TW201904767A - Laminated body with thermoplastic engineering plastic layer and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a laminate which comprises a thermoplastic engineering plastic layer having a thickness of 250 [mu]m or less and a method for producing this laminate; and the present invention specifically provides a thin engineering plastic film which has excellent thickness uniformity and surface smoothness. A thin engineering plastic film having a thickness of 250 [mu]m or less and a thickness accuracy of 15% or less is obtained by extrusion coating one surface of a release film, which has a tensile strength at break of 115 MPa or more and a tensile elongation at break of 190% or less in the production direction, with a molten engineering plastic material, and by removing the release film after the formation of a laminate.

Description

Laminated body with layer of thermoplastic engineering plastic and manufacturing method thereof

The present invention relates to a laminate having a layer of thermoplastic engineering plastics and a manufacturing method thereof. More specifically, it relates to a thin engineering plastic film with excellent thickness uniformity and surface smoothness and a manufacturing method thereof.

As for the method of manufacturing a thermoplastic engineering plastic film, it is generally widely used to clamp the melt-extruded resin with a nip roller, or to make it tightly contact with a large-diameter cooling drum to manufacture a film.

However, if the resin that is melt-extruded is nipped by the nip roll and allowed to cool to produce a film, uneven elongation will occur between the die outlet and the nip roll, making the end of the film extremely thin, or When the end thickened by the necking of the melt is cut by a cutter, the film may frequently break or elongate. In addition, when making a thin film in close contact with a large cooling drum, there is a problem that it is difficult to obtain a uniform thin film with a smooth surface. This is because when the film melted at a high temperature is cooled to room temperature, the molten film shrinks due to the temperature drop, and the molten film slides on the cooling drum, making it difficult to be uniformly cooled and solidified. Therefore.

On the other hand, a solvent casting method has been proposed in which a resin is diluted with a special solvent and coated to obtain a thin film (for example, Patent Document 1). However, it requires the recovery of used solvents, and the management of the operating environment has also become a problem.

As another method, a method has been proposed that involves co-extrusion of an engineering plastic melt and a resin melt having releasability with the melt, and peeling off the peelable resin film to obtain the target Engineering plastic film (for example, Patent Document 2). However, the release film extruded in the molten state must have good releasability for engineering plastics, and in order to obtain a good-looking film by co-extrusion, it must be a resin with similar flow characteristics when melted, so it can be used. The problem of limited types of resins.

On the other hand, in medical-related fields, food-related fields, electrical and electronic parts-related fields, etc., they require engineering plastic films with excellent hydrolysis resistance, hot water resistance, chemical resistance, electron beam resistance, gamma-ray resistance, etc. .

Prior technical literature Patent Literature

Patent Literature 1 Japanese Patent Application Publication No. 2009-226632

Patent Literature 2 Japanese Patent Application Publication No. 2007-21912

The invention relates to a layered body provided with a layer of thermoplastic engineering plastic of 250 μm or less and a manufacturing method thereof, in particular to provide a thin engineering plastic film with excellent thickness uniformity and surface smoothness.

The inventors of the present invention have concentrated on the above-mentioned subject, and found that the solution can be obtained by extruding one side of the peeling film and applying the engineering plastic melt and peeling off the peeling film after forming the laminate. The engineering plastic film, the subject of the invention, achieved the invention.

That is, the present invention for solving the aforementioned problems is composed of the following:

(1) A laminate which is one side of a peeling film having a tensile breaking strength of 115 MPa or more and a tensile breaking elongation of 190% or less in the production direction, and has a thickness of 250 μm or less and a thickness accuracy of 15% The following layers of thermoplastic engineering plastics.

(2) The laminate as described in (1) above, wherein the layer of the engineering plastic includes: selected from the group consisting of polyetheretherketone, polycarbonate, polyacrylate, polyacetal, polyphenylene sulfide, and polyether 、Polyphenol, polystyrene, polyether amide imide, polyamide amide imide, polyether ketone, polybenzimidazole, cycloolefin polymer, liquid crystal polymer and these modified groups One or more polymers or a mixture of two or more polymers selected from the aforementioned group.

(3) The laminate as described in (1) or (2) above, wherein the release film contains: selected from the group consisting of polypropylene, polyethylene terephthalate, polyethylene naphthalate, and polyamide One group of more than one polymer or a mixture of two or more polymers selected from the aforementioned group.

(4) The laminate according to any one of (1) to (3) above, wherein the arithmetic average surface roughness of the surface of the engineering plastic layer on the side in contact with the release film is 1.0 μm or less.

(5) A thin film, which is a layer of the engineering plastic including the laminate according to any one of (1) to (4).

(6) The thin film described in (5) above, which is a film for thin film capacitors.

