manufacturing method of the laminated body of this invention, manufacturing in non-oxidizing atmosphere is suitable. Thereby, the oxidative degradation and rust of the organic or inorganic material which comprises a laminated body can be prevented.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the laminated body from which sufficient adhesive strength is obtained can be provided.

  The method for producing a laminate of the present invention includes, for example, laminating at least one heat generating layer that generates heat due to an external factor when laminating a plurality of sheet-like or belt-like resin films (laminating step), and the production process thereof The heat generation layer generates heat due to external factors (heat generation process). Moreover, when laminating | stacking, you may laminate | stack functional layers, such as a metal layer for electromagnetic induction heating, and a silicone type hard-coat layer, as needed.

  First, as a constituent material of the resin film, for example, a heat resistant resin, an impact resistant resin, and the like are preferably exemplified.

  The heat-resistant resin includes polyester, polyethylene terephthalate, polyether sulfone, polyether ketone, polysulfone, polyimide, polyimide amide, polyamide, etc., but those classified as polyimide, aromatic polyamide, and thermotropic liquid crystal polymer. It is desirable to use it. Examples of the thermotropic liquid crystal polymer include fully aromatic polyester, aromatic-aliphatic polyester, aromatic polyazomethy, aromatic polyester-carbonate.

  Examples of the impact resistant resin include polyethylene, polypropylene, polystyrene, polycarbonate, polyethylene terephthalate, and polyethylene naphthalate. Among these, polyethylene terephthalate and polyethylene naphthalate are preferably used, and polyethylene terephthalate is particularly preferably used.

  As for the method for forming these heat-resistant resin and impact-resistant resin into a film, for thermoplastic materials, extrusion molding or centrifugal molding can be used in a molten state, and the polymer can be molded as a polymer solution or a polymer alloy solution. If it is a thing, it can be applied or cast to be formed into a film, and if it is formed using a precursor before drying and curing reaction, it is coated, dried and cured to form a film. The existing method according to the material can be used.

In addition, as an impact-resistant resin film, a film having Charpy impact strength (JIS K7111 method) of 10 kg ^- cm / cm ² or more is preferably used. In this case, the impact-resistant resin film may be a single layer having a Charpy impact strength of 10 kg ^- cm / cm ² or more, or a single layer having a Charpy impact strength of 10 kg ^- cm / cm ² or less. Even if it exists, it may be laminated and become 10 kg ^- cm / cm ² or more.

  The resin film is generally 6 to 200 μm, more preferably about 50 to 150 μm. Moreover, the resin film may be colored or vapor-deposited as desired, and may contain an ultraviolet absorber. By including the ultraviolet absorber, the weather resistance of the film can be improved. Ultraviolet absorbers absorb ultraviolet rays with high energy, convert them to harmless energy, re-radiate them, thereby providing an ultraviolet blocking effect and improving the light resistance and weather resistance of plastics. , Salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and others. Examples of salicylate ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like. Examples of benzophenone ultraviolet absorbers include 2,2'-dihydroxy-4- Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- And hydroxy-4-octoxybenzophenone. Examples of benzotriazole ultraviolet absorbers include 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3). '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- ( 2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5' Methylphenyl) benzotriazole, 2- [2′-hydroxy-5 ′-(1,1,3,3-tetramethyl) phenyl] benzotriazole, and the like. Examples of substituted acrylonitrile ultraviolet absorbers include 2 -Ethyl cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.

  Further, as other ultraviolet absorbers, for example, resorcinol monobenzoate, 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, N- (2-ethylphenyl) -N '-(2-Ethoxy-5-t-butylphenyl) succinic acid diamide and the like can be mentioned.

  In addition, as the ultraviolet absorber, a light stabilizer such as a hindered amine type which improves light resistance and weather resistance may be used in combination as desired.

  These ultraviolet absorbers may be used alone or in combination of two or more. Moreover, there is no restriction | limiting in particular in content of the ultraviolet absorber in a resin film, Although it selects suitably according to the kind of ultraviolet absorber, the kind of film, etc., Usually 0.01 to 10 weight%, Preferably It is in the range of 0.05 to 5% by weight. When the light stabilizer is used in combination, the total content of the ultraviolet absorber and the light stabilizer is preferably in the range of 0.01 to 10% by weight, particularly preferably in the range of 0.05 to 5% by weight.

