JP6709302B2 - High heat resistance and high slidability film - Google Patents

Description

The present invention relates to a highly heat resistant and highly slidable film having excellent heat resistance and slidability.

Polyetheretherketone (PEEK) resin film has mechanical properties, heat resistance, chemical resistance, radiation resistance, hydrolysis resistance, electrical insulation, low water absorption, flame retardancy, water vapor barrier property, gas barrier property. It is an excellent film, and in view of its characteristics, it has been proposed or used in a wide range of fields such as electric/electronic devices, medical devices, automobiles and aircrafts.

Specifically, in the field of electrical and electronic equipment, for example, diaphragms of micro speakers, circuit boards, base films of adhesive tapes, dielectrics of film capacitors, various belts used in copiers, printers and printers. In the field of medical equipment, for example, it has been proposed or used as a base film for laser marking labels and the like. Further, in the field of automobiles, for example, slot insulation paper for oil-tangenators, films for covering rectangular electric wires used in drive motors for hybrid electric vehicles and electric vehicles, diaphragms for high-performance speakers or films for carbon fiber composite materials, etc. In the field of aircraft, it has been proposed and used as a film for heat insulating and soundproof brackets, a film for carbon fiber composite materials, and the like.

By the way, in the above-mentioned fields, high heat resistance and high slidability are demanded. With this demand, resin films such as polyether ether ketone resins used in the fields concerned also have high heat resistance and high slidability. Is being requested. As a method for producing a highly slidable polyetheretherketone resin molded article, for example, a fluororesin is added to a polyetheretherketone resin to prepare a resin composition, and a high sliding property is obtained by using this resin composition. A method for producing a molded product of a polymerizable polyether ether ketone resin has been proposed and implemented (see Patent Documents 1 and 2).

In the method for producing a highly slidable polyether ether ketone resin molded article of Patent Document (1), the melt flow index at 360° C. and 2.16 kg has a value of 2.0 to 30.0 g/10 min. Molded product from a polyether aromatic ketone resin composition comprising 60 to 99 parts by mass of an ether aromatic ketone resin and a fluororesin having a melt flow index (400° C., 10 kg) of 3.0 kg/10 min or less. Is a method of manufacturing.

On the other hand, in the production method of Patent Document (2), the polyether aryl ketone resin-containing polyarylketone resin contains 70 to 99% by mass and the fluororesin 30 to 1% by mass, and is dispersed in the resin composition. Is a method for molding from a resin composition in which the average particle size of the fluororesin is 0.1 to 30 μm.

JP-A-6-136255 JP 2006-274073 A

However, although the polyether ether ketone resin films obtained by the methods of Patent Documents 1 and 2 have excellent slidability, they are polyether ketone (PEK) resins, polyether ether ketone resins, polyether ketone ketone (PEKK) resins, Polyarylene ketone resins such as ether ether ketone ketone (PEEKK) resins have a low glass transition point of 140 to less than 170° C., and therefore, when used for applications at 170° C. or higher, the film may be deformed or torn. There is. That is, the conventional polyetheretherketone resin film has a problem in heat resistance, and there is a problem in that it cannot be obtained by combining excellent heat resistance and slidability.

The present invention has been made in view of the above, and an object of the present invention is to provide an inexpensive high heat resistant/high slidable film having excellent heat resistance and slidability.

The inventors of the present invention have completed the present invention by paying attention to the fact that the polyetheretherketone resin and the specific polyetherimide resin show good compatibility as a result of intensive studies to solve the above problems.

冷却されたフィルムの特性は、耐熱性〔貯蔵弾性率（Ｅ’）の第一変曲点温度〕が１７０℃以上、２８０℃における貯蔵弾性率が１×１０^５Ｐａ以上、摺動性がＪＩＳ Ｋ７１２５−１９９９に準拠して測定した静的摩擦係数で１．０以下であるとともに、ＪＩＳＫ７１２５−１９９９に準拠して測定した動的摩擦係数で１．０以下であることを特徴としている。 That is, in the present invention, in order to solve the above problems, a polyether ether ketone resin having a repeating unit represented by the chemical formula [Chemical Formula 1] and a repeating unit represented by the chemical formula [Chemical Formula 2], The polyetherimide resin having a point of 200° C. or higher is fluorine based on 100 parts by mass of the resin composition composed of 5 to 70% by mass of the polyetheretherketone resin and 95 to 30% by mass of the polyetherimide resin in a composition mass ratio. 1 to 30 parts by mass of a resin is added,

The properties of the cooled film are heat resistance [the first inflection point temperature of storage elastic modulus (E′)] is 170° C. or more, storage elastic modulus at 280° C. is 1×10 ⁵ Pa or more, and slidability is JIS. The static friction coefficient measured according to K7125-1999 is 1.0 or less , and the dynamic friction coefficient measured according to JIS K7125-1999 is 1.0 or less .

The thickness of the cooled film is preferably 3 to 1000 μm.

Here, the high heat resistance and high slidability film in the claims is used in the field of electric equipment, for example, as a diaphragm of a micro speaker, a circuit board, a base film of an adhesive tape, a dielectric of a film capacitor, a copying machine. For various belts used in printing machines and printers, it can be used as a base film for laser marking labels in the field of medical equipment. Further, in the field of automobiles, for example, slot insulation paper for oil-tanators, films for covering rectangular electric wires used in hybrid electric vehicles and drive motors for electric vehicles, diaphragms for high-performance speakers, films for carbon fiber composite materials, etc. In the field of aircraft, it can be used as a film for heat insulating and soundproof brackets, a film for carbon fiber composite materials, and the like.

According to the present invention, a high heat resistance and high slidability film is extruded from a predetermined polyether ether ketone resin, and a melted mixture of a polyether imide resin and a fluororesin, so that excellent heat resistance and slidability are obtained. Can be obtained at low cost.

According to the present invention, there is an effect that a highly heat resistant and highly slidable film having excellent heat resistance and slidability can be obtained at low cost. Further, the slidability of the cooled film is 1.0 or less as a static friction coefficient measured according to JIS K7125-1999, and is 1. 0 as a dynamic friction coefficient measured according to JIS K7125-1999. Since it is 0 or less, a highly heat-resistant and highly slidable film having sufficient slidability can be obtained.

According to the invention of claim 2, since the cooled film has a thickness of 3 to 1000 μm, it is possible to eliminate the possibility that the high heat resistant/high slidability film may be broken during molding due to the decrease in the strength of the film. You can Furthermore, since the thickness of the high heat resistant/high slidable film is less than 1000 μm, it is possible to prevent the molding speed of the high heat resistant/high slidable film from decreasing and the productivity from deteriorating.

FIG. 1 is an overall explanatory view schematically showing an embodiment of a method for producing a highly heat resistant and highly slidable film according to the present invention. It is a graph which shows the change curve of the storage elastic modulus in the Example of the manufacturing method of the high heat resistance and high slidability film which concerns on this invention.

Hereinafter, a preferred embodiment of the present invention will be described with reference to the drawings. A method for producing a highly heat-resistant and highly slidable film 1 according to the present embodiment is represented by a chemical formula [Chemical formula 1] as shown in FIG. Melting molding material 2 composed of a polyetheretherketone resin having a repeating unit represented by the formula, a polyetherimide resin having a repeating unit represented by the chemical formula [Chemical Formula 2] and having a glass transition point of 200° C. or higher, and a fluororesin. A high heat resistant/high slidability film 1 is continuously extruded from a T die 13 of a melt extrusion molding machine 10 using this molding material 2 and the extruded high heat resistant/sliding property is obtained. The film 1 is sequentially wound around the pressure roll 16, the cooling roll 17, and the winding tube 19 of the winder 18, and the high heat-resistant and highly slidable film 1 is sandwiched between the pressure roll 16 and the cooling roll 17. By cooling, the highly heat resistant and highly slidable film 1 is manufactured.

The molding material 2 of the highly heat resistant and highly slidable film 1 has a polyether ether ketone resin having a repeating unit represented by the chemical formula [Chemical Formula 1] and a repeating unit represented by the chemical formula [Chemical Formula 2], Polyetherimide resin having a glass transition point of 200° C. or higher is used with respect to 100 parts by mass of a resin composition composed of 5 to 70% by mass of polyetheretherketone resin and 95 to 30% by mass of polyetherimide resin in a composition mass ratio. It is prepared by adding 1 to 30 parts by mass of the fluororesin.

The molding material 2 includes polyimide resin such as polyimide (PI) resin and polyamide-imide (PAI) resin, polyamide 4T (PA4T) resin, polyamide 6T (PA6T) resin, modified polyamide 6T (modified PA6T) resin, polyamide 9T ( PA9T) resin, polyamide 10T (PA10T) resin, polyamide 11T (PA11T) resin, polyamide 6 (PA6) resin, polyamide 66 (PA66) resin, polyamide 46 (PA46) resin and other polyamide resins, polyetherketone (PEK) resin , Polyetherketoneketone (PEKK) resin, polyetheretherketoneketone (PEEKK) resin and other polyarylketone resins, polysulfone (PSU) resins, polyethersulfone (PES) resins, polyphenylenesulfone (PPSU) resins, etc. A polyarylene sulfide resin such as a polysulfone resin, a polyphenylene sulfide (PPS) resin, a polyphenylene sulfide ketone resin, a polyphenylene sulfide sulfone resin, a polyphenylene sulfide ketone sulfone resin, a liquid crystal polymer (LCP) or the like can be added.

Polyetheretherketone resin having a repeating unit represented by the chemical formula [Chemical Formula 1], polyetherimide resin having a repeating unit represented by the chemical formula [Chemical Formula 2] and having a glass transition point of 200° C. or higher, and fluorine The molding material 2 made of a resin melt-kneaded product contains, in addition to the above resins, an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer, a lubricant, a flame retardant, an antistatic agent, as long as the characteristics of the present invention are not impaired. Agents, heat resistance improvers, inorganic compounds, organic compounds and the like are selectively added.

The polyether ether ketone resin is not particularly limited, but is a resin having a repeating unit represented by the chemical formula [Formula 1].

The melting point of the polyether ether ketone resin is usually 320 to 360°C, preferably 335 to 345°C. From the viewpoint of mechanical properties, n in the chemical formula [Formula 1] in the polyether ether ketone resin is preferably 10 or more, and more preferably 20 or more. The polyether ether ketone resin may be a homopolymer consisting only of the repeating unit of the chemical formula [Chemical formula 1] or may have a repeating unit other than the chemical formula [Chemical formula 1].

