Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
  • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
  • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/02—Physical, chemical or physicochemical properties
  • B32B7/023—Optical properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
  • B32B2307/514—Oriented
  • B32B2307/518—Oriented bi-axially
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
  • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

• the present invention relates to a biaxially-oriented laminated film which is less scratched, excellent in transparency of a film after high-temperature heat treatment, and excellent in suppression of thermal deformation.
• Polyester films are excellent in transparency, dimensional stability, mechanical properties, heat resistance, electrical properties and the like, and are used in various fields. In particular, in recent years, it has been increasingly used as a substrate of a transparent conductive laminate used for touch panels, electronic paper and the like and a surface protective film thereof.
• a base film used for a transparent electrode of a touch panel is hard-coated on the substrate film to provide a transparent conductive layer, which is used as a transparent electrode and incorporated in a liquid crystal display device as a touch panel module. Since a touch panel visually recognizes a liquid crystal display through a transparent electrode, in order to obtain a touch panel having a clear display, a base film used for a transparent electrode of the touch panel is required to be highly transparent and have no surface defect.
• Patent Document 1 In general, a film with less surface defects reduces scratches and defects on the film surface by increasing the slipperiness of the film surface. Although it is necessary to add particles to the film in order to increase the slipperiness of the film, it is very difficult to achieve both high transparency and reduction of surface defects, since the addition of particles contributes to the reduction of transparency. (Patent Document 1).
• the transparent conductive film in which the transparent conductive film which consists of ITO (indium tin oxide: Indium Tin Oxide) was formed is an annealing process, the crystallization process of ITO, the printing process of a resist.
• a chemical treatment step Patent Document 2
• low molecular weight substances (oligomers) remaining on the polyester film or generated by thermal decomposition are deposited on the surface to whiten the polyester film appearance, yield loss due to transfer to ITO, contamination of the process, washing, etc.
• the temperature of the heat treatment of the ITO has been increased to a high temperature for a long time, and a higher heat deformation resistance is required, and a smartphone equipped with a capacitive touch panel
• the demand for densification and appearance quality of conductive circuits of tablets and tablets is becoming increasingly sophisticated, and further control of oligomer deposition on the film surface is required.
• the haze of a film (hereinafter referred to as all haze) is classified into a haze due to scattering on the film surface (hereinafter referred to as surface haze) and a haze due to scattering inside the film (hereinafter referred to as internal haze). Since it contributes also after surface processings, such as a hard coat, when forming a touch panel, the subject to which visibility falls falls.
• the oligomer moves in a minute space inside the film, moves to the surface, crystallizes, and precipitates during heating, so that the increase of voids due to the addition of particles is caused during the heating step. It contributes to promoting the increase of haze.
• the present invention for achieving the above object is obtained by the following.
• a biaxially oriented laminated film which is a laminated film having (A layer) satisfies the following requirements (1) to (3).
• the internal haze is 0.5% or less.
• the 10-point average roughness SRz of the surface of the layer A opposite to the surface in contact with the layer B of the layer A is 250 nm or more.
• the biaxially-oriented laminated film which suppresses the yield fall by the flaw at the time of film forming, and the flaw during surface processing can be obtained, without impairing transparency. Therefore, the biaxially oriented laminated film of the present invention can be suitably used as a base film or a protective film of a transparent conductive laminate, and the industrial value of the present invention is high.
• film is used to include two-dimensional structures such as sheets, plates, and membranes.
• thermoplastic resin A having a thickness of 0.5 ⁇ m or more and 2.0 ⁇ m or less as a main component and inactive particles on at least one side of a layer (B layer) containing thermoplastic resin B as a main component
• a layer (A layer) it is necessary to be a laminated film having a layer (A layer) to be contained.
• the thickness of layer A is 2.0 ⁇ m or more, it is necessary to add particles of 2 ⁇ m or more in order to form protrusions on the film surface, and when such particles are added, it leads to an increase in internal haze. Not desirable.
• the film is subjected to a step of orienting the film (generally, a stretching step), but the particles added for forming the projections on the film surface are the film in the stretching step.
• voids occur around the particles.