  The resin film can be subjected to surface treatment on one side or both sides by an oxidation method or a concavo-convex method, if desired, for the purpose of improving the adhesion with other layers laminated on the surface. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of the base film, but generally, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  Moreover, as a resin film, you may apply the fluororesin film | membrane of the following solid structure. Examples of solid-state fluororesin films include polytetrafluoroethylene (PTFE) films, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA) films, and tetrafluoroethylene-hexafluoropropylene copolymer (FEP) films. Can be mentioned.

  These solid fluororesin films have the following characteristics.

  The porosity is preferably 5 to 98%, more preferably 20 to 96%. The porosity is based on the apparent density measurement of JIS K 6885, and is calculated from the measured apparent density (ρ) by the following formula: porosity (%) = (2.2−ρ) /2.2×100. This is the value obtained.

  The surface roughness (Ra) (value) is preferably 0.5 to 15 μm, more preferably 1 to 10 μm. This surface roughness (Ra) is a value determined according to JIS B 0601.

The tensile strength is preferably 10 N / mm ² or more, more preferably 50 N / mm ² or more. The tensile strength is a value measured according to JIS K 7127 (the test piece is a No. 2 test piece, the test speed is 50 mm / min, the average value of vertical and horizontal).

  The thickness is preferably 1 to 30 μm, more preferably 5 to 25 μm.

  A solid structure fluororesin film having such characteristics is excellent in releasability, strength, wear resistance, and the like.

  Next, a method for manufacturing a solid structure fluororesin film will be described. For example, full-structure PFA and FEP are heat-meltable, and are, for example, full-structure thin films obtained by the extrusion inflation method, casting method, or the like. Further, a solid structure PTFE is a thin film having a solid structure obtained by hot pressing an expanded porous PTFE (ePTFE) film. In particular, a solid PTFE film produced by hot pressing an ePTFE film is particularly preferable because of its excellent heat resistance, releasability, strength, wear resistance, and the like.

  Here, the ePTFE film is a paste formed by mixing PTFE fine powder with a molding aid, after removing the molding aid, stretching at a high temperature and high speed, and further firing if necessary. In the case of uniaxial stretching, the nodes (folded crystals) are thin islands perpendicular to the stretching direction, and the fibrils (folded crystals are unwound by stretching) so as to connect the nodes. The drawn linear molecular bundle is oriented in the stretching direction. And it has a fibrous structure in which spaces defined between fibrils or between fibrils and nodes become holes. In the case of biaxial stretching, the fibrils spread radially, the nodes connecting the fibrils are scattered in islands, and a cobweb-like fibrous structure in which many spaces defined by the fibrils and the nodes exist. ing.

  The ePTFE film may be a uniaxially stretched ePTFE film or a biaxially stretched ePTFE film, but is preferably a biaxially stretched ePTFE film. Since the biaxially stretched ePTFE film is stretched in the biaxial direction, it has lower anisotropy than the uniaxially stretched ePTFE film, and is in the TD direction (film width direction) and MD direction (film length direction). In both cases, a high-strength PTFE membrane can be obtained.

In order to manufacture a solid structure PTFE membrane, for example, first, in the first compression step, the ePTFE film is compressed (pressed) at a temperature lower than its melting point to obtain a rolled film. In this case, the compression temperature is not particularly limited as long as it is lower than the melting point of PTFE, but it is usually 1 ° C. or higher, preferably 100 ° C. or lower. When the compression temperature exceeds the melting point, the shrinkage of the solid film increases. The compression conditions are such that the resulting film has a porosity of 5 to 98% or less, preferably 20 to 96%, more preferably 40 to 95%. The compressive force is a surface pressure, for example, 0.05 to 120 N / mm ² , preferably 0.1 to 100 N / mm ² .

Next, the rolled film obtained in the first compression step is compressed (pressurized) at a temperature equal to or higher than the melting point of PTFE, for example, in the second compression step. In this case, the compression temperature is not particularly limited as long as it is a temperature equal to or higher than the melting point of PTFE, but is usually 1-100 ° C., preferably 20-80 ° C. higher than the melting point. By heating the ePTFE film above the melting point, the smoothness of the solid film surface can be enhanced. The compression temperature is preferably lowered to a temperature lower than the melting point when the pressure is released. When the pressure is released at a temperature higher than the melting point, the shrinkage of the solid film increases and wrinkles easily occur. The compression condition is such a condition that the porosity of the obtained film having a full structure is in the above range. The compressive force is a surface pressure, for example, about 5 to 50 N / mm ² , preferably about 5 to 30 N / mm ² .