(7) The thin film described in (5) above is a film for a speaker diaphragm.

(8) The thin film described in (5) above is a film for a circuit board.

(9) The thin film described in (5) above, which is a film for heater insulation.

(10) The thin film described in (5) above, which is a film for glass protection.

(11) A method for manufacturing the aforementioned laminate, which is to extrude a thermoplastic engineering plastic melt on one side of a peeling film with a tensile breaking strength of 115 MPa or more and a tensile breaking elongation of 190% or less in the production direction, and A method for manufacturing a laminated body of a layer of thermoplastic engineering plastic with a layer thickness of 250 μm or less and a thickness accuracy of 15% or less, characterized in that the temperature when the thermoplastic engineering plastic melt contacts the release film is Tx, and the temperature of the release film When the glass transition temperature is Tg1 and the melting point of the release film is Tm, the relationship of Tg1≦Tx≦Tg1+180° C≦Tm is satisfied.

(12) The method for manufacturing the laminate described in (11) above, wherein the layer of the engineering plastic includes: selected from the group consisting of polyetheretherketone, polycarbonate, polyacrylate, polyacetal, and polyphenylene sulfide 、Polyether socks, poly socks, polystyrene socks, polyether amide imine, poly amide amide imide, polyether ketone, polybenzimidazole, cycloolefin polymer, liquid crystal polymer and their modified products One group of more than one polymer or a mixture of two or more polymers selected from the aforementioned group.

(13) The method for manufacturing the laminate according to (11) or (12), wherein the release film contains: a material selected from the group consisting of polypropylene, polyethylene terephthalate, and polyethylene naphthalate 1. A group of more than one polymer of polyamide or a mixture of two or more polymers selected from the aforementioned group.

(14) The method for manufacturing the laminate as described in any one of (11) to (13) above, wherein the arithmetic average surface roughness of the surface of at least the side of the engineering plastic layer in contact with the release film is 1.0 Below μm.

(15) A method for manufacturing a thin engineering plastic film, characterized in that after the layered body is obtained by the method for manufacturing a layered body described in any one of (11) to (14) above, the release film is separated from The aforementioned laminate is peeled off and removed.

(16) The thin film described in (5), which is subjected to any treatment of hot water, chemicals, sterilization, and ozone.

(17) The thin film described in (5) has a tensile elongation retention rate of 35% or more under a pressure cooker condition of 120°C, 100% RH, 96 hours before and after the pressure cooker test.

(18) The thin film according to (5), which is subjected to any treatment of electron beam irradiation or gamma irradiation.

(19) The thin film described in (5), which is a film for home appliance parts.

(20) The thin film described in (5) is a film for automobile parts and components.

The thin engineering plastic film of the present invention has excellent thickness homogeneity with a so-called thickness deviation (thickness accuracy) of 15% or less, although the thickness is as thin as 250 μm or less. The engineering plastic film of this kind of film with excellent thickness homogeneity is used for applications requiring high precision such as film capacitors, speaker vibration plates or circuit board materials.

Forms for carrying out the invention

The laminate having the thin engineering plastic film of the present invention is a laminate obtained by extrusion coating a thermoplastic engineering plastic melt on a peeling film. In addition, the thin engineering plastic film in the present invention is characterized by a thin engineering plastic film obtained by peeling off a peeling film from a laminate. The present invention is explained in detail by the following preferred examples, but it is not limited thereto.

<Engineering Plastic>

The thermoplastic resin constituting the thermoplastic engineering plastic film is not limited to crystalline and amorphous, but can be suitably selected from polyetheretherketone, polycarbonate, polyacrylate, polyacetal, polyphenylene sulfide, Polyether sulfone, poly sulfone, polystyrene sulfonate, polyether amide imide, polyamide amide imide, polyether ketone, polybenzimidazole, cyclic olefin polymer, liquid crystal polymer and the modified products of these A group of more than one polymer or a mixture of two or more polymers selected from the aforementioned group.

<release film>

The tensile breaking strength of the peeling film in the production direction is preferably 115 MPa or more, more preferably 120 MPa or more, even more preferably 130 MPa or more, and particularly preferably 140 MPa or more in order to prevent the fracture of the laminate after extrusion coating. The best is more than 150MPa.

The tensile elongation at break in the production direction of the release film is preferably 190% or less, more preferably 170% or less, and even more preferably 160% or less in order to prevent the elongation and deformation of the laminate after extrusion coating. The best is 150% or less, and the best is 100 or more and less than 110%.