However, in the polyether ether ketone resin, the ratio of the chemical structure of the chemical formula [Formula 1] is preferably 50 mol% or more, more preferably 70 mol% or more, and more preferably 80 mol% with respect to 100 mol% of the polyether ether ketone. Optimal. Specific examples of the polyetheretherketone resin include trade names manufactured by Victor Wreck: Victorex Peak series, trade names manufactured by Daicel-Evonik: vestakeep series, trade names manufactured by Solvay Specialty Polymers: KetaSpire polyether ether Ketone series can be mentioned.

Examples of the method for producing a polyether ether ketone resin include, for example, JP-A-50-27897, JP-A-51-119797, JP-A-5238000, JP-A-54-90296, and JP-B-KOKAI. The methods described in Japanese Patent No. 55-23574, Japanese Patent Publication No. 56-2091, etc. are applicable. A block copolymer, a random copolymer, or a modified product with another copolymerizable monomer may be used as long as the polyether ether ketone resin does not impair the effects of the present invention.

As the polyetherimide resin having a glass transition point of 200° C. or higher, a polyetherimide resin having a repeating unit of the chemical formula [Chemical Formula 2] is preferably used.

It is known that the polyetheretherketone resin having the repeating unit of the chemical formula [Chemical formula 1] and the polyetherimide resin having the repeating unit of the chemical formula [Chemical formula 2] have very good compatibility (patent). No. 4201965). On the other hand, it is known that the polyetheretherketone resin having a repeating unit represented by the chemical formula [Chemical Formula 1] and the polyetherimide resin having a repeating unit represented by the chemical formula [Chemical Formula 3] have poor compatibility (patent). No. 4201965).

Since the melt-kneaded product of the polyether ether ketone resin having the repeating unit of the chemical formula [Chemical formula 1] and the polyetherimide resin having the repeating unit of the chemical formula [Chemical formula 3] is inferior in compatibility, the melt-kneaded product is It is known that the peak temperature of loss tangent (tan δ) obtained by dynamic viscoelasticity measurement originates from the polyether ether ketone resin and polyether imide resin components mixed between 140 to 250° C., and at least two are observed. (See Japanese Patent No. 4201965). The fact that two loss tangents are observed means that two glass transition points derived from the polyetheretherketone resin and the polyetherimide resin component are also observed. The kneaded product cannot have higher heat resistance than the polyether ether ketone resin having the repeating unit represented by the chemical formula [Formula 1]. Further, since the compatibility is poor, the mechanical properties of the film are deteriorated, and the thin-wall moldability of the film is poor.

Specific examples of the polyetherimide resin having a repeating unit represented by the chemical formula [Chemical Formula 2] include ULTEM 1010-1000-NB [product name manufactured by SABIC Innovative Plastics Co., Ltd.] and ULTEM 9011-1000-NB [the same]. The method for producing the polyetherimide resin having the repeating unit represented by the chemical formula [Chemical Formula 2] is not particularly limited, but is usually 4,4′-[isopropylidene bis(p-phenyleneoxy)diphthalic acid dianhydride. Compound] and m-phenylenediamine.

Specific examples of the polyetherimide resin having a repeating unit represented by the chemical formula [Chemical Formula 3] include ULTEM CRS5001-1000-NB [trade name of SABIC Innovative Plastics]. As a method for producing a polyetherimide resin having a repeating unit represented by the chemical formula [Chemical Formula 3], 4,4′-[isopropylidene bis(p-phenyleneoxy)diphthalic acid dianhydride] and p-phenylenediamine are polycondensed. Manufactured by a known method.

A polyetherimide resin having a repeating unit of the chemical formula [Chemical Formula 3] can be added to the polyetherimide resin having a repeating unit of the chemical formula [Chemical Formula 2] within a range that does not impair the effects of the present invention. Further, it is possible to add a block copolymer, a random copolymer, or a modified product with another copolymerizable monomer such as an amide group, an ester group, a sulfonyl group, or a siloxane group. For example, a polyetherimide sulfone copolymer having a glass transition point of 238[deg.] C., ULTEM XH6050-1000 [SABIC Innovative Plastics Co., Ltd. product name], a polyetherimide/siloxane copolymer ULTEM STM1.
700-1000 [SABIC Innovative Plastics Co., Ltd. product name] and the like can be mentioned.

A polyetheretherketone resin having a repeating unit represented by the chemical formula [Chemical Formula 1] and a polyetherimide resin having a repeating unit represented by the chemical formula [Chemical Formula 2] and having a glass transition point of 200° C. or higher, It is composed of 5 to 70% by mass of polyether ether ketone resin and 95 to 30% by mass of polyetherimide resin in a composition mass ratio. This is because when the polyetheretherketone resin exceeds 70% by mass or the polyetherimide resin is less than 30% by mass, the heat resistance of the high heat resistance/high slidability film 1 cannot be enhanced. On the other hand, when the content of the polyether ether ketone resin is less than 5% by mass and the content of the polyetherimide resin exceeds 95% by mass, the heat resistance at a temperature of 280° C. or higher is poor, which is not preferable.

The fluororesin is preferably solid at a temperature below the melting point. This is because in the case of a liquid fluororesin, it exudes from the film after molding and contaminates the contact product that is in contact with the high heat resistance/high slidability film 1. Specific examples of the fluororesin include polytetrafluoroethylene resin having a melting point of 320 to 327° C. (tetrafluoroethylene resin, hereinafter referred to as PTFE resin, continuous maximum operating temperature: 260° C.), and melting point of 302 to 310° C. Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, hereinafter referred to as PFA resin, continuous maximum operating temperature: 260° C.), tetrafluoroethylene having a melting point of 250 to 275° C. Fluoroethylene-hexafluoropropylene copolymer resin (tetrafluoroethylene-hexafluoropropylene copolymer resin, hereinafter referred to as FEP resin, continuous maximum operating temperature: 205°C), tetrafluoroethylene having a melting point of 218 to 270°C -Ethylene copolymer resin (tetrafluoroethylene-ethylene copolymer resin, ETFE resin, continuous maximum operating temperature: 150°C), polychlorotrifluoroethylene resin having a melting point of 210 to 216°C (trifluorochloroethylene resin) , PCTFE resin, continuous maximum operating temperature: 120°C), melting point 160-180°C polyvinylidene fluoride resin (vinylidene fluoride resin, PVdF resin, continuous maximum operating temperature: 120°C), melting point 120-250°C Vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene copolymer resin (continuous maximum operating temperature: 80 to 120° C.) and the like.

Among such fluororesins, the melting point is 250° C. or higher, and the continuous maximum operating temperature is 200° C. or higher, which is excellent in heat resistance, and from the viewpoint of easy availability, handleability, and cost, PTFE resin, PFA resin, and FEP resin Is preferred. The PTFE resin, PFA resin, and FEP resin can be used alone or as a blend.

The addition amount of the fluororesin is 1 to 30 parts by mass, preferably 5 to 25 parts by mass with respect to 100 parts by mass of the total amount of the polyether ether ketone resin and the polyether imide resin. This is based on the reason that when the addition amount of the fluororesin is less than 1 part by mass, the slidability cannot be sufficiently imparted to the high heat resistance/high slidability film 1. On the contrary, when it exceeds 30 parts by mass, the melt-kneaded product cannot be extruded into a shape such as a strand shape or a sheet shape, so that the molding material 2 cannot be obtained.

The molding material 2 made of a polyetheretherketone resin, a polyetherimide resin, and a fluororesin includes, in addition to the above resins, an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer as long as the characteristics of the present invention are not impaired. , Lubricants, flame retardants, antistatic agents, heat resistance improvers, inorganic compounds, organic compounds, etc. are selectively added.

In the above, in the case of producing the highly heat resistant and highly slidable film 1, the method for preparing the molding material 2 made of polyetheretherketone resin, polyetherimide resin, and fluororesin is (1) polyetheretherketone resin, A method of preparing a molding material 2 by stirring and mixing a polyetherimide resin and a fluororesin at room temperature and melt-kneading, (2) once, a polyetheretherketone resin and a polyetherimide resin are stirred and mixed at room temperature. Then, a melt-kneaded product is produced by melt-kneading and dispersing, and the melt-kneaded product and the fluororesin are again stirred and mixed at room temperature and melt-kneaded to prepare a molding material 2, (3) polyether ether ketone A method of preparing a molding material 2 by stirring and mixing a resin and a polyetherimide resin at room temperature, melting the stirring mixture, adding a fluororesin to a molten kneaded product in a molten state, and melt kneading the mixture. Once, the polyether ether ketone resin (or polyether imide resin) and the fluororesin are stirred and mixed at room temperature and melt-kneaded to prepare a melt-kneaded product, and the melt-kneaded product and polyether imide resin (or (Ether ether ketone resin) is stirred and mixed at room temperature and melt-kneaded to prepare molding material 2. (5) Once, polyether ether ketone resin (or polyether imide resin) and fluorine resin are stirred and mixed. Examples of the method include melt-kneading, adding a polyetherimide resin (or polyether ether ketone resin) to a melt-kneaded product in a molten state, and melt-kneading to prepare the molding material 2. In addition, in this specification, "normal temperature" refers to a temperature range of about 0 to 50°C.

Explaining the method (1), a tumbler mixer, a Hensyl mixer, a V-type mixer, a Nauter mixer, a ribbon blender, and a universal mixer are used for stirring and mixing the polyether ether ketone resin, the polyether imide resin, and the fluororesin. A known stirring mixer such as a mixer is used. The molding material 2 made of a polyether ether ketone resin, a polyether imide resin, and a fluororesin is a stirring roll, a pressure kneader, or a uniaxial mixer made of a stirring mixture of a polyether ether ketone resin, a polyether imide resin, or a fluororesin. It can be prepared by melt-kneading with a melt-kneader comprising an extruder, a twin-screw extruder, a three-screw extruder, a four-screw extruder, a multi-screw extruder such as an eight-screw extruder. it can.