  At this time, after compressing the ePTFE film, a temperature higher than the melting point of PTFE is applied, and then it is preferably cooled to a temperature lower than the melting point of PTFE while maintaining the pressure, thereby producing a solid film in one pass. Can do. According to this method, even if a temperature higher than the melting point of PTFE is applied to the ePTFE film from the start of compression, it is cooled to a temperature lower than the melting point of PTFE before the pressure applied to the ePTFE film is released. There is almost no shrinkage in the solid film. For example, if a belt press apparatus is used, a solid film with small shrinkage can be obtained by applying a temperature equal to or higher than the melting point of PTFE while the ePTFE film is compressed between the belts and then cooling to a temperature lower than the melting point. Can do.

  In addition, according to this method, a transparent PTFE thin film having a thin film (for example, 50 μm or less), which has been difficult by the skiving method, can be easily obtained. Further, the surface roughness (Ra) of the obtained PTFE film is determined mainly by compression (pressurization) means in the second compression step (when the press plate is used for hot pressing, the press plate, The surface roughness (Ra) of the heat resistant film).

  Note that a full-structure fluororesin film can be manufactured according to Japanese Patent Application Laid-Open No. 2003-254324.

  Next, the heat generating layer is not particularly limited as long as it generates heat due to an external factor. However, in consideration of handleability and heat generation efficiency, 1) at least a part of light from the ultraviolet region to the infrared region is emitted. Heat generation layer containing a light-to-heat conversion material that generates heat upon absorption (hereinafter referred to as a light-to-heat conversion material-containing heat generation layer) 2) Heat generation layer made of metal that generates heat by electromagnetic induction (hereinafter referred to as a metal heat generation layer) 3) Heat generation by microwaves A heat generating layer that retains moisture (hereinafter referred to as a water retaining heat generating layer) is preferably used. Further, two or more of these heat generating layers may be laminated in the laminated body regardless of the same kind or different kinds. The external factors in these heat generation layers correspond to light, electromagnetic waves, and microwaves, respectively.

  The heat-generating layer containing a light-to-heat conversion material is a layer containing a light-to-heat conversion material in a binder resin, for example. This photothermal conversion material is a material that generates heat by absorbing at least a part of light from the ultraviolet region to the infrared region, and emits light such as ultraviolet rays, visible rays, infrared rays, white rays, etc. according to the wavelength of the irradiation light. Any material that can be absorbed and converted to heat can be used. Specific examples include carbon black, carbon graphite, pigment, phthalocyanine pigment, iron powder, graphite powder, iron oxide powder, lead oxide, silver oxide, chromium oxide, iron sulfide, chromium sulfide, and the like.

  Among these, an infrared absorber that effectively absorbs infrared rays in a wavelength region of 760 to 1200 nm is preferable. Such an infrared absorber is not particularly limited as long as it is a dye that absorbs infrared light and generates heat, and various dyes known as infrared absorbers can be used.

  As the infrared absorber, commercially available dyes and known dyes described in literature (for example, “Dye Handbook” edited by Organic Synthetic Chemistry Association, published in 1970) can be used. Specific examples include azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, and cyanine dyes. Examples of dyes that absorb such infrared light or near infrared light include, for example, JP-A-58-125246, JP-A-59-84356, JP-A-60-78787, US Pat. Cyanine dyes described in Japanese Patent No. 4,973,572, etc., methine described in JP-A Nos. 58-173696, 58-181690, 58-194595, etc. Dye, JP-A 58-112793, JP-A 58-224793, JP-A 59-48187, JP-A 59-73996, JP-A 60-52940, JP-A 60-63744 A naphthoquinone dye described in each publication, a squarylium dye described in JP-A-58-112792, and a cyanine dye described in British Patent No. 434,875. It can gel.