The thickness of the release film is not specifically defined. However, if it is too thin, the tensile strength at break in the production direction is reduced or the tensile elongation at break is increased, and wrinkles are generated during winding. If it is too thick, it is peeled off due to the elasticity of the film during winding. The film will be peeled off by the laminate, the winding itself becomes impossible, and the cost will increase. Therefore, the thickness of the release film is preferably 12 μm or more and 100 μm or less, more preferably 12 μm or more and 80 μm or less, still more preferably 13 μm or more and 70 μm or less, particularly preferably 14 μm or more and 60 μm or less, and most preferably 15 μm or more and 50 μm or less.

As for the material of the peeling film, at least one kind of polymer selected from polypropylene, polyethylene terephthalate, polyethylene naphthalate, and polyamide or selected from the foregoing group can be suitably used A mixture of two or more polymers. In particular, from the viewpoint of tensile breaking strength or tensile breaking elongation in the production direction, it is more preferable to use a uniaxially stretched or biaxially stretched film for the production direction. In addition, to improve the adhesion between the peeling film and the thermoplastic engineering plastic film, corona treatment, plasma treatment, ozone treatment, flame treatment, alkali treatment, evaporation treatment, and primer treatment can be applied to the surface of the peeling film Zhou Zhizhi then proceeded. On the other hand, to improve the releasability of the release film and the thermoplastic engineering plastic film, a well-known release treatment such as applying a release agent can be applied to the surface of the release film.

<additive>

Thermoplastic engineering plastics and release films may also contain additives such as antioxidants, ultraviolet absorbers, light stabilizers, lubricants, antistatic agents, inorganic fillers, colorants, nucleating agents, flame retardants, plasticizers and the like. The blending amount of these additives is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 30% by mass or less with respect to 100% by mass of thermoplastic engineering plastics or resin components constituting the release film. The best is 20% by mass or less, and the best is 10% by mass or less. If the blending amount of the additive exceeds 40% by mass, the appearance or formability of the film may be significantly reduced.

<Engineering Plastic Film>

The thermoplastic engineering plastic film of the present invention is characterized in that the thickness after peeling off the peeling film is preferably 250 μm or less, more preferably 150 μm or less, still more preferably 50 μm or less, particularly preferably 30 μm or less, and most preferably 20 μm or less.

Furthermore, the thermoplastic engineering plastic film of the present invention is characterized in that the thickness accuracy after peeling off the peeling film is preferably 15% or less, more preferably 12% or less, still more preferably 10% or less, particularly preferably 7% Below, the best is below 5%. The thickness accuracy referred to here is an index indicating the thickness error. The lower the value, the higher the thickness accuracy. The thickness accuracy of the present invention can be based on JIS K 7130, and the Mitutoyo company's system gauges that can measure up to 1 μm can be measured at 20 points at equal intervals to obtain the average (dave), maximum (dmax), and minimum (dmin) , And calculated by the following formula: thickness accuracy (%) = ((dmax-dmin)/dave)×100.

The thermoplastic engineering plastic film of the present invention has an arithmetic average surface roughness of at least the surface in contact with the release film is preferably 1.0 μm or less, more preferably 0.8 μm or less, even more preferably 0.6 μm or less, particularly preferably 0.5 μm or less , The best is 0.2μm or less. Especially for thin films used for thin film capacitor applications, if the arithmetic average surface roughness is greater than 1.0 μm, the capacity or withstand voltage will be significantly reduced, making it difficult to obtain sufficient performance when used as thin film capacitors.

<Formation of Engineering Plastic Film>

For the method of forming the thermoplastic engineering plastic film of the present invention, extrusion coating is preferably used. The resin or resin composition constituting the thermoplastic engineering plastic melt can be laminated by a single uniaxial extruder or biaxial extruder by a single-layer or multi-manifold die or feeding sleeve. The two or more layers are extruded on the peeling film, and the peeling film is peeled off after forming the laminate to obtain a thin thermoplastic engineering plastic film.

At this time, the temperature (Tx (℃)) of the extruded thermoplastic engineering plastic melt contacting the release film is relative to the glass transition temperature (Tg1 (℃)) and melting point (Tm (℃)) of the release film, and Satisfaction is preferably Tg1≦Tx≦Tg1+180°C≦Tm, more preferably Tg1+5°C≦Tx≦Tg1+180°C≦Tm, and even more preferably Tg1+10°C≦Tx≦Tg1+180°C≦Tm, Particularly preferably, the relationship of Tg1+15°C≦Tx≦Tg1+180°C≦Tm, and the best relationship is Tg1+20°C≦Tx≦Tg1+180°C≦Tm. When Tx is lower than Tg1, good adhesion strength between the thermoplastic engineering plastic film and the peeling film cannot be obtained, and it may cause breakage or elongation deformation or wrinkles during the step or winding. On the other hand, if Tx exceeds Tg1+180°C, the peeling strength will be too high to peel off the peeling film, and the shrinkage of the peeling film will increase to cause wrinkles, and if Tx exceeds Tm, the peeling film Will melt.