The temperature in the case of melt-kneading the polyether ether ketone resin, the polyether imide resin, and the fluororesin is the melting point of the polyether ether ketone resin, the glass transition point of the polyether imide resin, or the melting point of the fluororesin to 430° C., preferably Is preferably 350 to 400°C. This is, when the temperature of the melt kneading is lower than the melting point of the polyetheretherketone resin, lower than the glass transition point of the polyetherimide resin, or lower than the melting point of the fluororesin, the polyetheretherketone resin, the polyetherimide resin, and This is because the fluororesin cannot be uniformly dispersed by melt-kneading. On the other hand, when the temperature exceeds 430° C., the fluororesin is decomposed violently, which is not preferable.

A molding material 2 made of a polyetheretherketone resin, a polyetherimide resin, and a fluororesin is extruded into a shape such as a strand shape or a sheet shape, and then powdered, granulated, pelletized, or the like with a crusher or a cutter. It is used after being processed into a form suitable for film forming.

Explaining the method of (2), a tumbler mixer, a Hensyl mixer, a V-type mixer, a Nauter mixer, a ribbon blender, a universal stirring mixer, etc. can be used for stirring and mixing the polyether ether ketone resin and the polyether imide resin. Known stirring mixers are used. Further, a melt-kneaded product composed of a polyetheretherketone resin and a polyetherimide resin is, after stirring and mixing, a mixing roll, a pressure kneader, a single screw extruder, a twin screw extruder, a three screw extruder, It can be prepared by melt-kneading with a melt-kneader comprising a multi-screw extruder such as a twin-screw extruder or an eight-screw extruder.

When preparing a melt-kneaded product composed of a polyetheretherketone resin and a polyetherimide resin, the temperature is from the melting point of the polyetheretherketone resin or the glass transition point of the polyetherimide resin to 430° C., preferably 350. ~400°C is good. This melt-kneaded product is used after being extruded into a shape such as a strand shape or a sheet shape, and then processed into a powder shape, a granule shape, a pellet shape or the like by a crusher or a cutter. This is because when the temperature of the melt kneading is lower than the melting point of the polyetheretherketone resin or lower than the glass transition point of the polyetherimide resin, the polyetheretherketone resin and the polyetherimide resin are uniformly melt-kneaded. This is because they cannot be dispersed. On the other hand, if it exceeds 430° C., the polyether ether ketone resin or the polyether imide resin is decomposed, which is not preferable.

The above known stirring mixer is used for stirring and mixing the melt-kneaded product composed of the polyetheretherketone resin and the polyetherimide resin and the fluororesin, and the stirring mixture is mixed roll, pressure kneader, single-screw extrusion molding. And a twin-screw extruder, a three-screw extruder, a four-screw extruder, an eight-screw extruder, and other multi-screw extruders.

The temperature when melt-kneading the melt-kneaded material composed of the polyether ether ketone resin and the polyether imide resin and fluorine is the melting point of the polyether ether ketone resin, the glass transition point of the polyether imide resin, or the melting point of the fluorine resin. ~430°C, preferably 350-400°C. This is, when the temperature of the melt-kneaded material is lower than the melting point of the polyetheretherketone resin, lower than the glass transition point of the polyetherimide resin, or lower than the melting point of the fluororesin, the polyetheretherketone resin and the polyetherimide resin are This is because it cannot be uniformly dispersed by melt-kneading. On the other hand, if the temperature exceeds 430° C., the fluororesin will be severely decomposed, which is not preferable.

Explaining the method (3), a tumbler mixer, a Hensyl mixer, a V-type mixer, a Nauter mixer, a ribbon blender, a universal stirring mixer, etc. can be used for stirring and mixing the polyether ether ketone resin and the polyether imide resin. Known stirring mixers are used.

Further, the polyether ether ketone resin and the polyether imide resin, the stirring mixture mixing roll, pressure kneader, single-screw extruder, twin-screw extruder, three-screw extruder, four-screw extruder, Melt kneading with a melt kneader composed of a multi-screw extruder such as an eight-screw extruder, and then melt-kneading by adding a fluororesin to a melt-kneaded product of polyetheretherketone resin and polyetherimide resin in a molten state. By doing so, the molding material 2 made of a polyether ether ketone resin, a polyether imide resin, and a fluororesin can be prepared.

The temperature in the case of preparing the molding material 2 composed of a polyether ether ketone resin, a polyether imide resin and a fluororesin is a melting point of the polyether ether ketone resin, a glass transition point of the polyether imide resin, or a melting point of the fluororesin to 430. C., preferably 350 to 400.degree. This is, if the temperature of the melt-kneaded material is lower than the melting point of the polyetheretherketone resin, lower than the glass transition point of the polyetherimide resin, or lower than the melting point of the fluororesin, the polyetheretherketone resin, the polyetherimide resin, And the fluororesin cannot be uniformly dispersed by melt-kneading. Further, when the temperature exceeds 430° C., the fluororesin is severely decomposed.

Explaining the method (4), a tumbler mixer, a Hensyl mixer, a V-type mixer, a Nauter mixer, a ribbon blender, and a mixer are used for stirring and mixing the polyether ether ketone resin (or polyether imide resin) and the fluororesin. A known stirring mixer such as a universal stirring mixer is used. Further, the melt-kneaded product composed of the polyetheretherketone resin (or polyetherimide resin) and the fluororesin is mixed with a stirring roll composed of the polyetheretherketone resin (or polyetherimide resin) and the fluororesin. Melt-kneading with a melt-kneader consisting of a pressure kneader, a single-screw extruder, a twin-screw extruder, a three-screw extruder, a four-screw extruder, a multi-screw extruder such as an eight-screw extruder. Can be prepared by

The temperature for preparing a melt-kneaded product composed of polyetheretherketone resin (or polyetherimide resin) and fluorine is the melting point of the polyetheretherketone resin (or the glass transition point of the polyetherimide resin), or the fluororesin. Melting point to 430°C, preferably 350 to 400°C. This is because when the temperature of the melt-kneaded product is lower than the melting point of the polyetheretherketone resin (or lower than the glass transition point of the polyetherimide resin) or lower than the melting point of the fluororesin, the polyetheretherketone resin (or This is because the ether imide resin) and the fluororesin cannot be uniformly dispersed by melt-kneading. On the other hand, when the temperature exceeds 430° C., the fluororesin is decomposed violently, which is not preferable.

Melt-kneaded material consisting of polyetheretherketone resin (or polyetherimide resin) and fluororesin is extruded into a shape of strand, sheet, etc., and then powdered, granulated or pelletized by a crusher or cutting machine. It is used after being processed into other forms. Regarding the stirring and mixing of the melt-kneaded material consisting of the polyether ether ketone resin (or polyether imide resin) and the fluororesin and the polyether imide resin (or polyether ether ketone resin), a tumbler mixer, a Hensyl mixer, a V-type mixing A known stirring and mixing machine such as a machine, a Nauta mixer, a ribbon blender, a universal stirring mixer, or the like is used.

The melt-kneaded mixture of the polyether ether ketone resin (or polyether imide resin) and the fluoro-resin melt-kneaded product and the polyether imide resin (or polyether ether ketone resin) is a mixing roll, a pressure kneader, Prepared by melt-kneading with a melt-kneader consisting of a single-screw extruder, a twin-screw extruder, a three-screw extruder, a four-screw extruder, a multi-screw extruder such as an eight-screw extruder. be able to.

The temperature for preparing a melt-kneaded product of a melt-kneaded product of polyetheretherketone resin (or polyetherimide resin) and a fluororesin and a polyetherimide resin (or polyetheretherketone resin) is The melting point of the ether ether ketone resin, the glass transition point of the polyether imide resin, or the melting point of the fluororesin to 430°C, preferably 350 to 400°C.

This is because when the temperature of the melt-kneaded material is lower than the melting point of the polyether ether ketone resin (or lower than the glass transition point of the polyetherimide resin) or lower than the melting point of the fluororesin, the polyether ether ketone resin (or polyether This is because the imide resin) and the fluororesin cannot be uniformly dispersed by melt-kneading. On the other hand, when the temperature exceeds 430° C., the fluororesin is decomposed violently, which is not preferable.

Explaining the method (5), a tumbler mixer, a Hensyl mixer, a V-type mixer, a Nauter mixer, a ribbon blender, and a mixer are used for stirring and mixing the polyether ether ketone resin (or polyether imide resin) and the fluororesin. A known stirring mixer such as a universal stirring mixer is used. Further, the polyether ether ketone resin (or polyether imide resin) and the fluororesin are prepared by mixing the above stirring mixture with a mixing roll, a pressure kneader, a single screw extruder, a twin screw extruder, a three screw extruder, Melt kneading with a melt kneader consisting of a multi-screw extruder such as a twin-screw extruder or an eight-screw extruder, and add polyetherimide resin (or polyetheretherketone resin) to the melt-kneaded product in a molten state. It can be prepared by melt-kneading.

When preparing the polyether ether ketone resin (or polyether imide resin) and fluorine, the temperature is the melting point of the polyether ether ketone resin (or the glass transition point of the polyether imide resin) or the melting point of the fluororesin to 430°C. It is preferably 350 to 400°C. This is because when the temperature of the melt-kneaded product is lower than the melting point of the polyetheretherketone resin (or lower than the glass transition point of the polyetherimide resin) or lower than the melting point of the fluororesin, the polyetheretherketone resin (or polyether) is used. The imide resin) and the fluororesin cannot be uniformly dispersed by melt-kneading. If it exceeds 430° C., the fluororesin will be severely decomposed, which is not preferable.

The temperature at which a melt-kneaded product comprising a polyetheretherketone resin (or a polyetherimide resin) and a fluororesin and a polyetherimide resin (or a polyetheretherketone resin) is prepared depends on the glass transition of the polyetherimide resin. The point (or the melting point of the polyetheretherketone resin) or the melting point of the fluororesin to 430° C., preferably 350 to 400° C. This is because when the temperature of the melt-kneaded product is lower than the melting point of the polyetheretherketone resin (or lower than the glass transition point of the polyetherimide resin) or lower than the melting point of the fluororesin, the polyetheretherketone resin (or the polyetheretherketone resin). This is because it is not possible to uniformly disperse the melt-kneaded product composed of the ether imide resin) and the fluororesin and the polyether imide resin (or the polyether ether ketone resin). Further, when the temperature exceeds 430° C., the fluororesin is severely decomposed.