  Further, a near infrared absorption sensitizer described in US Pat. No. 5,156,938, a substituted arylbenzo (thio) pyrylium salt described in US Pat. No. 3,881,924, Trimethine thiapyrylium salt described in JP-A-57-142645, JP-A Nos. 58-181051, 58-220143, 59-41363, 59-84248, 59-84249, 59-14663 Pyryllium compounds described in JP-A-59-146061, cyanine dyes described in JP-A-59-216146, pentamethinethiopyrylium described in US Pat. No. 4,283,475 US Pat. No. 4,756,993, such as salts and pyrylium compounds described in Japanese Patent Publication Nos. 5-13514 and 5-19702. Also suitable are near-infrared absorbing dyes described as formulas (I) and (II) in the specification, commercially available products Epolight III-178, Epolight III-130, and Epolight III-125 manufactured by Eporin. Can be mentioned.

  Another particularly preferable example of the dye is a near-infrared absorbing dye described as formulas (I) and (II) in US Pat. No. 4,756,993.

  The addition amount of the photothermal conversion material (particularly infrared absorber) is 0.01 to 50% by weight, preferably 0.1 to 30% by weight, particularly preferably 1.0 to 30% by weight, based on the total solid content. Can be added. When the addition amount is less than 0.01% by weight, the sensitivity (exothermic property) is lowered, and when it exceeds 50% by weight, the uniformity is lost.

  Specific examples of the light-to-heat conversion material-containing heat generating layer include, for example, those in which a light-to-heat conversion material is included in the resin film. Further, the heat-generating layer containing the photothermal conversion material is not limited to the form in which the photothermal conversion material is included in the resin film (binder resin), and the photothermal conversion material may be deposited by a vapor deposition technique or directly applied. It may be a single layer of photothermal conversion material formed by coating, vacuum plating, or dispersing the photothermal conversion material in a solvent (for example, isopropyl alcohol), applying and drying.

  The light-to-heat conversion material-containing heat generating layer having such a configuration can be heated from the inside of the laminate by generating light by the light-to-heat conversion material absorbing at least a part of the light by light irradiation.

As a light source for irradiating the heat-generating layer containing the photothermal conversion material, there are a normal halogen lamp, mercury lamp, flash lamp, infrared laser, etc., but irradiation with the flash lamp can instantaneously heat the photothermal conversion material. It is ideal for saving energy. The light emission energy of this flash lamp is preferably in the range of 1.0 to 7.0 J / cm ² .

Here, the emission energy per unit area of flash light indicating the lamp intensity of xenon is expressed by the following equation.
Formula: S = ((1/2) × C × V ² ) / (u × L) / (n × f)
Number of lamps: n (books)
Lighting frequency: f (Hz)
Input voltage: V (V)
Capacitor capacity: C (μF)
Process transfer speed: u (mm / s)
Print width: L (mm)
Energy density: S (J / cm ² )

  Moreover, the light source can adjust the irradiation light quantity (irradiation time and illumination intensity), and can control the emitted-heat amount of a heat-generating layer containing a photothermal conversion material.

  The metal heat generating layer is a metal layer made of a metal that generates heat by electromagnetic induction, and as its constituent material, for example, nickel, iron, copper, gold, silver, aluminum, steel, chromium, or the like can be selected. Of these, copper, nickel, aluminum, iron, and chromium are suitable in consideration of cost, heat generation performance, and workability, and copper is particularly preferable. The metal heat generating layer also functions as a functional layer as a metal layer for electromagnetic induction heating, which will be described later.

  The metal heat generating layer is not limited to a single metal layer, and may be a laminate of a plurality of metal layers, or a laminate of different metal layers at that time.

  The metal heating layer can be formed by, for example, electrolytic plating, electroless plating, vapor deposition, sputtering, or the like. The metal heating layer may be formed by laminating a metal foil separately formed by rolling, plating, or the like.

  The metal heat generating layer having such a configuration generates an eddy current in the metal heat generating layer (metal layer) by applying an alternating current to the electromagnetic induction coil to change the generated magnetic field by an excitation circuit. And this eddy current is converted into heat (Joule heat) by the electric resistance of the metal heat generating layer (metal layer) to generate heat, and can be heated from the inside of the laminate.

  Note that an electromagnetic induction heating device that electromagnetically induces a metal heat generating layer can control the amount of heat generated by the metal heat generating layer, for example, by its frequency, output power, electromagnetic wave irradiation time, and the like.