The temperature of the metal roller (Ty(℃)) is relative to the glass transition temperature of the thermoplastic engineering plastics (Tg2(℃)), and satisfies Tg2-120℃≦Ty≦Tg2+20℃, more preferably Tg2 -115℃≦Ty≦Tg2+15℃, more preferably Tg2-110℃≦Ty≦Tg2+12℃, especially Tg2-110℃≦Ty≦Tg2+10℃, the best is Tg2-100℃≦ The relationship of Ty≦Tg2+5℃ is better. When Ty is lower than Tg2-120℃, it will become difficult to obtain good adhesion strength between the thermoplastic engineering plastic film and the peeling film, and if Ty exceeds Tg+20℃, the thermoplastic engineering plastic film will adhere to the metal roller and become It is difficult to peel off the film smoothly from the metal roller, and the appearance of the film becomes easily deteriorated.

The peel strength of the peeling film in the laminate is preferably 3 g/cm or more and 1000 g/cm or less. In addition, the peel strength of the peeling film in the laminate is preferably 3 g/cm or more and less than 10 g/cm, or 100 g/cm or more and 1000 g/cm or less, but most preferably 10 g/cm or more and less than 100 g/cm. If the peel strength is less than 3g/cm, the film will peel off during the winding process, and it may cause breakage, elongation, and wrinkles. On the other hand, if the peel strength is greater than 1000 g/cm, the peeling film cannot be peeled off, and the film may break.

<Use of Engineering Plastic Film>

Examples of applications of the thin engineering plastic film of the present invention include film capacitors, speaker diaphragms, circuit boards, heater insulation materials, glass protective films, home appliance parts, and automobile parts parts.

In the application of thin film capacitors, the thin film of the present invention functions as a dielectric and is used for engineering plastic thin film laminated conductor layers. This conductor layer is formed by, for example, vapor deposition, sputtering, and lamination with metal foil. The thickness of the dielectric and its accuracy will greatly affect the capacity or withstand voltage, so it is required to have a film thickness of 10 μm or less and a thickness accuracy of 15% or less. The thin engineering plastic film of the present invention can meet these requirements.

In the application of the speaker vibration plate, the film of the present invention functions as a vibration plate, and for the engineering plastic film, it is required that the natural vibration caused by the division vibration or resonance is less and the conversion efficiency is good. Therefore, the film is required to have high thickness accuracy in addition to the high Young's modulus, but if it is the thin engineering plastic film of the present invention, it can be suitable for this purpose due to the thickness accuracy of 15% or less.

In the circuit board application, the film of the present invention functions as a base film of a laminate, and a metal layer, a ceramic layer, a resin layer, etc. are laminated. For example, in the case of FPC (Flexible Printed Circuits), a metal layer for wiring is formed on the surface of the substrate film by dry lamination, gold plating, evaporation, sputtering, etc. The engineering plastic film of the present invention is excellent in heat deformation resistance, heat resistance dimensional stability and heat resistance toughness due to the resin and the resin composition. Therefore, the film of the present invention is used as a laminate of a base film, and warpage is sufficiently suppressed. The peeling of the laminated metal layer or the like is unlikely to occur, and cracking or breakage due to reduced flexibility is also unlikely to occur. In addition, since the thickness accuracy is high, the homogeneity of the withstand voltage characteristics within the layered body is excellent.

In the application of the heater insulation material, the film of the present invention functions as a base film. Since the film of the present invention has high thickness accuracy, it has excellent uniformity in voltage resistance characteristics within the surface of the laminate.

In the use of glass protective films, the film of the present invention functions as a base film, and an adhesive layer mainly composed of acrylic or polysilicon is laminated. The film of the present invention is bonded to the glass plate with an adhesive layer therebetween to prevent the glass from scattering when it breaks. Since the film of the present invention is thin and has excellent thickness accuracy or surface smoothness, it can be useful for obtaining a good appearance even when it is bonded to glass.

In automotive component applications, the resin-based resin film of the present invention functions as a component used in an environment around 200° C. such as an engine peripheral component or a gearbox component. In addition, since the amount of outgas generated during heating is small, it has little influence on other electronic devices and is useful.

For applications such as food packaging components and conditioning equipment components, especially in thermoplastic engineering plastics, resin compositions containing satin resins are used. For example, the ballast-based resin film is used as a component used in the sterilization/sterilization step, and is required to be irradiated with hot water, chemicals, high-pressure steam, circulating steam, dry heat, ultraviolet radiation, and gamma radiation. , Electron beam irradiation, ethylene oxide gas, ozone and other treatments will not cause physical deterioration, but because it can meet this requirement if it is the satin resin film of the present invention, it can be used as a food packaging bag, for example (Steaming bags, etc.), household conditioning equipment (microwave oven conditioning equipment, etc.), business conditioning equipment, vending machines, water purifiers, etc.