• the voids generated here raise the internal haze of the film more than the particles. Therefore, in the case of biaxially orienting a film in which many particles are added, the internal haze is raised not only by the increase of the internal haze by the particles but also by the void generated around the particles.
• the layer A is preferably at least one surface layer of the laminated film. More preferably, the A layer is on both surfaces.
• the layer thickness of the layer A is preferably 2 ⁇ m or less, more preferably 1.5 ⁇ m or less.
• the thickness of the layer A is less than 0.5 ⁇ m, it is necessary to add particles of 0.5 ⁇ m or more in order to set the 10-point average roughness (SRz) to 250 nm or more. Particles are likely to fall off. As a result, it is not preferable because the particle drop-off portion may become a defect as it is.
• the internal haze is a r / d of 0.1 or more and 2 or less It is preferable because the slipperiness of the film surface can be improved while suppressing the increase of
• the internal haze of the laminated film of the present invention needs to be 0.5% or less.
• the internal haze can be determined by immersing the film in a solvent and measuring it according to the method described in JIS-K-7105 (1985) in the measurement method described later to cancel and measure the surface haze.
• the total haze increases and decreases depending on the surface roughness because it also contributes to light scattering, but the internal haze is essentially more important because the film surface is often surface-processed and used.
• the internal haze is preferably 0.4% or less, more preferably 0.3% or less.
• the 10-point average roughness SRz of the surface of the layer A opposite to the side in contact with the layer B needs to be 250 nm or more.
• SRz of the A layer is 250 nm or more, generation of flaws in film formation can be suppressed, and yield can be improved.
• SRz is preferably 400 nm or more, more preferably 500 nm or more.
• SRz In order to improve SRz, the relationship between the thickness of the particle added layer and the particle diameter is important. On the other hand, when SRz is increased too much, when the present film is used as an ITO substrate, the transparent conductive layer may be broken and the function of the conductive layer may be deteriorated. In addition, in the case of using as a protective film, the conductive layer surface may be scratched and broken due to the projections of the particles, so SRz is preferably 1000 nm or less.
• the laminated film of the present invention is heat-treated at 150 ° C. for 30 minutes, and the amount of change in total haze before and after quenching (the amount of change in total haze of the film before heating and after heating at 150 ° C. for 30 minutes) ( ⁇ Hz 150 ° C. for 30 minutes Needs to be 2.0% or less.
• the cyclic trimer contained in the resin is precipitated on the film surface to raise the haze.
• ⁇ Hz 150 ° C. for 30 minutes exceeds 2.0%, many cyclic trimers are deposited on the surface of the film, and therefore, they are laminated with other members to form a protective film of a transparent conductive laminate.
• the precipitated cyclic trimer is transferred to the surface of the other member, which may deteriorate the product quality. Moreover, since the visibility in the case of setting it as a transparent electrode board
• the laminated film of the present invention changes the total haze before and after 150 ° C. for 180 minutes (after heating at 150 ° C. for 180 minutes and the change in the total haze of the film before heating) ⁇ Hz 150 ° C. for 180 minutes is 2.0 It is preferable that it is% or less.
• the heating stability for a longer time is required, more preferably 1.0% or less, and still more preferably 0.5% or less.
• the total haze of the laminated film of the present invention is preferably 1.0% or more and 3.0% or less.
• the total haze of the film is the total haze value after film formation, and a film having excellent transparency can be obtained by setting the total haze to 3.0% or less.
• the total haze value is preferably 2.5% or less.
• the laminated film of the present invention preferably has a difference of 0.8% or more between the total haze and the internal haze.
• the laminated film of the present invention is often used by applying an adhesive layer or a hard coat layer on its surface. In that case, since the surface of the laminated film is covered with the adhesive layer or the hard coat layer, the surface haze of the film depending on the surface roughness of the laminated film is canceled, so the internal haze becomes more important.
• the conventional method when protrusions are formed on the film surface by particle addition in order to suppress flaws during film formation and flaws during surface processing, not only the surface haze but also the internal haze rises, so all the haze is inevitable. It is easy to get bigger.