  The moisture retaining heat generating layer is not limited as long as it can retain moisture. However, a water absorbing polymer generally used for paper diapers and the like (for example, Aquakeep (Sumitomo Seika Co., Ltd.) comprising a crosslinked sodium salt of an acrylic acid polymer. Aqua coke (manufactured by Sumitomo Seika Co., Ltd., etc.) made of modified alkylene oxide). The moisture retaining heat generating layer is composed of a porous material [a full-structure fluororesin (ePTFEt made by Japan Gore-Tex) or a foamed polyimide] in which moisture is retained in a physically existing hole in advance by capillary action or the like. May be.

  When the moisture holding heat generating layer having such a structure is irradiated with microwaves, the contained water molecules vibrate the water molecules, generate heat by the frictional heat, and can be heated from the inside of the laminate.

  Note that the microwave heating apparatus that irradiates the moisture holding heat generation layer with microwaves can control the heat generation amount of the moisture holding heating layer according to the frequency, output power, microwave irradiation time, and the like.

  Next, the functional layer will be described. Examples of the functional layer include a metal layer for electromagnetic induction heating and a silicone hard coat layer for protecting the surface so that the laminate can generate heat when used as a fixing member or an intermediate transfer member of an electrophotographic apparatus. It is done.

  The metal layer for electromagnetic induction heating can also serve as the metal heat generating layer as the heat generating layer, and the configuration is the same.

On the other hand, the silicone-based hard coat layer is a layer containing a silicon compound having a siloxane bond, and is preferably a layer mainly composed of, for example, an inorganic silica compound (including polysilicic acid) and / or a polyorganosiloxane compound. Can be mentioned. This inorganic silica-based compound, polyorganosiloxane-based compound, or a mixed system thereof can be produced by various methods as described below. For example, the general formula [1]: R ₁ nSi (OR ₂ ) _4-n [1] [wherein R1 is a non-hydrolyzable group, and includes an alkyl group, a substituted alkyl group (substituent: halogen atom, An epoxy group, a (meth) acryloyloxy group, etc.), an alkenyl group, an aryl group or an aralkyl group, R ₂ is a lower alkyl group, and n is an integer of 0 or 1-3. When there are a plurality of R ₁ and OR ₂ , the plurality of R ₁ may be the same or different, and the plurality of OR ₂ may be the same or different. A method of partially or completely hydrolyzing and polycondensing the alkoxysilane compound represented by the above using an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as oxalic acid or acetic acid is preferably used. In this case, an inorganic silica binder can be obtained by completely hydrolyzing a compound in which n is 0, that is, tetraalkoxysilane, and a polyorganosiloxane binder or inorganic silica and polyorganosiloxane can be obtained by partial hydrolysis. A mixed system binder is obtained. On the other hand, since a compound having n of 1 to 3 has a non-hydrolyzable group, a polyorganosiloxane-based binder can be obtained by partial or complete hydrolysis. At this time, an appropriate organic solvent may be used in order to perform hydrolysis uniformly.

  Examples of the alkoxysilane compound represented by the general formula [1] include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraisobutoxysilane, tetra -Sec-butoxysilane, tetra-tert-butoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, butyl Trimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloylio Shi trimethoxysilane, dimethyl dimethoxysilane, methylphenyl dimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, divinyl dimethoxysilane, divinyl diethoxy silane, trivinyl silane, such as trivinyl silane and the like. These may be used alone or in combination of two or more. At this time, if necessary, an appropriate amount of an aluminum compound such as aluminum chloride or trialkoxyaluminum can be added. Furthermore, as another method, sodium metasilicate, sodium orthosilicate or water glass (sodium silicate mixture) is used as a raw material silicon compound, and an acid such as hydrochloric acid, sulfuric acid or nitric acid or a metal compound such as magnesium chloride or calcium sulfate is added. A method of acting and hydrolyzing can be used. By this hydrolysis treatment, free silicic acid is produced, which is easily polymerized and is a mixture of chain, ring, and network, depending on the type of raw material. The polysilicic acid obtained from water glass is mainly composed of a chain structure represented by the general formula [2] (where m represents the degree of polymerization and R represents hydrogen, silicon or a metal such as magnesium or aluminum) .)

In this way, a complete inorganic silica-based binder is obtained. Silica gel (SiO _x .nH ₂ O) can also be used as the inorganic silica binder. In this hard coat layer, since hard coat performance is regarded as important, a layer containing as much inorganic silica compound as possible is preferable as long as necessary adhesion is maintained. In addition, the hard coat layer may contain an inorganic ultraviolet scattering agent or the like as desired as long as the scratch resistance is not impaired.