In addition, the thermoplastic engineering plastic film of the present invention can also be used as a molded product. For example, the ballast-based resin film can meet general molding requirements. As for the molding method, in addition to insert molding and in-mold molding, a method of heating and softening the resin sheet in a vacuum state and opening to atmospheric pressure to nest (mold) the surface of an existing molded product, etc. As a general vacuum forming, pressure forming or these applications, but not limited to these. In addition, as a method of heating and softening the sheet before forming, a well-known sheet heating method such as non-contact heating by radiant heating by an infrared heater or the like can be applied. In the vacuum pressure forming of one embodiment, for example, the resin sheet is heated at a surface temperature of 60°C to 310°C for 20 seconds to 480 seconds, and then formed on the surface of the existing molded product, and can be drawn according to the shape of the surface Stretching is 1.05~2.50 times.

<Stone-based resin composition>

It is preferable that the resin composition constituting the resin sheet of the resin sheet contains 80% by mass or more of one selected from the group consisting of modified resins such as poly-ballast, polyether-ballast, polyphenylene-sulfide, and the like More than one kind of resin composition.

The ballast-based resin is not particularly limited, and it is preferably a polyphenylene ballast having a repeating unit represented by formula (1), or a polyether ballast having a repeating unit represented by formula (2). You can choose more than one type of polystyrene and/or polyether ballast to use.

Polyphenylene sulfonate (PPSU) may be a homopolymer including only the chemical structure of formula (1), or may include one or more chemical structures selected from formulas (2) to (10). However, since the proportion of the chemical structure of formula (1) in polystyrene is higher, the film strength, heat resistance, and forming processability are better. Therefore, the total unit of formula (1) to (10) is 100 Mo Ear %, preferably the unit of formula (1) is 50 mole% or more, more preferably 60 mole% or more, even more preferably 70 mole% or more, particularly preferably 75 mole% or more, the best is More than 80% mole. Polyphenylene sulfide is a copolymer containing the chemical structure of formulas (2) to (10). The copolymerization form can be any of block copolymers, random copolymers, and alternating copolymers. Alternatively, it may be a terminal modified product having only another chemical structure at the polymer terminal. As a specific example of polystyrene, a trade name made by SOLVAY SPECIALTY POLYMERS company: Radel R series, a trade name made by BASF company: Ultrason P series.

Polyether sulfone (PES) may be a homopolymer containing only the chemical structure of formula (2), or may include one or more chemical structures selected from (1) and (3) to (10). However, in the polyether ballast, the ratio of the chemical structure of formula (2) is preferably 100 moles relative to the units of formula (1) to (10) from the viewpoint of excellent film strength, heat resistance, and formability. %, the unit of formula (2) is 50 mol% or more, more preferably 60 mol% or more, even more preferably 70 mol% or more, particularly preferably 75 mol% or more, most preferably 80% mol %the above. In the case where the polyether ballast has a single or multiple chemical structures selected from (1) and (3) to (10) to form a copolymer, the copolymerization form can be block copolymer, random copolymer, alternating copolymer Any kind. Alternatively, it may be a terminal modified product having only another chemical structure at the polymer terminal. Specific examples of polyether tarnish include Sumitomo Chemical's trade name: SUMIKAEXCEL PES series, BASF's trade name: Ultrason E series, SOLVAY SPECIALTY POLYMERS company's Veradel R series.

[Example]

Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these.

In the examples and comparative examples, the following were used as thermoplastic engineering plastics and release films.

<Thermoplastic Engineering Plastics>

Polyetheretherketone (PEEK): manufactured by Daicel-Evonik, glass transition temperature 140℃, melting point 345℃

Polyphenylene sulfide (PPS): manufactured by TORAY, glass transition temperature 90℃, melting point 280℃

Polyether ballast (PES): made by BASF, glass transition temperature 225℃, no melting point

Polystyrene (PPSU): made by BASF, glass transition temperature 220℃, no melting point

PSU (PSU): BASF company, glass transition point 187 ℃, no melting point

<release film>

Biaxially stretched polyamide film (O-Ny1): manufactured by UNITIKA, tensile breaking strength 200 MPa, tensile breaking elongation 100%, glass transition temperature 120°C, melting point 305°C, thickness 25 μm

Biaxially stretched polyamide film (O-Ny2): manufactured by Toyobo, tensile breaking strength 200 MPa, tensile breaking elongation 110%, glass transition temperature 70°C, melting point 230°C, thickness 25 μm