A molding material 2 composed of a polyether ether ketone resin, a polyether imide resin and a fluororesin is extruded into a shape such as a strand shape or a sheet shape, and then powdered, granulated or pelletized by a crusher or a cutter. It is used after being processed into a form suitable for film forming.
It is also possible to disperse any one of a polyether ether ketone resin, a polyether imide resin, or a fluororesin in a predetermined amount or more to prepare a master batch.

When the high heat-resistant and high-sliding film 1 is manufactured using the molding material 2 made of polyetheretherketone resin, polyetherimide resin, and fluorine, the high-heat-resistant and high-sliding film 1 made of the molding material 2 is A known manufacturing method such as a melt extrusion molding method, a calendar molding method, or a casting molding method can be employed. Among these manufacturing methods, continuous extrusion molding is performed by the melt extrusion molding method from the viewpoints of improving the thickness accuracy, productivity, and handling of the high heat resistant/sliding film 1 and simplifying the equipment. Is preferred.

Here, the melt extrusion molding method, as shown in FIG. 1, melt-kneads the molding material 2 by using the melt extrusion molding machine 10, and from the T die 13 at the tip end of the melt extrusion molding machine 10, to obtain high heat resistance and high heat resistance. It is a method of continuously extruding the slidable film 1.

The melt extrusion molding machine 10 is composed of, for example, a single-screw extrusion machine, a twin-screw extrusion machine, or the like, and functions to melt-knead the input molding material 2. A raw material inlet 11 for the molding material 2 is installed in the upper rear part of the melt extrusion molding machine 10. The raw material inlet 11 is inert to helium gas, neon gas, argon gas, krypton gas, nitrogen gas and the like. An inert gas supply pipe 12 for supplying a gas (see the arrow in FIG. 1) as necessary is connected, and the inflow of the inert gas through the inert gas supply pipe 12 causes oxidative deterioration of the molding material 2 and oxygen. Crosslinking is effectively prevented.

The temperature at the time of melt kneading of the melt extruder 10 is adjusted to the melting point of the polyether ether ketone resin, the glass transition point of the polyether imide resin, or the melting point of the fluororesin to 430°C, preferably 360 to 400°C. If the melting point is lower than the melting point of the polyetheretherketone resin, the glass transition point of the polyetherimide resin, or lower than the melting point of the fluororesin, the polyetheretherketone resin, the polyetherimide resin, and the fluororesin are melt-kneaded. This is because it is impossible to uniformly disperse. If the temperature exceeds 430° C., the polyether ether ketone resin, the polyether imide resin, or the fluororesin will decompose.

The T-die 13 is attached to the front end of the melt extrusion molding machine 10 via a connecting pipe 14, and functions to continuously push out the belt-shaped high heat resistant/high slidable film 1. A gear pump 15 mounted on the connecting pipe 14 is located upstream of the T die 13, and the gear pump 15 transfers the molding material 2 to the T die 13 at a constant speed and with high accuracy. The temperature during extrusion of the T-die 13 is adjusted to the melting point of the polyetheretherketone resin, the glass transition point of the polyetherimide resin, or the melting point of the fluororesin to 430°C, preferably 360°C to 400°C. When the temperature is lower than the melting point of the polyetheretherketone resin, the glass transition point of the polyetherimide resin, or lower than the melting point of the fluororesin, the strip-shaped uniformly dispersed high heat-resistant and highly slidable film 1 is continuously formed. Based on the fact that it cannot be extruded into. On the other hand, when the temperature exceeds 430° C., the reason is that the polyether ether ketone resin, the polyether imide resin, or the fluororesin may be decomposed.

A pair of pressure bonding rolls 16 is rotatably supported below the T die 13 so as to sandwich the cooling roll 17. A winding tube 19 of a winder 18 that winds the high heat resistant and highly slidable film 1 is rotatably installed downstream of the downstream pressure bonding roll 16 of the pair of pressure bonding rolls 16. A slit blade 20 that forms a slit in a side portion of the high heat resistant and highly slidable film 1 is arranged between the and the winding tube 19 of the winder 18 so as to be movable up and down. A necessary number of rotatable tension rolls 21 for applying a tension to the high heat resistance and high slidability film 1 and smoothly winding the film are supported between the winding tube 19 of the winding machine 18 and the winding tube 19.

From the viewpoint of improving the adhesion between the high heat resistant/high slidability film 1 and the cooling roll 17, at least the natural rubber, isoprene rubber, butadiene rubber, norbornene rubber, acrylonitrile butadiene rubber, and A rubber layer such as nitrile rubber, urethane rubber, silicone rubber, or fluororubber is formed by coating as necessary, and an inorganic compound such as silica or alumina is selectively added to this rubber layer. Among these, it is preferable to use silicone rubber or fluororubber having excellent heat resistance.

As a method for forming fine irregularities on the high heat-resistant/sliding film 1, (1) high heat-resistant/sliding with a cooling roll 17 having fine irregularities and a pressure bonding roll 16 having fine irregularities Method for forming fine irregularities by sandwiching the flexible film 1, (2) Fine zirconia, glass, an inorganic compound such as stainless steel, a polycarbonate, nylon, or an organic material such as a plant seed on the highly heat resistant and highly slidable film 1. Examples include a method of spraying a compound to form fine unevenness, and (3) a method of forming fine unevenness by press-molding the high heat-resistant and highly slidable film 1 with a mold having fine unevenness. Among these methods, the method (1) is preferable from the viewpoints of simplification of equipment, accuracy of unevenness size, uniformization of unevenness, ease of unevenness formation, and continuous unevenness formation.

The method (1) will be described in more detail. (1-1) A molding mixture 2 is obtained by melt-kneading a stirring mixture of (1-1) polyetheretherketone resin, polyetherimide resin, and fluororesin with a melt extrusion molding machine 10. The molding material 2 is prepared and discharged from the T-die 13 of the melt extrusion molding machine 10 onto a cooling roll 17 having fine irregularities on its peripheral surface, and this discharge product is cooled roll 17 and fine irregularities on the peripheral surface. A method in which the high heat-resistant and high-sliding film 1 is sandwiched with the provided pressure-bonding roll 16 and simultaneously molded with the melt extrusion molding. (1-2) The molded high-heat-resistant and high-sliding film 1 is surrounded by fine irregularities. A method of forming the unevenness by sandwiching it between the cooling roll 17 provided on the surface and the pressure-bonding roll 16 provided with the fine unevenness on the peripheral surface is preferable, but the method (1) is preferable from the viewpoint of simplification of equipment.

The pressure bonding roll 16 is adjusted to a temperature of 270° C. or lower, preferably 50 to 230° C., and is brought into sliding contact with the high heat resistant/high slidability film 1 and pressed against the cooling roll 17. The temperature of the pressure-bonding roll 16 is within such a range that when the temperature of the pressure-bonding roll 16 exceeds 270° C., the high heat-resistant and high-sliding film 1 adheres to the pressure-bonding roll 16, Is likely to break. On the contrary, when the temperature is lower than 50° C., the pressure-bonding roll 16 is condensed, which is not preferable. Examples of the method for adjusting the temperature and cooling the pressure bonding roll 16 include a method using a heat medium such as air, water and oil, an electric heater, a dielectric heating roll and the like.

The cooling roll 17 is made of, for example, a metal roll having a diameter larger than that of the pressure bonding roll 16, and the high heat resistant/high slidability film 1 rotatably supported below the T die 13 and extruded is used as the pressure bonding roll 16. It is sandwiched between them, and functions to control the thickness within a predetermined range while cooling the high heat resistant and high slidability film 1 together with the pressure bonding roll 16.

This cooling roll 17 is adjusted to a temperature of 270° C. or lower, preferably 50° C. to 230° C., and slidably contacts the high heat resistant/high slidability film 1, like the pressure bonding roll 16. This is because when the temperature of the chill roll 17 exceeds 270° C., the high heat resistant/high slidable film 1 may stick to the chill roll 17 and break during the production of the high heat resistant/high slidable film 1. Because there is. Also, if the temperature is lower than 50° C., the cooling roll 17 will be condensed, which is not preferable. Examples of the temperature adjustment and cooling method of the cooling roll 17 include a method using a heat medium such as air, water and oil, an electric heater, and dielectric heating.

In the above, when manufacturing the high heat resistant/high slidability film 1, as shown in FIG. 1, the molding material 2 is fed to the raw material charging port 11 of the melt extrusion molding machine 10 and the inert gas indicated by the arrow in FIG. The material is charged while being supplied, and the molding material 2 is melt-kneaded by the melt extrusion molding machine 10 in a heated and pressurized state, and the belt-shaped high heat resistance and high slidability film 1 is continuously extruded from the T die 13. At this time, the water content of the molding material 2 before melt-kneading is adjusted to 2000 ppm or less, preferably 1000 ppm or less, more preferably 500 ppm or less. This is because when the water content of the molding material 2 before melt-kneading exceeds 2000 ppm, the highly heat resistant and highly slidable film 1 may foam.

After extrusion molding the high heat resistance/high slidability film 1, it is sequentially wound around a pair of pressure bonding rolls 16, cooling rolls 17, tension rolls 21, and a winding pipe 19 of a winder 18, and also has high heat resistance/high sliding properties. The flexible film 1 is cooled by a cooling roll 17, both sides of the highly heat resistant and highly slidable film 1 are cut by slit blades 20, respectively, and wound on a winding tube 19 in sequence to form a polyetheretherketone resin, a polyether. It is possible to manufacture the high heat resistance and high slidability film 1 made of a melt-kneaded product of an imide resin and a fluororesin.

The fine irregularities on the surface of the highly heat resistant and highly slidable film 1 have an arithmetic average roughness (Ra) of 0.2 to 5.0 μm, preferably 0.25 to 4.5 μm. This is because if the arithmetic average roughness (Ra) is less than 0.20 μm, the desired slidability cannot be obtained. Further, if the arithmetic average roughness (Ra) exceeds 5.0 μm, the strength of the high heat resistance/high slidability film 1 is lowered, and there is a possibility that breakage may occur during molding.

The heat resistance of the high heat resistance/high slidability film 1 can be represented by the first inflection point temperature of the storage elastic modulus and the storage elastic modulus at 280°C. The first inflection point temperature of this storage elastic modulus is 170° C. or higher, preferably 180° C. or higher. This is because when the first inflection point temperature of the storage elastic modulus is less than 170° C., sufficient heat resistance of the high heat resistance/high slidability film 1 cannot be obtained. The storage elastic modulus at 280° C. is 1×10 ⁵ Pa or more, but this is because when the storage elastic modulus at 280° C. is less than 1×10 ⁵ Pa, sufficient heat resistance cannot be obtained in a high temperature range. is there.