• the film is made to have a specific configuration and the particles are contained, projections are formed on the film surface and the surface haze is increased, but the internal haze is hardly increased. Therefore, the difference between the total haze and the internal haze tends to be large. The larger the difference, the easier it is to suppress the generation of flaws on the surface, and the transparency can be ensured even after processing. In particular, if the difference is 0.8% or more, it is preferable because both transparency and scratch control can be achieved. More preferably, it is 1.0% or more, and more preferably 1.2% or more and 2.5% or less.
• thermoplastic resins polyester resins are excellent in transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, etc.
• polyester films made of polyester resins are, for example, surface protective films for conductive films, and transparent It can be preferably used for conductive substrate film applications.
• the main component means a component that can be 50% by mass or more with respect to the entire layer.
• Polyester resin is a general term for polymers having an ester bond as the main bond of the main chain, and ethylene terephthalate, ethylene-2,6-naphthalate, butylene terephthalate, ethylene- ⁇ , ⁇ -bis (2-chlorophenoxy) At least one component selected from ethane-4,4'-dicarboxylate or the like is used as a main component, and these components may be used alone or in combination of two or more. In consideration of the economy and the like comprehensively, it is preferable to use polyethylene terephthalate as the main component. Further, in these polyester resins, other dicarboxylic acid components and diol components may be partially copolymerized, preferably 20 mol% or less.
• the molar ratio (M / P) to the content P (mol / ton) is preferably in the range of 2.0 to 5.4. (Wherein, M represents an alkali metal element, an alkaline earth metal element, and P represents the total number of moles of phosphorus element per 10 6 g of polyester).
• the cation of a monovalent metal element is 1: 3 and the cation of a divalent metal element is 2: 3 and the cation of a trivalent metal element Is considered to interact 1: 1.
• the phosphorus element derived from the phosphorus compound such as phosphoric acid is required as interacting with the cation of the metal element as a divalent anion (M / P)
• M / P divalent anion
• the anion by the phosphorus element is 1: 2 with the cation of the monovalent metal element, 1: 1 with the cation of the divalent metal element, and 3: 2 with the cation of the trivalent metal element
• M / P is 2.0 or more, the volume resistivity at the time of melting of the polyethylene terephthalate resin composition becomes low, and the electrostatic application casting method is suitably applied at the time of film forming.
• M / P is 5.4 or less, regeneration of cyclic trimer at melting and suppression of residual catalyst residue in the film are easily suppressed, so the initial stage after film formation The total haze value and the total haze value after heating can be suppressed low.
• the M / P is more preferably in the range of 2.5 to 4.5.
• the intrinsic viscosity (IV) of the thermoplastic resin used for the laminated film of the present invention is preferably 0.55 or more and 0.75 or less.
• the intrinsic viscosity (IV) is in the above range, the thickness unevenness of the film is suppressed, and the film can be stably formed.
• the intrinsic viscosity (IV) is less than 0.55, the melt viscosity is reduced, and local thickness unevenness is likely to occur until the landing of the resin onto the drum for melting and cooling the resin from the extrusion port, If the IV) exceeds 0.75, pressure is applied to the extrusion site in the extrusion process at the time of film formation of the film, and thickness unevenness tends to occur.
• intrinsic viscosity (IV) is 0.60 or more and 0.70 or less. Further, as the thickness unevenness of the film is smaller, the variation of the refractive index can be pushed in the longitudinal refractive index nMD, the width direction refractive index nTD, and the surface vertical refractive index nZD of the film, and the occurrence of the interference unevenness is suppressed. It becomes easy to do.
• the thickness unevenness of the film is preferably 5.0% or less in both the longitudinal direction of the film (the film forming direction of the film) and the width direction (the direction perpendicular to the film forming direction of the film), and more preferably 3. It is 0% or less.
• the layer B of the laminated film of the present invention preferably has a cold crystallization temperature (Tcc) of 150 ° C. or more and less than 165 ° C.
• the cold crystallization temperature refers to a crystallization peak of 2nd run determined by differential scanning calorimetry described later.
• Tcc cold crystallization temperature
• the initial haze value the total haze value before heating the film
• ⁇ Hz is the difference between all the haze values before and after heating the film at 150 ° C. for 180 minutes, to 2.0% or less.