Biaxially stretched polypropylene film (O-PP): manufactured by Mitsui Chemicals Tohcello, tensile breaking strength 130 MPa, tensile breaking elongation 170%, glass transition temperature -20°C, melting point 170°C, thickness 40 μm

Biaxially stretched polyethylene terephthalate film (O-PET): manufactured by TORAY, tensile breaking strength 153MPa, tensile breaking elongation 105%, glass transition temperature 69℃, melting point 263℃, thickness 16μm

Unstretched polyamide film (C-Ny): manufactured by Mitsubishi Plastics Corporation, tensile breaking strength 140 MPa, tensile breaking elongation 300%, glass transition temperature 70°C, melting point 230°C, thickness 25 μm

Unstretched polypropylene film (C-PP): manufactured by Mitsui Chemicals Tohcello, tensile breaking strength 80 MPa, tensile breaking elongation 700%, glass transition temperature -20°C, melting point 170°C, thickness 40 μm

<Measurement of tensile breaking strength and tensile breaking elongation>

In accordance with JIS K 7127, a tensile tester manufactured by Toyo Seiki Co., Ltd. was used to measure the film production direction, and the tensile breaking strength and tensile breaking elongation were obtained from the obtained stress-strain curve.

<Determination of glass transition temperature and melting point>

Using the differential scanning calorimeter "DSC3100SA" manufactured by Bruker, the temperature and melting point of the thermoplastic engineering plastics and the release film were measured by DSC (Differential scanning) from room temperature to 370°C at a heating rate of 10°C/min under a nitrogen atmosphere calorimetry (differential scanning heat) measurement, the glass transition point is taken at the intersection of the following two lines: in the DSC curve, from the extended line of each baseline from the straight line equidistant to the longitudinal axis, the stepped change from the glass transition Curve.

(Example 1)

The polyether ether ketone (PEEK) for thermoplastic engineering plastics will be extruded by a uniaxial extruder with a caliber of 40 mm, and the temperature of the die, the amount of resin discharged, the line speed, and the distance between the die and the roller will be adjusted to The temperature at which the polyamide film (O-Ny) was stretched and contacted was axially 175°C, and the temperature of the metal roll was controlled to 90°C to obtain a laminate. Thus, the laminate was stripped of the biaxially stretched polyamide film to produce an engineering plastic film with a thickness of 50 μm.

(Examples 2-12, Comparative Examples 1-8, Comparative Example 11, Comparative Examples 13-15, Comparative Examples 17, 18)

The types of the release film, the type and thickness of the thermoplastic engineering plastic, the temperature at which the extruded molten resin contacts the release film, and the temperature of the metal roll cooling the laminate are changed as described in Tables 1 and 3. An engineering plastic film was produced in the same manner as in Example 1.

(Example 13)

Polystyrene (PPSU) for thermoplastic engineering plastics is extruded by a uniaxial extruder with a caliber of 40 mm, and the temperature of the mold, the amount of resin discharged, the line speed, and the distance between the die and the roller are adjusted to make it biaxial The temperature at which the polyamide film (O-Ny) was stretched and brought into contact was 190°C, and the temperature of the metal roller was controlled to 115°C to obtain a laminate. Thus, the laminate was stripped of the biaxially stretched polyamide film, and an engineering plastic film with a thickness of 25 μm was produced.

(Examples 14 to 23)

The types of the release film, the type and thickness of the thermoplastic engineering plastic, the temperature at which the extruded molten resin contacts the release film, and the temperature of the metal roll that cools the laminate are changed as described in Table 2. In the same manner as in Example 1, an engineering plastic film was produced.

(Comparative examples 9, 10, 12, 16)

Except that no release film is used, polyetheretherketone (PEEK) or polyphenylene sulfide (PPS), or polyethersulfone (PES), which is a thermoplastic engineering plastic, is extruded by a uniaxial extruder with a caliber of 40 mm, and A single-layer engineering plastic film was produced in the same manner as in Example 1, except that the temperature of the metal roller cooling the extruded molten resin was changed as described in Table 3.

<assessment method>

The heat-resistant films produced in the examples and comparative examples were evaluated as shown below. The results are summarized and shown in Table 1 to Table 3.

<Measurement of thickness>

According to JIS K 7130, the Mitutoyo system gauges that can be measured to 1 μm are used to measure 20 points at equal intervals and take the average value.

<Measurement of thickness accuracy>

According to JIS K 7130, 20 points were measured at equal intervals with a Mitutoyo company gauge that can measure up to 1 μm, and the average value (dave), maximum value (dmax), and minimum value (dmin) were taken, and the thickness accuracy was calculated according to the following formula degree(%).