The slidability of the high heat-resistant and highly slidable film 1 can be expressed by the static friction coefficient with various resin films and the dynamic friction coefficient. The coefficient of static friction is preferably 1.0 or less. This is because if the static friction coefficient exceeds 1.0 and the dynamic friction coefficient exceeds 1.0, sufficient slipperiness cannot be obtained.

The thickness of the high heat resistance/high slidability film 1 is 3 to 1000 μm, preferably 10 to 1000 μm. This is because when the thickness is less than 3 μm, the strength of the film is remarkably reduced, so that the high heat resistance/high slidability film 1 is ruptured during molding, etc. This is because the molding of No. 1 becomes difficult. If the thickness of the highly heat resistant and highly slidable film 1 exceeds 1000 μm, the molding speed is remarkably reduced and the productivity is deteriorated, which is not preferable.

The heat resistance and the high slidability of the film 1 can be improved by adjusting the crystallinity. As a method for adjusting the crystallinity of the high heat resistant/sliding film 1, for example, (1) a melt kneaded product of a polyether ether ketone resin, a polyether imide resin, and a fluororesin is melted by a melt extrusion molding machine 10. The melt-kneaded mixture of the polyetheretherketone resin, the polyetherimide resin, and the fluororesin, which has been melt-kneaded, is cooled from the T-die 13 to 270° C. or lower, preferably at a temperature of 50° C. to 230° C. A method of adjusting the crystallinity at the same time as molding the high heat resistance/high slidability film 1 by extruding and closely adhering the film, (2) after manufacturing the high heat resistance/high slidability film 1, 270° C. or lower, preferably A method of adhering onto a cooling roll 17 adjusted to a temperature of 50° C. to 230° C. to adjust the crystallinity, (3) after producing the high heat resistant/high slidability film 1, 270° C. or lower, preferably There is a method of adjusting the crystallinity by passing it through an infrared heating furnace adjusted to a temperature of 230° C. or lower, more preferably 50° C. to 230° C., or a hot air oven.

Either method can be adopted, but the equipment is simplified, the crystallization time of the high heat resistant/sliding film 1 is shortened, or the thickness accuracy of the high heat resistant/sliding film 1 is controlled. From the viewpoint of easiness, the method (1) is preferable. The cooling roll 17 is set to a temperature range of 50° C. to 270° C., because when the temperature of the cooling roll 17 exceeds 270° C., the high heat resistance/high slidability film 1 adheres to the cooling roll 17, This is because the high heat resistance/high slidability film 1 may be broken. Further, if the temperature is lower than 50° C., the cooling roll 17 is condensed, which is not preferable.

According to the above, since the high heat resistance/sliding film 1 is composed of a molten mixture of polyetheretherketone resin, polyetherimide resin, and fluororesin, it has excellent heat resistance and slidability. The moving film 1 can be obtained at low cost.

[Example 1]
First, a polyetheretherketone resin [Product name: KetaSpire polyetheretherketone grade: KT-851NL SP] manufactured by Solvay Specialty Polymers (hereinafter abbreviated as "KT-851NL SP") and a polyetherimide resin [SABIC Innovative Plastics] Product name: ULTEM 1010-1000-NB, glass transition point: 211° C.] (hereinafter, abbreviated as “1010-1000”) is a composition mass ratio of polyetheretherketone resin: 65% by mass, polyetherimide resin: It was weighed so as to be 35% by mass, and further, as a fluororesin, a PFA resin [manufactured by Asahi Glass Co., Ltd., product name: Fluon PFA grade: P-62XP (hereinafter abbreviated as “P-62XP”) was used as a polyether ether ketone resin and a polyresin. The total amount of the ether imide resin was weighed to be 5 parts by weight based on 100 parts by weight, and after weighing, three kinds of resins were put into a tumbler mixer.

After the addition, the tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture. The glass transition point of the polyetherimide resin is determined by using a differential scanning calorimeter [manufactured by SII Nano Technology Co., Ltd.: product name High-sensitivity differential scanning calorimeter X-DSC7000] according to JIS K7121 and a heating rate of 10°C/ It was measured under the condition of minutes. The measurement of the glass transition point was the same for the following examples and comparative examples.

After preparing the stirring mixture by stirring and mixing the polyether ether ketone resin, the polyether imide resin, and the PFA resin, the stirring mixture is fed to a twin-screw extruder with a vacuum pump, melt-kneaded under reduced pressure, and twin-screwed. A pellet-shaped molding material was prepared by extruding into a rod shape from a die at the tip of the extruder, cooling with water, and then cutting. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 360 to 380° C., a die temperature of 385° C., and a temperature of a connecting pipe connecting the twin-screw extruder and the die of 380° C. to prepare a molding material.

Then, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a highly heat-resistant and highly slidable film into a strip shape.

At this time, the water content of the molding material was measured by the Karl Fischer titration method using a trace moisture measuring device [product name CA-100 type manufactured by Mitsubishi Chemical Co.]. As a result of the measurement, the water content of the molding material when dried was 225 ppm. The water content of this molding material was measured in the same manner in the following examples and comparative examples. The single-screw extruder was L/D=32, compression ratio: 2.5, screw: full flight screw type. The cylinder temperature of this single screw extruder was adjusted to 360 to 380° C., the temperature of the T die was 385° C., and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 380° C.

Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T-die was measured, and it was 376° C. when measured. When the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

In this way, after extruding the high heat resistance and high slidability film into a strip shape, both ends of the continuous high heat resistance and high slidability film are cut with slit blades and wound sequentially on the winding tube of the winder. A highly heat resistant and highly slidable film having a length of 100 m and a width of 620 mm was produced. At this time, the high heat resistance/high slidability film has a pair of pressure-sensitive adhesive rolls made of silicone rubber having an arithmetic average roughness (Ra) of 0.44 to 0.47 μm, and has an arithmetic average roughness (Ra) of 1 on the peripheral surface. A metal roll, which is a cooling roll at 205° C. having a convex pattern of 0.86 μm, and a 6-inch take-up tube located downstream of these rolls were sequentially wound, and sandwiched between a pressure roll and a metal roll.

When a high heat resistance/high slidability film was obtained, the film thickness, surface roughness, heat resistance, and slidability of this high heat resistance/high slidability film were evaluated and shown in Table 1. The surface roughness of the high heat resistance and high slidability film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

・Film thickness of high heat resistance/sliding film The thickness of the high heat resistance/sliding film with a film thickness of 2 to 10 μm can be measured using a contact-type thickness meter [Mahr: product name Electronic Micrometer MIRO Ton 1240]. Further, the thickness of the highly heat-resistant and highly slidable film having a film thickness of more than 10 μm and up to 150 μm was measured using a micrometer [Mitutoyo's product name: coolant proof micrometer code MDC-25PJ]. ..

In the measurement, the thickness of the high heat resistant/high slidable film at a predetermined position where the extrusion direction and the width direction (the direction perpendicular to the extrusion direction) intersect was measured at 100 points, and the average value was taken as the film thickness. The measurement points in the extrusion direction were 100 mm, 200 mm, 300 mm, 400 mm, and 500 mm at 100 mm intervals from the tip of the high heat resistance and high slidability film.

On the other hand, the measurement point in the width direction is 25 mm from the left end of the high heat resistance and high slidability film, and then at 30 mm intervals, 55 mm, 85 mm, 115 mm, 145 mm, 175 mm, 205 mm, 235 mm, 265 mm, 295 mm, 325 mm, 355 mm. The positions were 385 mm, 415 mm, 445 mm, 475 mm, 505 mm, 535 mm, 565 mm, and 595 mm.

-Surface roughness of high heat resistance/high slidability film The surface roughness of the high heat resistance/high slidability film was evaluated by arithmetic average roughness (Ra). This arithmetic average roughness (Ra) was measured according to JIS B0601-2001 in the extrusion direction of the high heat resistance and high slidability film on the metal roll surface side and the pressure bonding roll surface side.

・Heat resistance of high heat resistance/high slidability film The heat resistance of high heat resistance/high slidability film was evaluated by the first inflection point temperature of the storage elastic modulus (E') and the storage elastic modulus at 280°C. .. The storage elastic modulus of this high heat resistance/high slidability film was measured in the extrusion direction and width direction (direction perpendicular to the extrusion direction) of the high heat resistance/high slidability film.

Specifically, when measuring the storage elastic modulus in the extruding direction of a high heat resistant/sliding film, the extruding direction is 60 mm×width 6 mm, and when the storage elastic modulus in the width direction is measuring, the extruding direction 6 mm× The measurement was performed by cutting into a size of 60 mm in width. When measuring the storage elastic modulus, a frequency was 3 Hz, strain was 0.1%, and a temperature rising rate was in a tensile mode using a viscoelasticity spectrometer [Product name: RSA-G2 manufactured by TS Instruments Japan Co., Ltd.]. The measurement was performed under the conditions of 3° C./minute, a measurement temperature range of −60 to 360° C., and a check interval of 21 mm.

As shown in FIG. 2, the first inflection point temperature was the temperature at the intersection of two straight line portions with respect to the change curve of the storage elastic modulus. When obtaining the first inflection point temperature, the straight line part of the storage elastic modulus before the first sharp decrease is extended to the high temperature side and the first straight line a is drawn, and the storage elastic modulus first sharply decreases. After that, the straight line part of the intermediate line is extended to the low temperature side, a second straight line b is drawn, and a vertical line at the intersection of these two lines a and b is drawn on the temperature axis of the horizontal axis, and the temperature is first changed. It was determined as the point temperature.

The storage elastic modulus at 280° C. was obtained from the storage elastic modulus curve. The storage elastic modulus was obtained in the extrusion direction and the width direction. And, when the storage elastic modulus is 1.0×10 ⁷ Pa or more, it is ◯, when less than 1.0×10 ⁷ Pa to 1.0×10 ⁵ Pa or more, and when it is less than 1.0×10 ⁵ Pa. Was designated as x.

・High heat resistance/high slidability Film surface slidability (high heat resistance/high slidability between films)
The slidability between the high heat resistance and high slidability film surfaces was evaluated by the static friction coefficient (μs) and the dynamic friction coefficient (μk).