• ⁇ Hz is the difference between all the haze values before and after heating the film at 150 ° C. for 180 minutes, to 2.0% or less.
• cyclic oligomers contained in the film are present as a plurality of multimers, and the cyclic oligomers are precipitated on the surface of the film, whereby the total haze value of the film is deteriorated. It is for.
• cyclic oligomers are mainly described because cyclic oligomers are mostly cyclic trimers.
• Tcc cold crystallization temperature
• the flatness of the film after heating may be affected. More preferably, the temperature is 150 ° C. or more and 160 ° C. or less.
• the cold crystallization temperature (Tcc) is measured by measuring 10 mg of a film sample with an electronic balance, sandwiching it with aluminum packing, and using a thermal differential scanning meter by Seiko Instruments Inc. Robot DSC-RDC220, data
• the analysis shows the value obtained by performing according to JIS-K-7121 (1987) using a disk session SSC / 5200 manufactured by the same company.
• the temperature is raised from 25 ° C. to 300 ° C. at 20 ° C./min, then it is rapidly cooled to 25 ° C., and the temperature is raised again to 300 ° C. at 20 ° C./min (2nd Run)
• the peak temperature (Tcc) is determined as the peak temperature of the crystallization peak.
• the crystallization peak apex temperature showing the maximum peak area determined by JIS-K-7122 is measured, and this is repeated three times, and the average value is crystallized. Peak temperature (Tcc).
• Tcc Peak temperature
• the means for setting the cold crystallization temperature (Tcc) to 150 ° C. or more but less than 165 ° C. is not particularly limited, but in the present invention, when a polyester resin is used as the thermoplastic resin constituting the B layer, polyester A preferred method is to adjust the average molecular weight, particle content and cyclic oligomer content of the resin.
• the average molecular weight there are number average molecular weight and mass average molecular weight, but according to the study by the present inventors, if the mass average molecular weight is small (the polymer with a long molecular chain is small), the crystallinity of the film tends to be high.
• the cold crystallization temperature (Tcc) tends to decrease, and conversely, if the mass average molecular weight is large (more polymers with long molecular chains), the crystallinity of the film tends to be low, and the cold crystallization temperature (Tcc) is It turned out that it tends to rise.
• Tcc cold crystallization temperature
• the cold crystallization temperature (Tcc) changes depending on the content of particles and cyclic trimer present in the polyester layer of the present invention. For example, if the particle content is increased, the particles become nuclei to promote crystallization of the film, so the cold crystallization temperature (Tcc) of the polyester resin is lowered. On the other hand, it is believed that the cold crystallization temperature (Tcc) tends to be high because the crystallization of the film is also suppressed if the particle content is reduced.
• the cyclic trimer when the content is small, the amount of those that inhibit the oriented crystal of the molecular chain of the polymer is small, so crystallization tends to be easy, and the cold crystallization temperature (Tcc) tends to be low.
• the cyclic trimer content when the cyclic trimer content is large, it is considered that crystallization tends to be difficult because the component that inhibits the oriented crystal of the molecular chain of the polymer is large, and the cold crystallization temperature (Tcc) tends to be high.
• the cold crystallization temperature (Tcc) fluctuates depending on the particle content.
• the particle content increases, the particles become nuclei to promote crystallization, so the cold crystallization temperature (Tcc) tends to decrease, and when the particle content decreases, nuclei decrease, so cold crystals
• the conversion temperature (Tcc) tends to be higher.
• the mass average molecular weight of the polyester layer constituting the present invention is 30,000 or more and 50,000 or less, preferably 40,000 or less.
• the content of the cyclic trimer is preferably 0.01% by mass or more and 1.00% by mass or less. More preferably, it is 0.5 mass% or less.
• the initial haze value which is an indicator of film transparency
• the cyclic trimer is 1.00% by mass or less, the initial haze value, which is an indicator of film transparency, is 3.0% or less, and further, after heating the film (150 ° C. for 180 minutes It becomes easy to make the haze value of after 3.0%.