Thickness accuracy (%)=((dmax-dmin)/dave)×100

<Measurement of peel strength>

The test piece (100 mm long axis×10 mm short axis) cut out from the laminate in the production direction was obtained by the force when peeling was performed at a peeling angle of 180 degrees using a peeling tester manufactured by Vanguard Systems. Those with a peel strength of 10g or more and less than 100g/cm were rated as "excellent", those with a 3g or more and less than 10g or 100g or more and 1000g or less/cm were rated as "good", and those with 0g or more and less than 3g/cm Or more than 1000g/cm is rated as "bad".

<Measurement of arithmetic average surface roughness>

The surface of the engineering plastic film contacting the peeling film was observed with a laser microscope manufactured by KEYENCE at a magnification of 1000 times, and the arithmetic average surface roughness was calculated according to JIS B 0601:1994.

<Measurement of temperature of laminate>

The temperature of the junction between the melt of the engineering plastic and the peeling film was measured using a contact thermometer made by Anritsu Instruments Co., Ltd. at 3 points in the width direction, and the average value was calculated.

<surface temperature of metal roller>

The surface temperature of the metal roll was measured using a contact thermometer made by Ricoh Industrial Co., Ltd., and three points in the width direction of the metal roll were measured, and the average value was calculated.

<winding wrinkle of laminate>

After the laminate was wound by a winding machine for 100 m, the full width was confirmed, and those who had winding wrinkles on the appearance were rated as “yes”. Those who are not confirmed are rated as "none".

<Fracture of laminate>

The case where the layered body was wound by 100 m in the step was rated as “yes”, and the case where it did not occur was rated as “no”.

<hydrolysis resistance evaluation>

The thin film (thermoplastic engineering plastic film from which the peeling film was peeled off from the laminate) was cut into A4 size, using a pressure cooker tester (SPY-4016 manufactured by ALP), and maintained at 120°C and 100% RH for 96 hours . Thereafter, a tensile test was carried out in an environment of 23° C. and 50% RH in accordance with JIS K 7127. If the elongation retention rate is 35% or more, it is judged that there is no problem in actual use.

The elongation retention rate is calculated by the following formula: elongation retention rate=[(tensile elongation after pressure cooker test)/(tensile elongation before pressure cooker test)]×100.

<Hot water resistance evaluation>

The thin film (thermoplastic engineering plastic film from which the peeling film was peeled off from the laminate) was cut into A4 size, and immersed in hot water controlled by a thermostat at 90°C for 168 hours. Thereafter, in an environment of 23°C and 50% RH, a tensile test was performed in accordance with JIS K 7127, and if the elongation retention rate was 50% or more, it was judged as good.

The elongation retention rate is calculated by the following formula: elongation retention rate=[(tensile elongation after warm water immersion)/(tensile elongation before warm water immersion)]×100.

<drug resistance evaluation>

The thin film (thermoplastic engineering plastic film from which the peeling film was peeled off from the laminate) was cut into A4 size and immersed in sulfuric acid (20% concentration) for 2 hours. Thereafter, the film sample was taken out, and it was judged from the appearance whether "whitening", "cracking", etc. occurred. Those that did not occur were rated as "○", and those that did occur were rated as "×".

<e-beam resistance evaluation>

The thin film (thermoplastic engineering plastic film from which the peeling film was peeled off from the laminate) was subjected to electron beam irradiation using an electron beam irradiation device (manufactured by Iwasaki Electric Co., Ltd.) under the irradiation conditions of acceleration voltage: 200 kV, dose: 50 kGy and 100 kGy. Thereafter, in an environment of 23° C. and 50% RH, a tensile test was carried out in accordance with JIS K 7127. If the elongation retention rate is 50% or more, it is judged that there is no problem in actual use.

The elongation retention rate is calculated by the following formula: elongation retention rate = [(tensile elongation after irradiation with electron beam)/(tensile elongation before irradiation with electron beam)]×100.

<gamma ray resistance evaluation>

For a thin film (thermoplastic engineering plastic film from which the release film was peeled off), gamma irradiation was carried out at Japan Irradiation Service. Γ-rays were irradiated under irradiation conditions of doses: 50 kGy and 100 kGy. Thereafter, in an environment of 23° C. and 50% RH, a tensile test was carried out in accordance with JIS K 7127. If the elongation retention rate is 50% or more, it is judged that there is no problem in actual use.

The elongation retention rate is calculated by the following formula: elongation retention rate = [(tensile elongation after γ-ray irradiation)/(tensile elongation before γ-ray irradiation)]×100.

The laminates obtained in Examples 1 to 12 have no wrinkle generation or breakage during winding and are excellent in formability (film-forming properties). The thin engineering plastic film obtained by peeling off the peeling film from the laminate is the thickness Thin film with excellent accuracy and smooth surface. In particular, the thin engineering plastic films of Examples 6, 10, and 12 are the temperature Tx (℃) of the contact point between the engineering plastic melt and the peeling film, the metal roller temperature Ty (℃), and the total thickness satisfying the optimal conditions. Excellent precision and smooth surface.