  This hard coat layer is obtained by applying a hard coat agent-containing coating solution on a laminate using a known method such as a bar coat method, a knife coat method, a roll coat method, a blade coat method, a die coat method, or a gravure coat method. It can be formed by coating and heating to cure. The thickness of the hard coat layer thus formed is usually 0.05 to 30 μm, preferably 1.0 to 20 μm.

  The hard coat layer is preferably formed on one surface of the laminate. When the laminate is a laminate of a weather resistant resin film and an impact resistant resin film, it is particularly preferable to provide a hard coat layer on the surface of the weather resistant resin film. For the purpose of improving the adhesion between the laminate and the hard coat layer, the surface of the laminate on which the hard coat layer is provided may be subjected to a surface treatment on one or both sides by an oxidation method or an uneven method, if desired. it can. Examples of the oxidation method include corona discharge treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment and the like, and examples of the unevenness method include sand blast method and solvent treatment method. Is mentioned. These surface treatment methods are appropriately selected according to the type of the laminate, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  Moreover, you may provide the primer layer in the surface of the laminated body in which a hard-coat layer is provided as needed. The primer is not particularly limited, and conventionally known primers such as acrylic, polyester, polyurethane, silicone, and rubber can be used. From the viewpoint of durability and adhesion, acrylic System and polyester primers are preferred. This primer can contain an ultraviolet absorber and a light stabilizer, if necessary. The thickness of the primer layer is preferably in the range of 0.1 to 10 [mu] m, particularly preferably in the range of 0.5 to 5 [mu] m, from the viewpoints of uniform coatability and adhesion.

  In the method for producing a laminate of the present invention, one or more selected from the resin film, one or more selected from the heat generating layer, and a functional layer as necessary are laminated. The thickness is not particularly limited and may be appropriately selected depending on the purpose of use, and is usually 350 μm or less, preferably 100 to 250 μm.

  The laminating method is performed by various general-purpose means, and may be, for example, laminating using an adhesive or a pressure-sensitive adhesive, or may be dry lamination not using an adhesive or the like, or a combination thereof. . Moreover, after apply | coating the liquid substance which forms the other film on one film, a resin film can also be laminated | stacked by hardening a liquid substance.

  As the adhesive or pressure-sensitive adhesive, conventionally known acrylic, polyether-based, silicone-based, rubber-based adhesives or pressure-sensitive adhesives are used without any particular limitation. When using an adhesive or a pressure-sensitive adhesive, the amount used is not particularly limited, but it is used so that the total thickness of the laminate falls within the above range.

  Moreover, when laminating | stacking only the same kind as a some resin film, the film which consists of a polyimide or a polyamideimide especially among resin films is used preferably. On the other hand, when different types are laminated, it is preferable to use a combination of films having different characteristics.

  The heat generating layer of the laminated body thus laminated is heated and heated from the inside. This heating may be performed at the time of lamination (each lamination) or before and after lamination. As a result, it is possible to efficiently heat from the inside of the laminate and to reduce or reduce the thermal resistance of the different resin or metal or the resin-metal contact surface. Even if layers are present, sufficient adhesive strength can be obtained between the layers. In addition, the adhesive strength can be more effectively obtained by heating in advance and releasing released gas such as moisture and unreacted monomers present in the material.

  In the case of dissimilar films, lubricating oil may be applied for protection, and it is costly to use it by wiping it with an organic solvent. This can be removed and the cleaned surface can be provided for bonding.

  Moreover, you may utilize the heating by a heat-emitting layer for the hardening reaction and solvent removal at the time of application | coating formation of a resin film, and the residual solvent removal of a laminated body. Moreover, the heating by the heat generating layer may be laminated, for example, in a semi-cured state of the resin film and contribute to the complete curing. Thereby, a laminated body is obtained efficiently.

  Furthermore, it is preferable to manufacture the laminate in a non-oxidizing atmosphere in order to prevent a part or all of the laminate from being oxidized. This non-oxidizing atmosphere can be realized, for example, by filling an inert gas such as nitrogen or argon at 2 atm or normal pressure. Thereby, it is possible to effectively prevent oxidative deterioration and rust of the organic or inorganic material (particularly the metal layer) constituting the laminate.

  In addition, the obtained laminated body can be utilized in various fields by the material type and shape (sheet shape or belt shape) of the resin film. The obtained laminate can also be used as a heating element having a heating layer as a heating source.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention.