• the content of the cyclic trimer is small, the cyclic trimer is less likely to precipitate on the surface of the film at the time of film forming or film processing, and the transparency of the film after heating is also easily maintained.
• the lower limit of the content of the cyclic trimer is not particularly limited, but in the present invention, it is 0.01% by mass or more. In the case of less than 0.01% by mass, the increase in the intrinsic viscosity of the resin becomes large because the time taken for the solid phase polymerization to reduce the cyclic trimer is long, and the laminated film of the present invention is used Intrinsic viscosity also becomes high, the load at the time of melt extrusion becomes large, and the thickness unevenness of a film may be caused. When the cyclic trimer exceeds 1.0% by mass, the initial haze value of the film and the haze value after heating may exceed 3.0%.
• the laminated film of the present invention preferably has a haze value of 3.0% or less after heating (after heating at 150 ° C. for 180 minutes). More preferably, it is 2.5% or less.
• the laminated film of the present invention preferably has a thickness of 16 ⁇ m to 300 ⁇ m.
• the thickness of the laminated film of the present invention is more preferably 18 ⁇ m or more and 260 ⁇ m or less, still more preferably 20 ⁇ m or more and 250 ⁇ m or less, and particularly preferably 20 ⁇ m or more and 200 ⁇ m or less.
• the thickness ratio per layer A to layer B (A / B) is preferably 0.001 to 0.10 because the transparency and the scratch resistance become good.
• the laminated film of the present invention preferably has a refractive index of 1.63 or more and 1.69 or less.
• the refractive index is less than 1.63, the heat deformation resistance may not be sufficient because crystallization of the film is difficult to progress, etc., and it is used as a surface protection film for a conductive film or a transparent conductive substrate film. In some cases, sufficient mechanical properties can not be obtained.
• the refractive index exceeds 1.69, film breakage is likely to occur during the stretching step in the film production process, and the production stability may be deteriorated.
• the refractive index of the laminated film of the present invention is particularly preferably 1.65 or more and 1.67 or less.
• the refractive index means the average value of the refractive index of a film longitudinal direction, and the refractive index of a film width direction.
• the refractive index can be measured with an Abbe refractometer, using sodium di line (wavelength 589 nm) as a light source and diiodomethane as an intermediate liquid.
• the method to make a refractive index into said range is not specifically limited, Generally, it can control by adjusting the draw ratio and temperature at the time of extending
• the laminated film of the present invention is not limited in its film constitution as long as the important requirements of the present invention are satisfied, and, for example, a laminated film of A layer / B layer, that is, a two kind two layer laminated film, A layer / B layer / A
• Examples of the configuration include a laminated film of layers, that is, a two-kind three-layer laminated film, and a laminated film of A layer / B layer / C layer, that is, a three-kind three-layer laminated film. It is preferable that the A layer be on at least one surface layer.
• the lamination method of the laminated film of the present invention is not limited, and examples thereof include a lamination method by co-extrusion method, a lamination method by lamination, a method by a combination thereof, and the like. It is preferable to employ a co-extrusion method from the viewpoint of In the case of forming a laminate, different resin configurations may be used in order to provide different functions to the respective layers. For example, in the case of a laminated film of A layer / B layer / A layer, that is, a two-kind three-layer laminated film, the B layer is composed of homopolyethylene terephthalate from the viewpoint of transparency, and the A layer is provided with slipperiness And methods such as adding particles.
• a biaxially oriented film is biaxially stretched, that is, a sheet in an unstretched state is stretched by about 2.5 to 5.0 times in the sheet longitudinal direction and width direction respectively, and then heat treatment is performed to complete crystal orientation. It can be obtained by Moreover, as a biaxial stretching method, a sequential biaxial stretching method may be used, or a simultaneous biaxial stretching method may be used. Furthermore, after performing biaxial stretching, you may re-stretch the film longitudinal direction or film width direction again, and may perform the re-stretching method.
• the laminated film constituting the present invention does not inhibit the effects of the present invention, and various additives such as an antioxidant, a heat resistant stabilizer, a weather resistant stabilizer, an ultraviolet light absorber, an organic lubricant, a pigment and a dye Organic or inorganic fine particles, fillers, antistatic agents, nucleating agents, crosslinking agents and the like may be added.