The static friction coefficient and the dynamic friction coefficient were measured according to JIS K7125-1999. Specifically, using a surface property measuring instrument HEDO N-14 [Shinto Kagaku Co., Ltd.: product name], in an environment of 23° C. and 50% RH, test speed: 100 mm/min, load: 200 g, contact Area: Measured under the condition of 63.5 mm×63.5 mm. Then, under these conditions, the metal roll surface side of the high heat resistance/high slidability film is fixed to the moving table side, and the pressure bonding roll surface side of the high heat resistance/high slidability film is fixed to the plane indenter side, and a load of 200 g is applied. Then, the static friction coefficient and the dynamic friction coefficient were measured at a speed of 100 mm/min.

・High heat resistance/sliding property Sliding property of film surface (sliding property between high heat resistance/sliding film and other resin film)
The slidability between the surface of the highly heat resistant and highly slidable film and the surface of the other resin film was evaluated by the static friction coefficient (μs) and the dynamic friction coefficient (μk). The static friction coefficient and the dynamic friction coefficient were measured according to JIS K7125-1999. Specifically, using a surface property measuring instrument HEDO N-14 [Shinto Kagaku Co., Ltd.: product name], in an environment of 23° C. and 50% RH, test speed: 100 mm/min, load: 200 g, contact Area: Measured under the condition of 63.5 mm×63.5 mm. Then, various kinds of commercially available resin films were fixed to the metal roll surface side of the high heat resistant/sliding film on the moving table side and the flat indenter side, and a static friction coefficient was applied at a speed of 100 mm/min by applying a load of 200 g. And the dynamic friction coefficient was measured. In the table, μs is the static friction coefficient and μk is the dynamic friction coefficient.

Various resin films/polyamide 9T resin film [Shin-Etsu Sepla Film PA9T-NA manufactured by Shin-Etsu Polymer Co., Ltd., hereinafter referred to as PA9T resin sheet]
-Polyether ether ketone resin film [Shin-Etsu Polymer Co., Ltd., Shin-Etsu SEPLA Film PEEK, abbreviated as PEEK resin film]
-Polyimide resin film [Toray-Dupont, product name: Kapton, product number: 100H, hereinafter referred to as PI resin film]
-Polyethylene terephthalate resin film (manufactured by Toray, product name: Lumirror 100S10, hereinafter referred to as PET resin film)
・Thin hard vinyl chloride sheet [Mataei Kako Co., Ltd., hereinafter referred to as PVC resin sheet]
・6 nylon sheet [manufactured by DSM Japan Engineering Plastics, hereinafter referred to as PA6 resin sheet] ・Polycarbonate sheet [manufactured by Takiron, referred to as PC resin sheet]
・Polypropylene sheet [Kyoei Resin Co., Ltd., called PP resin sheet]
The thin hard vinyl chloride sheet, 6-nylon sheet, polycarbonate sheet, and polypropylene sheet were purchased from Sands Corporation.

[Example 2]
First, a polyetheretherketone resin [Product name: KetaSpire polyetheretherketone grade: KT-820NL] (manufactured by Solvay Specialty Polymers, Inc.) (hereinafter abbreviated as "KT-820NL") and a polyetherimide resin [SABIC Innovative Plastics Co., Ltd. Product name: ULTEM 9011-1000-NB glass transition point: 210° C.] (hereinafter, abbreviated as “9011-1000”) is a compositional mass ratio of polyetheretherketone resin: 50% by mass, polyetherimide resin: 50% by mass. In addition, PTFE resin [manufactured by Kitamura, product name: KTL-620 (hereinafter abbreviated as “KTL-620”] as a fluororesin is added in a total amount of 100 mass of polyetheretherketone resin and polyetherimide resin. It was weighed to be 10 parts by weight per part, and after weighing, three kinds of resins were put into a tumbler mixer.

After charging, a tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture. The glass transition point of the polyetherimide resin was measured by the same method as in Example 1. After preparing the stirring mixture by stirring and mixing the polyether ether ketone resin, the polyether imide resin, and the PTFE resin, the stirring mixture is supplied to a twin-screw extruder with a vacuum pump, melt-kneaded under reduced pressure, A pellet-shaped molding material was prepared by extruding into a rod shape from a die at the tip of the extruder, cooling with water, and then cutting. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 360 to 380° C., a die temperature of 380° C., and a temperature of a connecting pipe connecting the twin-screw extruder and the die of 380° C. to prepare a molding material.

Then, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a highly heat-resistant and highly slidable film into a strip shape. The water content of the molding material when dried was 254 ppm. The single screw extruder and the screw were the same as in Example 1.

The cylinder temperature of the single screw extruder was adjusted to 360 to 380°C, the temperature of the T die was 385°C, and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 380°C. Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T die was measured, and it was 375° C. when measured. When the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

In this way, the high heat resistant and high slidability film was extruded in the shape of a strip, and in the same manner as in Example 1, both sides were cut with slit blades and sequentially wound on the winding tube of the winder, and the length was 100 m. A strip-shaped film with a width of 620 mm was produced. At this time, the strip-shaped film was sequentially applied to a pair of pressure-bonding rolls made of silicone rubber, a metal roll which was a cooling roll at 210° C. having unevenness on the peripheral surface, and a 6-inch winding tube located downstream of these rolls. It was wound around and sandwiched between a pressure roll and a metal roll. The pressure roller made of silicone rubber and the metal roll were the same as in Example 1.

Once the high heat resistant/high slidability film was obtained, the film thickness, surface roughness, heat resistance and slidability of this high heat resistant/high slidability film were evaluated in the same manner as in Example 1. It is described in Table 1. The surface roughness of the high heat resistance and high slidability film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

[Example 3]
First, the polyetheretherketone resin and the polyetherimide resin of Example 1 were weighed so that the polyetheretherketone resin was 40% by mass and the polyetherimide resin was 60% by mass, and the PFA resin [Daikin Industry Co., Ltd. Product name: NEOFLON PFA AP-210 (hereinafter abbreviated as "AP-210") is weighed so as to be 25 parts by mass based on 100 parts by mass of the total amount of the polyetheretherketone resin and the polyetherimide resin. After that, three kinds of resins were charged into a tumbler mixer, and after the mixing, the tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

After preparing the stirring mixture by stirring and mixing the polyether ether ketone resin, the polyether imide resin, and the PFA resin, the stirring mixture is fed to a twin-screw extruder with a vacuum pump, melt-kneaded under reduced pressure, and twin-screwed. A pellet-shaped molding material was prepared by extruding into a rod shape from a die at the tip of the extruder, cooling with water, and then cutting. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 350 to 370° C., a die temperature of 370° C., and a temperature of a connecting pipe connecting the twin-screw extruder and the die of 370° C. to prepare a molding material.

Then, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a highly heat-resistant and highly slidable film into a strip shape. The water content of the molding material when dried was 237 ppm. The single screw extruder and the screw were the same as in Example 1. The cylinder temperature of this single screw extruder was adjusted to 360 to 370°C, the temperature of the T die was 375°C, and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 370°C.

Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T die was measured, and it was 364° C. when measured. When the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

In this way, the high heat resistant and high slidability film was extruded in the shape of a strip, and in the same manner as in Example 1, both sides were cut with slit blades and sequentially wound on the winding tube of the winder, and the length was 100 m. A strip-shaped film with a width of 620 mm was produced. At this time, the strip-shaped film was sequentially applied to a pair of pressure-bonding rolls made of silicone rubber, a metal roll which was a cooling roll at 210° C. having irregularities on its peripheral surface, and a 6-inch winding tube located downstream thereof. It was wound around and sandwiched between a pressure roll and a metal roll. The pressure roller made of silicone rubber and the metal roll were the same as in Example 1.

Once the high heat resistant/high slidability film was obtained, the film thickness, surface roughness, heat resistance, and slidability of the high heat resistant/high slidability film were evaluated by the same method as in Example 1 and evaluated. It was described in 1. The surface roughness of the high heat resistance and high slidability film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

[Example 4]
First, polyetheretherketone resin [Product name: Vestakeep Grade: 3300G manufactured by Daicel-Evonik Co., Ltd. (hereinafter abbreviated as "3300G") and the polyetherimide resin used in Example 1 are polyether in a composition mass ratio. Etherketone resin: 30% by mass, polyetherimide resin: 70% by mass, and further, as a fluororesin, FEP resin [manufactured by Daikin Industries, Ltd., product name: NEOFLON FEP NP-20 (hereinafter "NP-20" Is abbreviated] to 20 parts by mass based on 100 parts by mass of the total amount of the polyether ether ketone resin and the polyether imide resin, and the three kinds of resins are charged into the tumbler mixer after the measurement. The mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

After preparing the stirring mixture by stirring and mixing the polyether ether ketone resin, the polyether imide resin, and the FEP resin, the stirring mixture is supplied to a twin-screw extruder equipped with a vacuum pump, melt-kneaded under reduced pressure, and twin-screwed. A pellet-shaped molding material was prepared by extruding into a rod shape from a die at the tip of the extruder, cooling with water, and then cutting. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 350 to 370° C., a die temperature of 370° C., and a temperature of a connecting pipe connecting the twin-screw extruder and the die of 370° C. to prepare a molding material.

Then, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a highly heat-resistant and highly slidable film into a strip shape. The water content of the molding material when dried was 243 ppm. The single screw extruder and the screw were the same as in Example 1. The cylinder temperature of this single screw extruder was adjusted to 350 to 370° C., the temperature of the T die was 375° C., and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 370° C.

Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T die was measured, and it was 361° C. when measured. Further, when the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

After extruding the high heat-resistant and high-sliding film into a strip shape, both sides are cut by slit blades in the same manner as in Example 1 and sequentially wound on a winder tube of a winder to obtain a length of 100 m and a width. A 620 mm strip-shaped film was produced. At this time, the band-shaped film was a pair of pressure-bonding rolls made of silicone rubber, a metal roll which was a cooling roll at 150° C. having irregularities with an arithmetic mean roughness (Ra) of 2.90 μm on the peripheral surface, and these. It was successively wound around a 6-inch winding tube located downstream and held between a pressure roll and a metal roll. The pressure roller made of silicone rubber was the same as in Example 1.