Example 1
First, an infrared absorber (C.I.I.) was added to a solution obtained by reacting 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and aromatic diamine in N-methyl-2-pyrrolidone. Pigment Blue 15, α-type copper phthalocyanine) is added at 5 parts by weight with respect to 100 parts by weight of resin to prepare a polyimide precursor solution, which is irradiated with 5 J / cm ² light from a xenon lamp for 30 minutes. The viscosity of the solution is adjusted to 300 poise by increasing the viscosity of the infrared absorber by generating heat. In addition, a resistivity adjusting conductive agent (tin oxide) was added to the polyimide precursor solution at 5 parts by weight with respect to 100 parts by weight of the resin content.

  Next, a centrifugal molding apparatus having a heatable rotating drum and a light source composed of a xenon lamp that irradiates light into the rotating drum is prepared, and a coating film having a desired thickness is formed while first rotating the rotating drum at room temperature. A predetermined amount of the polyimide precursor solution obtained in advance is poured into the rotating drum so as to be obtained. When the injection of a predetermined amount is completed, the rotation is gradually accelerated to reach the required rotation speed, and then the entire drum is gradually heated, and the rotation speed is maintained for a predetermined time after reaching a predetermined temperature. The various conditions such as the predetermined time were such that the rotation speed was 300 rpm and the drum temperature was 60 ° C.

At this time, along with the heating of the rotating drum, the coating film is heated by irradiating the coating film of the polyimide precursor solution with light of 3 J / cm ² from the light source for 120 minutes and causing the blended infrared absorber to generate heat. The solvent evaporates from the coating film by this heating.

  Next, when a predetermined time elapses in the heating state, the heating is stopped, and the rotation is stopped when the whole is cooled to room temperature.

  Next, the rotating drum is heated, the temperature of the polyamic acid belt-like material of the polyamic acid is raised to a predetermined temperature, and heating is continued at that temperature for a predetermined time. The temperature was 350 ° C. to 500 ° C., and the time was 3 to 30 minutes. When heating for a predetermined time is finished, the heating is stopped and cooled to room temperature. In this way, the residual solvent is completely removed, and a belt of polyimide acid is obtained.

Then, while heating the rotating drum and irradiating light from a light source to the belt-like material of polyamic acid at an illuminance of 7.5 J / cm ² at intervals of 200 ms, the blended infrared absorber is heated to raise the belt-like material. Warm up. Thus, the belt-like product was heated at a temperature of 120 ° C. for 5 hours to remove the residual solvent and imidize, thereby forming a belt molded body made of a polyimide resin having a thickness of 10 μm.

Next, a solid PTFE film having a thickness of 8 μm was laminated on the inner surface of the belt molded body. At this time, the belt-shaped article was heated to 400 ° C. by irradiating the belt molded body with light at an illuminance of 7.5 J / cm ² from the light source at an interval of 200 ms to generate heat.

Here, a solid PTFE film having a thickness of 8 μm was produced as follows. First, the ePTFE membrane (porosity 60%, thickness 15 μm) was compressed with a calender roll device at a roll temperature of 70 ° C., a linear pressure of 18 N / mm ² , a feed rate of 1 m / min, and a porosity of 55% and a thickness of 20 μm. A rolled film was obtained.

  The obtained rolled film was sandwiched between two polyimide films (Ube Industries, Upilex 20S), and hot-pressed with a hot press device at a press plate temperature of 120 ° C. and a surface pressure of 1 MPa for 2 seconds, surface roughness Ra of 5 μm, empty A solid PTFE film having a porosity of 50% and a thickness of 8 μm was obtained.

  One side of this solid PTFE film was subjected to corona discharge treatment and laminated on the inner wall of the belt molded body so that the corona treatment surface was on the outside.

  This operation was repeated three times to obtain a laminate having a thickness of 54 μm in which three layers of a belt molded body made of polyimide resin and a solid PTFE film were alternately laminated.

  The adhesive strength of the obtained laminate was 0.8 kN / m. In addition, this adhesive strength is measured by removing a part (width 10 mm, length 100 mm) of the layers (excluding the metal layer (metal plating)) constituting the front and back surfaces of the laminate, and holding the grip (Toyo Baldwin) , 100 kg Tensilon device) and measured the load when peeled off in the vertical direction at about 50 mm at room temperature. The same applies hereinafter.