• various additives such as an antioxidant, a heat resistant stabilizer, a weather resistant stabilizer, an ultraviolet light absorber, an organic lubricant, a pigment and a dye
• organic or inorganic fine particles, fillers, antistatic agents, nucleating agents, crosslinking agents and the like may be added.
• the particle size distribution of the inactive particles contained in the layer A is measured, the particle diameter is plotted on the horizontal axis, and the particle abundance ratio is plotted on the vertical axis, the particle diameter is 0.8 to 2.0 ⁇ m. It is preferred to have one or more local maxima in the range.
• the diameter having the maximum value of the inactive particles contained in the layer A is too large, it may lead to an increase in internal haze and an increase in surface defects due to particle detachment during film formation.
• the particle size distribution of the inactive particles contained in the layer A is measured, and the particle diameter is plotted on the horizontal axis, and the particle abundance ratio is plotted on the vertical axis. It is preferred to have one or more local maxima in the 5 ⁇ m range.
• particles having a number average particle diameter in the range of 0.1 ⁇ m to 0.5 ⁇ m as particles to be added to the layer A.
• particles having a number average particle diameter of 0.5 ⁇ m or less are contained in the surface layer having the above-mentioned layer thickness, it was found that they are unlikely to become voids even when stretched, so many particles can be contained.
• the particles can be dispersed on the entire surface of the film, thereby making it more difficult to scratch.
• the particle size distribution of the inert particles contained in the layer A is measured, and the particle diameter is plotted on the horizontal axis and the particle abundance ratio is plotted on the vertical axis, the particle diameter is 0.1 to 0.5 ⁇ m. It is preferred to have one or more maxima in the range and one or more maxima in the range of particle diameter 0.8 to 2.0 ⁇ m.
• particles to be added to layer A particles having a number average particle diameter in the range of 0.1 ⁇ m to 0.5 ⁇ m and a number average particle diameter in the range of 0.8 ⁇ m to 2.0 ⁇ m It can be mentioned to use in combination particles.
• the particle size distribution of the inert particles contained in the layer A is measured, and the particle diameter is plotted on the horizontal axis and the particle abundance ratio is plotted on the vertical axis, the particle diameter is 0.1 to 0.5 ⁇ m.
• ⁇ the maximum value of the largest abundance ratio in the range
• ⁇ / ⁇ is preferably 1 to 1,000. More preferably, it is 10 to 200.
• the content of inert particles in the layer A is preferably 0.01 to 0.5% by mass.
• the content of the inert particles is 0.01% by mass or more, it is easy to suppress the flaw during film formation and the flaw during surface processing.
• the content of the inert particles is 0.05% by mass or less, the effect of suppressing the influence of the internal haze increase by containing the inert particles of the present invention can be sufficiently obtained. More preferably, it is 0.1 to 0.3% by mass.
• the content of the inert particles in the B layer is preferably 0.1% by mass or less.
• the transparency can be improved. More preferably, it is 0.05 mass% or less.
• the inert particles include inorganic particles or organic particles.
• the inorganic particles include oxide particles such as silica, alumina and zirconia, and metal compound particles such as calcium carbonate.
• the organic particles include crosslinked styrene particles, epoxy particles, polyphenylene sulfide particles, and polyamideimide particles.
• particles containing a styrene component particularly, crosslinked styrene particles (refractive index: about 1.58)
• calcium carbonate particles reffractive index about 1.66) and the like are particularly preferable from the viewpoint of controlling the refractive index and particle diameter.
• the laminated film of the present invention has a value of 0.1 or more and 0.5 or less when two films are vertically stacked one on top of the other according to the method described in JIS K7125 and the dynamic friction coefficient is measured using a 200 g load. It is preferable that it becomes the following. If the coefficient of dynamic friction is too large, the film is less likely to slip, and the film tends to be damaged when transported. More preferably, it is 0.4 or less. On the other hand, when the dynamic friction coefficient is too small, it tends to cause winding deviation when wound on a roll. Moreover, when a dynamic friction coefficient is measured using a 1000-g load, it is preferable that the value is 0.2 or more and 0.5 or less.