The laminates obtained in Examples 13 to 23 did not generate or break wrinkles during winding, and were excellent in formability (film-forming properties). The film engineering plastics obtained by peeling off the peeling film from the laminate Resin) film is a film with excellent thickness accuracy and surface smoothness. Especially the thin engineering plastic films of Examples 14 to 17, the temperature Tx (℃) of the contact point between the engineering plastic melt and the peeling film, the metal roller temperature Ty (℃), and the total thickness satisfy the best conditions, and the thickness accuracy 3. Excellent surface smoothness. In addition, hydrolysis resistance, hot water resistance, chemical resistance, electron beam resistance, and γ-ray resistance are excellent, and can be suitably used, for example, in sterilization/sterilization applications.

Industrial availability

The thin engineering plastic film of the present invention is thin and has excellent thickness accuracy, so it can also be applied to, for example, film capacitors, speaker vibration plates, circuit boards, heater insulation materials, glass protective films, and household appliances that require high accuracy The use of films for product components and automotive components.

Claims (13)

A laminated body which is one side of a peeling film with a tensile breaking strength of 115 MPa or more and a tensile elongation at break of 190% or less in the production direction, and has a thermoplastic thickness of 250 μm or less and a thickness accuracy of 15% or less Engineering plastic layer. The laminate as claimed in claim 1, wherein the layer of the engineering plastic includes: selected from the group consisting of polyetheretherketone, polycarbonate, polyacrylate, polyacetal, polyphenylene sulfide, polyether sulfone, poly sulfone, poly Polymerization of at least one of the group consisting of benzophenone, polyetherimide, polyamidimide, polyetherketone, polybenzimidazole, cycloolefin polymer, liquid crystal polymer, and these modified products Or a mixture of two or more polymers selected from this group. The laminate according to claim 1 or claim 2, wherein the release film comprises: 1 selected from the group consisting of polypropylene, polyethylene terephthalate, polyethylene naphthalate, and polyamide More than one polymer or a mixture of two or more polymers selected from this group. The laminated body according to any one of claim 1 to claim 3, wherein the arithmetic average surface roughness of the surface of at least the side of the engineering plastic layer in contact with the release film is 1.0 μm or less. A thin film comprising the layer of the engineering plastic according to any one of claim 1 to claim 4. The thin film of claim 5 is a film for film capacitors, speaker diaphragms, circuit boards, heater insulation materials, glass protection, household electrical appliance parts, or automotive parts parts. A manufacturing method of the laminate, which is one side of a peeling film with a tensile breaking strength of 115 MPa or more and a tensile breaking elongation of 190% or less in the production direction, extruding a thermoplastic engineering plastic melt, and the laminated thickness is 250 μm The following is a method for manufacturing a laminate of a thermoplastic engineering plastic layer with a thickness accuracy of 15% or less, characterized in that the temperature when the thermoplastic engineering plastic melt contacts the release film is set to Tx, and the glass transition temperature of the release film When Tg1 is set and the melting point of the peeling film is set to Tm, the relationship of Tg1≦Tx≦Tg1+180° C≦Tm is satisfied. The method for manufacturing the laminate according to claim 7, wherein the layer of the engineering plastic includes: selected from the group consisting of polyetheretherketone, polycarbonate, polyacrylate, polyacetal, polyphenylene sulfide, polyether sulfone, Polyphenol, polystyrene, polyether amide imide, polyamide amide imide, polyether ketone, polybenzimidazole, cyclic olefin polymer, liquid crystal polymer and the group of these modified products 1 More than one polymer or a mixture of two or more polymers selected from this group. The method for manufacturing the laminate according to claim 7 or claim 8, wherein the release film comprises: a material selected from the group consisting of polypropylene, polyethylene terephthalate, polyethylene naphthalate, and polyamide A group of more than one polymer or a mixture of two or more polymers selected from the group. The method for manufacturing the laminated body according to any one of claim 7 to claim 9, wherein the arithmetic average surface roughness of the surface of at least the side of the engineering plastic layer in contact with the release film is 1.0 μm or less. A method for manufacturing a thin engineering plastic film, characterized in that after the layered body is obtained by the method for manufacturing a layered body according to any one of claim 7 to claim 10, the peeling film is peeled off from the layered body Remove. The thin film according to claim 5 is subjected to any treatment of hot water, chemicals, sterilization, ozone, electron beam irradiation, and γ-ray irradiation. As for the thin film of claim 5, the tensile elongation retention rate before and after the 96-hour pressure cooker test under an environment of 120°C and 100% RH is more than 35%.