Once the high heat resistant/high slidability film was obtained, the film thickness, surface roughness, heat resistance, and slidability of the high heat resistant/high slidability film were evaluated by the same method as in Example 1 and evaluated. It was described in 2. The surface roughness of the high heat resistance and high slidability film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

[Example 5]
First, a polyether ether ketone resin [Product name: Victrex PEEK381G manufactured by Victorex Co., Ltd.] (hereinafter, abbreviated as "381G") and a polyetherimide resin similar to that in Example 2 are in a composition mass ratio. 20% by mass, polyetherimide resin: Weighed so as to be 80% by mass, and further, as a fluororesin, the PFA resin used in Example 3 was added to 100 parts by mass of the total amount of the polyetheretherketone resin and the polyetherimide resin. On the other hand, the PFA resin was weighed to be 15 parts by mass, and after weighing, three kinds of resins were put into a tumbler mixer. After the addition, the tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

After stirring and mixing the polyether ether ketone resin, the polyether imide resin and the PFA resin to prepare a stirring mixture, the stirring mixture is supplied to a twin-screw extruder equipped with a vacuum pump, melt-kneaded under reduced pressure, and then twin-screwed. A pellet-shaped molding material was prepared by extruding into a rod shape from a die at the tip of the extruder, cooling with water, and then cutting. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 345 to 365° C., a die temperature of 365° C., and a temperature of a connecting pipe connecting the twin screw extruder and the die of 365° C. to prepare a molding material.

Next, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a highly heat-resistant and highly slidable film into a strip shape. The water content of the molding material when dried was 267 ppm. The single screw extruder and the screw were the same as in Example 1. The temperature of this single screw extruder was adjusted to 350 to 370° C., the temperature of the T die was 375° C., and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 370° C.

Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T die was measured, and it was 362° C. when measured. Further, when the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

After extruding the high heat resistance and high slidability film into a strip shape, this high heat resistance and high slidability film is used as a pair of pressure-bonding rolls made of silicone rubber and a cooling roll of 230° C. having irregularities on the peripheral surface. The rolls were sequentially wound around a metal roll and a 6-inch winding tube located downstream thereof, and sandwiched between a pressure roll and a metal roll. The pressure roll was used in Example 1 and the metal roll was used in Example 3.

The obtained high heat-resistant and high-sliding film is a pair of pressure-bonding rolls made of silicone rubber so that the metal roll surface side, which is a cooling roll, becomes the pressure-bonding roll surface side, and a cooling roll at 230° C. having irregularities on the peripheral surface. And a 6-inch winding tube located downstream of these metal rolls, and were sandwiched between the pressure roll and the metal roll. At this time, both sides of the continuous high heat resistance and high slidability film are cut with slit blades and sequentially wound on the winding tube of the winder, and the length of 100 m and the width of 620 mm are high heat resistance and high slidability. A film was produced.

Once the high heat resistance/high slidability film was obtained, the film thickness, surface roughness, heat resistance, and slidability of the high heat resistance/high slidability film were evaluated in the same manner as in Example 1 and evaluated. It was described in 2. The surface roughness of the high heat resistance/sliding film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

[Example 6]
First, the polyetheretherketone resin of Example 1 and the polyetherimide resin of Example 2 were weighed so that the compositional mass ratio was 10% by mass of polyetheretherketone resin and 90% by mass of polyetherimide resin. Further, as a fluororesin, a PFA resin [manufactured by Daikin Industries, Ltd., product name: NEOFLON PFA ACX-31 (hereinafter abbreviated as "ACX-31")] is added in a total amount of 100 parts by mass of a polyetheretherketone resin and a polyetherimide resin. To 18 parts by weight, and after weighing, three kinds of resins were put into a tumbler mixer. After the addition, the tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

After preparing the stirring mixture by stirring and mixing the polyether ether ketone resin, the polyether imide resin, and the PFA resin, the stirring mixture is fed to a twin-screw extruder with a vacuum pump, melt-kneaded under reduced pressure, and twin-screwed. A pellet-shaped molding material was prepared by extruding into a rod shape from a die at the tip of the extruder, cooling with water, and then cutting. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 345 to 365° C., a die temperature of 365° C., and a connecting pipe temperature of 365° C. for connecting the twin-screw extruder and the die to prepare a molding material.

Then, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a highly heat-resistant and highly slidable film into a strip shape. The water content of the molding material when dried was 251 ppm. The single screw extruder and the screw were the same as in Example 1. The temperature of the single screw extruder was adjusted to 345 to 365° C., the temperature of the T die was 370° C., and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 365° C.

Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T-die was measured, and it was 357° C. when measured. Further, when the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

After extruding the high heat resistance and high slidability film into a strip shape, this high heat resistance and high slidability film is used as a pair of pressure-bonding rolls made of silicone rubber and a cooling roll of 130° C. with unevenness on the peripheral surface. The rolls were sequentially wound around a metal roll and a 6-inch winding tube located downstream thereof, and sandwiched between a pressure roll and a metal roll. The pressure roll and the metal roll were the same as in Example 1.

The obtained high heat-resistant and high-sliding film is a pair of pressure-bonding rolls made of silicone rubber so that the metal roll surface side, which is a cooling roll, becomes the pressure-bonding roll surface side, and a cooling roll at 230° C. having irregularities on the peripheral surface. And a 6-inch winding tube located downstream of these metal rolls, and were sandwiched between the pressure roll and the metal roll. At this time, both sides of the continuous high heat resistance and high slidability film are cut with slit blades and sequentially wound on the winding tube of the winder, and the length of 100 m and the width of 620 mm are high heat resistance and high slidability. A film was produced. The pressure roll and the metal roll were the same as in Example 1.

Once the high heat resistant/high slidability film was obtained, the film thickness, surface roughness, heat resistance, and slidability of the high heat resistant/high slidability film were evaluated by the same method as in Example 1 and evaluated. It was described in 2. The surface roughness of the high heat resistance and high slidability film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

[Comparative Example 1]
The polyetheretherketone resin of Example 1 and the polyetherimide resin of Example 2 were weighed so that the compositional mass ratios were 40% by mass of polyetheretherketone resin and 60% by mass of polyetherimide resin. Further, as the fluororesin, the PFA resin used in Example 1 was weighed so as to be 5 parts by mass with respect to 100 parts by mass of the total amount of the polyetheretherketone resin and the polyetherimide resin. The resin was placed in a tumbler mixer. After the addition, the tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

After preparing the stirring mixture by stirring and mixing the polyetheretherketone resin, the polyetherimide resin, and the PFA resin, the stirring mixture is fed to a twin-screw extruder with a vacuum pump, melt-kneaded under reduced pressure, and twin-screw extruded. A pellet-shaped molding material was prepared by extruding into a rod shape from a die at the tip of the machine, cooling with water, and then cutting. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 350 to 370° C., a die temperature of 370° C., and a temperature of a connecting pipe connecting the twin-screw extruder and the die of 370° C. to prepare a molding material.

Then, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a highly heat-resistant and highly slidable film into a strip shape. The water content of the molding material when dried was 229 ppm. The single-screw extruder and screw are the same as in Example 1. The cylinder temperature of this single screw extruder was adjusted to 360 to 370°C, the temperature of the T die was 375°C, and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 370°C.

Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T-die was measured, and it was 367°C. Further, when the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

After extruding the high heat-resistant and high-sliding film into a strip shape, both sides are cut by slit blades in the same manner as in Example 1 and sequentially wound on a winder tube of a winder to obtain a length of 100 m and a width. A 620 mm strip-shaped film was produced. At this time, the strip-shaped film was sequentially applied to a pair of pressure-bonding rolls made of silicone rubber, a metal roll which was a cooling roll at 210° C. having irregularities on its peripheral surface, and a 6-inch winding tube located downstream thereof. It was wound around and sandwiched between a pressure roll and a metal roll. As the pressure-bonding roll, a mirror surface roll with a silicone rubber coated with a metal having an arithmetic average roughness of 0.04 μm was used, and as the metal roll, a mirror surface roll having an arithmetic average roughness (Ra) of 0.04 μm was used.

Once the high heat resistant/high slidability film was obtained, the film thickness, surface roughness, heat resistance, and slidability of the high heat resistant/high slidability film were evaluated by the same method as in Example 1 and evaluated. It was described in 3. The surface roughness of the high heat resistance and high slidability film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

[Comparative Example 2]
The composition ratio of the polyetheretherketone resin used in Example 1 and the polyetherimide resin used in Example 2 is 75% by mass of polyetheretherketone resin and 25% by mass of polyetherimide resin. Further, as a fluororesin, the same PFA resin used in Example 3 was weighed so as to be 25 parts by mass with respect to 100 parts by mass of the total amount of the polyetheretherketone resin and the polyetherimide resin, and after weighing, Three kinds of resins were put into a tumbler mixer. After the addition, this tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

After stirring and mixing the polyether ether ketone resin, the polyether imide resin and the PFA resin to prepare a stirring mixture, the stirring mixture is supplied to a twin-screw extruder equipped with a vacuum pump, melt-kneaded under reduced pressure, and then twin-screwed. A pellet-shaped molding material was prepared by extruding into a rod shape from a die at the tip of the extruder, cooling with water, and then cutting. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 350 to 370° C., a die temperature of 370° C., and a temperature of a connecting pipe connecting the twin-screw extruder and the die of 370° C. to prepare a molding material.

Then, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a high heat-resistant and highly slidable film into a strip shape. The water content of the molding material when dried was 232 ppm. The single-screw extruder and screw are the same as in Example 1. The cylinder temperature of this single screw extruder was adjusted to 360 to 370°C, the temperature of the T die was 375°C, and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 370°C.

Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T-die was measured, and it was 365° C. when measured. When the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

After extruding the high heat-resistant and high-sliding film into a strip shape, both sides are cut by slit blades in the same manner as in Example 1 and sequentially wound on a winder tube of a winder to obtain a length of 100 m and a width. A 620 mm strip-shaped film was produced. At this time, the strip-shaped film was sequentially applied to a pair of pressure-bonding rolls made of silicone rubber, a metal roll serving as a cooling roll of 205° C. having unevenness on the peripheral surface, and a 6-inch winding tube located downstream thereof. It was wound around and sandwiched between a pressure roll and a metal roll. The pressure-bonding roll made of silicone rubber and the metal roll are the same as in Example 1.