• a more preferable range is 0.2 or more and 0 or 4 or less.
• a polyester resin is prepared in the form of pellets or the like.
• the pellets are optionally dried in hot air or under vacuum and then fed to separate extruders.
• the resin heated and melted to the melting point or more is uniformed in the extrusion amount of the resin by a gear pump or the like, and foreign substances, denatured resin and the like are removed through a filter or the like.
• These resins are molded into a desired shape by a die and then discharged. And the sheet
• cooling bodies such as a casting drum etc.
• electrostatic force using a wire-like, tape-like, needle-like or knife-like electrode
• blow air from a slit-like, spot-like or plane-like device to adhere closely to a cooling body such as a casting drum to cause rapid solidification, or to closely adhere to a cooling body with a nip roll to cause rapid solidification.
• the laminated film which consists of several polyester resin when producing the laminated film which consists of several polyester resin, several resin is sent out from a different flow path using two or more extruders, and it is made to merge with a pinol.
• the pinol design has a structure of A / B / A, and the discharge amount is adjusted so that the thickness of the surface layer becomes a desired thickness.
• the molten multilayer laminate thus formed into a desired layer configuration is extruded into a sheet form from a T-shaped die, and wound around a mirror surface casting drum having a surface temperature of 10 to 60 ° C. using an electrostatic application casting method to cool and solidify.
• the unstretched PET film is prepared.
• This unstretched film is stretched 2.5 to 5.0 times in the longitudinal direction (also referred to as “the longitudinal direction of the film” and also “longitudinal direction”) between rolls heated to 70 to 100 ° C. Subsequently, the film is gripped by a clip and guided to a preheating zone, heated to a temperature of 75 to 95 ° C., and then continuously heated in a transverse direction at 90 to 115 ° C. (perpendicular to the film traveling direction) Direction is also referred to as “width direction”), and then it is stretched 3.0 to 5.0 times, then heat treated at a heating zone of 200 to 240 ° C. for 5 to 60 seconds, and cooled at 100 to 200 ° C. An oriented polyester film is obtained.
• Biaxial stretching may be either sequential stretching or simultaneous biaxial stretching, and may be re-stretched in either longitudinal or transverse direction after longitudinal or transverse stretching.
• the end of the obtained biaxially oriented laminated polyester film is cut and taken up as a winding intermediate product, and thereafter cut to a desired width using a slitter, and wound around a cylindrical core to obtain a polyester film roll of a desired length be able to.
• both ends of the film may be embossed in order to improve the winding shape.
• the laminated film of the present invention may be provided with an application layer on one side of the film or on both sides of the film.
• the coating layer may be a coating layer of two or more layers on one side, and in the case of providing a coating layer on both sides, different compositions are coated on one side and the opposite side. You may.
• Thickness The film was cut into A4 size, and an arbitrary 20 points were measured using a dial gauge (“No 2 110 S-10” manufactured by Mitutoyo Co., Ltd.), and the average value was defined as the thickness ( ⁇ m).
• the midpoint glass transition temperature was determined as the glass transition temperature (Tg), and the peak temperature of the crystallization peak was determined as the crystallization peak temperature (Tcc).
• Tg glass transition temperature
• Tcc crystallization peak temperature
• the crystallization peak apex temperature indicating the maximum peak area determined by JIS-K-7122 is used.
• the particle diameter that carries the horizontal axis is the class at every 10 nm interval starting from 0 nm
• A Scratches less than 0.5 ⁇ m in height difference and having a length of more than 0 mm but less than 2 mm
• B Scratches less than 0.5 ⁇ m in height difference and having a length of 2 mm or more and C; Scratches having height difference of 0.5 ⁇ m or more And, the length is more than 0 mm and less than 0.3 mm D; the height difference is 0.5 ⁇ m or more, and the length is 0.3 mm or more.
• the surface layer thickness of the film is a chip cut in the direction perpendicular to the surface of the film, and then a cross section thereof is taken with a field emission scanning electron microscope JSM-6700F (manufactured by JEOL Ltd.) The film was observed by magnifying at 10000 times and photographed, and the film thickness was taken as the place farthest from the surface.