(Example 2)
Next, the inside of the rotating drum 11 is immersed in a 2 g / L solution of carboxybenzotriazole (CBTA) at 30 ° C. for 30 seconds, and then taken out and washed with water. Thereby, a release layer is formed. In order to immerse in the solution, masking is performed on a portion where the release layer is unnecessary, such as the outer peripheral surface of the rotating drum, and the solution is immersed in a tank storing the solution.

  Next, copper plating with a thickness of 5 μm was formed on the surface of the formed release layer, and further, electroless nickel plating with a thickness of 1 μm was formed on the inner peripheral surface of the rotating drum on the copper plating.

  Then, a belt molded body made of a polyimide resin having a thickness of 10 μm was formed on the electroless nickel plating in the same manner as in Example 1. At this time, light irradiation is performed in the same manner as in Example 1, and the generated magnetic field is generated by applying an alternating current to the electromagnetic induction coil with the electromagnetic induction coil facing the belt molded body having copper plating and nickel plating. By changing the excitation circuit, the copper plating and nickel plating were heated to 100 ° C.

  In this way, copper plating, nickel plating, polyimide resin, nickel plating, copper plating, nickel plating, polyimide resin, nickel plating, copper plating, nickel plating, polyimide resin are repeatedly laminated on the inner surface of the rotating drum, A laminate having a thickness of 50 μm was obtained. This operation was performed in a nitrogen atmosphere so that the plating was not oxidized. The adhesive strength of the obtained laminate was 0.5 kN / m.

(Example 3)
In Example 1, instead of a solid PTFE film, aqua keep (made by Sumitomo Seika Co., Ltd.) made of a crosslinked sodium salt of an acrylic acid polymer that had been pre-hydrated was laminated at a thickness of 20 μm. A laminate was obtained in the same manner as in Example 1. However, at the time of laminating the aqua keep, as in Example 1, light irradiation was performed to heat the polyimide resin belt molded body, and the aqua keep was irradiated with microwaves to generate heat at 100 ° C. The adhesive strength of the obtained laminate was 0.8 kN / m.

Example 4
In Example 1, instead of a solid PTFE film, a silicone-based hard coat agent (Solguard NP-730 manufactured by Nippon Dacro Shamrock) was applied to a dry film thickness of 3 μm and dried at 130 ° C. for 3 minutes. A laminate was obtained in the same manner as in Example 1 except that the hard coat film was laminated. The adhesive strength of the obtained laminate was 0.6 kN / m.

(Comparative Example 1)
In Example 1, a laminate was obtained in the same manner as in Example 1 except that no infrared absorber was added to the polyimide resin precursor solution and no heat was generated by light irradiation. The adhesive strength of the obtained laminate was 0.1 kN / m.

  From these Examples and Comparative Examples, it can be seen that a strong adhesive strength can be obtained by laminating a heat generating layer and generating heat.

Claims (11)

Laminating a plurality of the same or different resin films and at least one heat generating layer that generates heat due to external factors;
Heating the heat generating layer due to external factors;
The manufacturing method of the laminated body characterized by having.   The method for manufacturing a laminate according to claim 1, wherein the heat generating layer includes a photothermal conversion material that generates heat by absorbing at least a part of light from an ultraviolet region to an infrared region.   The method for manufacturing a laminate according to claim 1, wherein the heat generating layer is made of a metal that generates heat by electromagnetic induction.   The method for manufacturing a laminate according to claim 1, wherein the heat generating layer holds moisture generated by microwaves.   The method for producing a laminate according to claim 1, wherein the plurality of resin films are the same resin film.   The method for producing a laminate according to claim 1, wherein the plurality of resin films are different kinds of the resin films.   The method for producing a laminate according to claim 1, wherein the plurality of resin films include a resin heat resistant resin film and an impact resistant resin film.   Furthermore, a functional layer is laminated | stacked, The manufacturing method of the laminated body of Claim 1 characterized by the above-mentioned.   The method for producing a laminate according to claim 8, wherein the functional layer is a silicone-based hard coat layer.   The method for producing a laminate according to claim 1, wherein the laminate is formed into a sheet shape or a belt shape.   It manufactures in a non-oxidizing atmosphere, The manufacturing method of the laminated body of Claim 1 characterized by the above-mentioned.