Once the high heat resistant/high slidability film was obtained, the film thickness, surface roughness, heat resistance, and slidability of the high heat resistant/high slidability film were evaluated by the same method as in Example 1 and evaluated. It was described in 3. The surface roughness of the high heat resistance and high slidability film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

[Comparative Example 3]
The polyetheretherketone resin of Example 5 and the polyetherimide resin of Example 1 were weighed so that the compositional mass ratios were 1% by mass of polyetheretherketone resin and 99% by mass of polyetherimide resin, Further, as the fluororesin, the PFA resin used in Example 1 was weighed so as to be 15 parts by mass with respect to 100 parts by mass of the total amount of the polyetheretherketone resin and the polyetherimide resin. Was charged into a tumbler mixer. After the addition, the tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

After preparing the stirring mixture by stirring and mixing the polyether ether ketone resin, the polyether imide resin, and the PFA resin, the stirring mixture is fed to a twin-screw extruder with a vacuum pump, melt-kneaded under reduced pressure, and twin-screwed. A rod-shaped extruded product was extruded from a die at the tip of the extruder, cooled with water, and then cut to prepare a molding material that was a pellet-shaped intermediate. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 340 to 360° C., a die temperature of 360° C., and a connecting pipe temperature of 360° C. for connecting a twin-screw extruder and a die to prepare a molding material.

Then, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a highly heat-resistant and highly slidable film into a strip shape. The water content of the molding material when dried was 230 ppm. The single-screw extruder was the same as in Example 1. The cylinder temperature of this single screw extruder was adjusted to 340 to 360° C., the temperature of the T die was 360° C., and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 365° C.

Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T die was measured, and it was 351° C. when measured. Further, when the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

After extruding the high heat-resistant and high-sliding film into a strip shape, both sides are cut by slit blades in the same manner as in Example 1 and sequentially wound on a winder tube of a winder to obtain a length of 100 m and a width. A 620 mm strip-shaped film was produced. At this time, the strip-shaped film was sequentially applied to a pair of pressure-bonding rolls made of silicone rubber, a metal roll which was a cooling roll at 210° C. having unevenness on the peripheral surface, and a 6-inch winding tube located downstream of these rolls. It was wound around and sandwiched between a pressure roll and a metal roll. The pressure-bonding roll made of silicone rubber and the metal roll are the same as in Example 1.

Once the high heat resistant/high slidability film was obtained, the film thickness, surface roughness, heat resistance, and slidability of the high heat resistant/high slidability film were evaluated by the same method as in Example 1 and evaluated. It was described in 3. The surface roughness of the high heat resistance and high slidability film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

[Comparative Example 4]
The polyether ether ketone resin of Example 5 and the polyether imide resin of Example 1 were weighed so that the compositional weight ratios were 20% by mass of polyetheretherketone resin and 80% by mass of polyetherimide resin, These two kinds of resins were put into a tumbler mixer. After the addition, the tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

After preparing the agitated mixture, this agitated mixture is supplied to a twin-screw extruder with a vacuum pump, melt-kneaded under reduced pressure, extruded into a rod shape from a die at the tip of the twin-screw extruder, water-cooled and cut, and pelletized. A molding material, which is an intermediate in shape, was prepared. The stirring mixture was melt-kneaded under the conditions of a cylinder temperature of 345 to 365° C., a die temperature of 365° C., and a connecting pipe temperature of 365° C. connecting the twin-screw extruder and the die to prepare a molding material.

Then, the molding material is put into a dehumidifying dryer heated to 150° C. and dried for 12 hours, and the dried molding material is set in a φ40 mm single-screw extruder equipped with a T die having a width of 900 mm and melt-kneaded. The melt-kneaded molding material was continuously extruded from a T-die of a single-screw extruder to extrude a highly heat-resistant and highly slidable film into a strip shape. The water content of the molding material when dried was 254 ppm. The single screw extruder and the screw were the same as in Example 1. The cylinder temperature of this single screw extruder was adjusted to 350 to 370° C., the temperature of the T die was 375° C., and the temperature of the connecting pipe connecting the single screw extruder and the T die was adjusted to 370° C.

Regarding the temperature of the molten molding material, the resin temperature at the inlet of the T-die was measured, and it was 365° C. when measured. Further, when the molding material was charged into the single-screw extruder, nitrogen gas of 18 L/min was supplied.

In this way, the high heat resistant and high slidability film was extruded in the shape of a strip, and in the same manner as in Example 1, both sides were cut with slit blades and sequentially wound on the winding tube of the winder, and the length was 100 m. A strip-shaped film with a width of 620 mm was produced. At this time, the strip-shaped film was sequentially applied to a pair of pressure-bonding rolls made of silicone rubber, a metal roll which was a cooling roll at 230° C. having irregularities on its peripheral surface, and a 6-inch winding tube located downstream thereof. It was wound around and sandwiched between a pressure roll and a metal roll. The pressure roller made of silicone rubber and the metal roll were the same as in Example 1.

The obtained high heat-resistant and high-sliding film is a pair of pressure-bonding rolls made of silicone rubber so that the metal roll surface side, which is a cooling roll, becomes the pressure-bonding roll surface side, and a cooling roll at 230° C. having irregularities on the peripheral surface. And a 6-inch winding tube located downstream of these metal rolls, and were sandwiched between the pressure roll and the metal roll. At this time, both sides of the continuous high heat resistance and high slidability film are cut with slit blades and sequentially wound on the winding tube of the winder, and the length of 100 m and the width of 620 mm are high heat resistance and high slidability. A film was produced. The pressure roller made of silicone rubber and the metal roll were the same as in Example 1.

Once the high heat resistant/high slidability film was obtained, the film thickness, surface roughness, heat resistance, and slidability of the high heat resistant/high slidability film were evaluated by the same method as in Example 1 and evaluated. It was described in 4. The surface roughness of the high heat resistance and high slidability film is the arithmetic mean roughness (Ra), the heat resistance is the first inflection point temperature and the storage elastic modulus at 280°C (E'), and the slidability is the static friction coefficient. (Μs) and dynamic friction coefficient (μk).

[Comparative Example 5]
The polyether ether ketone resin of Example 1 and the polyether imide resin of Example 2 were weighed in such a manner that the composition ratio of the polyether ether ketone resin was 40% by mass, and the polyetherimide resin was 60% by mass. Further, as the fluororesin, the PFA resin used in Example 3 was weighed so as to be 35 parts by mass with respect to 100 parts by mass of the total amount of the polyetheretherketone resin and the polyetherimide resin, and three kinds of resins were weighed after the measurement. Was charged into a tumbler mixer. After the addition, the tumbler mixer was stirred and mixed at 23° C. for 1 hour to prepare a stirred mixture.

After preparing the stirring mixture by stirring and mixing the polyether ether ketone resin, the polyether imide resin, and the PFA resin, the stirring mixture is fed to a twin-screw extruder with a vacuum pump, melt-kneaded under reduced pressure, and twin-screwed. A rod-shaped extruded product was extruded from a die at the tip of the extruder, cooled with water, and then cut to prepare a molding material as a pellet-shaped intermediate. The stirred mixture was melt-kneaded under the conditions of a cylinder temperature of 350 to 370° C., a die temperature of 370° C., and a temperature of a connecting pipe connecting the twin-screw extruder and the die of 370° C.

Since the melt-kneaded product has no melt tension, it was not possible to form a strand-shaped extrusion-molded product, so that a pellet-type molding material could not be produced. Therefore, a high heat resistance/high slidability film was not formed.

[Result]
The high heat resistance and high slidability films obtained in the respective examples have a first inflection point temperature of 170° C. or higher and can prevent deformation due to external force at a higher temperature than polyetheretherketone resin, and have storage elasticity at 280° C. Since the rate was 1×10 ⁵ Pa or more, excellent high temperature heat resistance could be obtained. Further, both the static friction coefficient and the dynamic friction coefficient were 1.0 or less, and excellent slidability could be obtained.

On the other hand, the high heat resistance/high slidability film of Comparative Example 1 has sufficient heat resistance, but the static friction coefficient and the dynamic friction coefficient with the PC resin sheet are 1.0 or more, which is insufficient. Only good slidability was obtained. Further, the high heat resistance/high slidability film of Comparative Example 2 had a problem with heat resistance because the first inflection point temperature was less than 170°C. The highly heat resistant and highly slidable film of Comparative Example 3 had heat resistance of the first inflection point temperature of 170° C. or higher, but the storage elastic modulus at 280° C. was less than 1×10 ⁵ Pa, which was unsatisfactory. It has sufficient heat resistance.

The high heat resistance/high slidability film of Comparative Example 4 has sufficient heat resistance as in Comparative Example 1, but the static friction coefficient and dynamic friction coefficient with the PC resin sheet are 1.0 or more, and It has a sufficient slidability. Furthermore, in Comparative Example 5, since the melt-kneaded product had no melt tension, it was not possible to form a strand-shaped extruded product. For this reason, a pellet-type molding material could not be manufactured, and a high heat resistance and high slidability film could not be molded.

The highly heat-resistant and highly slidable film according to the present invention is used in the manufacturing fields of electric/electronic equipment, information equipment, terminal equipment, medical equipment, automobiles, aircrafts and the like.

1 High heat resistance/high slidability film 2 Molding material 10 Melt extrusion molding machine (extrusion molding machine)
12 T dice
16 Crimping Roll 17 Cooling Roll 18 Winding Machine 19 Winding Tube 20 Slit Blade 21 Tension Roll

Claims (2)

A polyetheretherketone resin having a repeating unit represented by the chemical formula [Chemical Formula 1] and a polyetherimide resin having a repeating unit represented by the chemical formula [Chemical Formula 2] and having a glass transition point of 200° C. or higher, High heat resistance obtained by adding 1 to 30 parts by mass of a fluororesin to 100 parts by mass of a resin composition composed of 5 to 70% by mass of a polyether ether ketone resin and 95 to 30% by mass of a polyetherimide resin in a composition mass ratio.・High slidability film,

The properties of the cooled film are heat resistance [the first inflection point temperature of storage elastic modulus (E′)] is 170° C. or more, storage elastic modulus at 280° C. is 1×10 ⁵ Pa or more, and slidability is JIS. High heat resistance characterized by a static friction coefficient of 1.0 or less measured according to K7125-1999 and a dynamic friction coefficient of 1.0 or less measured according to JIS K7125-1999. Highly slidable film. The highly heat resistant and highly slidable film according to claim 1 , wherein the cooled film has a thickness of 3 to 1000 μm.

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