• Punching metal A Punching metal SUS304 made by Okuya Wire Mesh Works, Ltd. Embossing 1.5t x D 4.5 x P7.5 60 ° Chidori-Punching metal
• B Punching metal SUS304 made by Okuya Wire Mesh Manufacturing Co., Ltd. Embossing 2t x D 7 / H 1.3 x P 10 60 ° Plover [Evaluation criteria for heat distortion resistance]
• B In any of the punching metal A and the punching metal B, the reflected image of the fluorescent lamp was distorted at a part of the film surface at the embossing pitch of the punching metal.
• C In any case of punching metal A and punching metal B, the reflection image of the fluorescent lamp was distorted on the entire surface of the film at the embossing pitch of the punching metal.
• the esterification reaction product which is a reaction product of terephthalic acid and ethylene glycol is stored in advance in a molten state at 255 ° C., and further, a slurry of terephthalic acid and ethylene glycol such that the molar ratio of ethylene glycol to terephthalic acid is 1.15
• the reaction mixture was quantitatively supplied while maintaining the temperature of the esterification reaction tank, and the esterification reaction was carried out while distilling out water to obtain an esterification reaction product.
• the obtained esterification reaction product is transferred to a polymerization reaction tank, and an ethylene glycol solution containing phosphoric acid and an ethylene glycol solution containing magnesium acetate tetrahydrate, an ethylene glycol solution containing antimony trioxide, and potassium hydroxide are contained.
• an alkali metal element, an alkaline earth metal element, and a phosphorus element are separately added to the polyester resin to be obtained so that the M / P is 2.8 and the antimony element is 60 ppm, and the ethylene glycol solution is subsequently added.
• the inside of the polymerization reaction vessel was gradually depressurized to be 0.13 kPa or less in 30 minutes, and at the same time, the temperature was gradually raised to 280 ° C.
• the polycondensation reaction tank was returned to normal pressure with nitrogen gas, discharged in a strand shape into cold water from a die, pelletized into a cylindrical shape with an extrusion cutter, and precrystallized with a surface crystallization device to obtain a liquid phase polyester .
• solid phase polymerization was carried out at a temperature of 215 ° C. for 20 hours under a reduced pressure of 0.13 KPa by a rotary vacuum drying apparatus to obtain a polyester resin (PET-A).
• the intrinsic viscosity of the obtained polyester resin (PET-A) was 0.63
• the cyclic trimer content was 0.44% by mass
• the Tg was 80 ° C.
• PET-B A polyester resin (PET) is produced in the same manner as PET-A except that solid phase polymerization after obtaining liquid phase polyester is carried out using a continuous vacuum drying apparatus in the production process of polyester resin (PET-A) described above. -B) I got it.
• the intrinsic viscosity of the obtained polyester resin (PET-B) was 0.73, the cyclic trimer content was 0.40% by mass, and the Tg was 80 ° C.
• PET-C A polyester resin (PET-C) was obtained by the same method as the polyester resin (PET-A) except that the intrinsic viscosity was changed without carrying out solid phase polymerization.
• the intrinsic viscosity of the obtained polyester resin (PET-C) was 0.70, the cyclic trimer content was 1.07% by mass, and the Tg was 80 ° C.
• PET-D PET-C and calcium carbonate particles having an average particle diameter of 1.0 ⁇ m were mixed, and the mixture was melt-kneaded to obtain a master pellet.
• the amount of particles was adjusted to 1% by mass.
• PET-E PET-C and cross-linked polystyrene particles having an average particle diameter of 0.3 ⁇ m were mixed, and the mixture was melt-kneaded and used as a master pellet. Here, the amount of particles was adjusted to 2% by mass.
• PET-F PET-C and silica particles having an average particle diameter of 2.0 ⁇ m were mixed, and the mixture was melt-kneaded to obtain a master pellet.
• the amount of particles was adjusted to 1% by mass.
• PET-G PET-C and cross-linked polystyrene particles having an average particle size of 0.8 ⁇ m were mixed, and the mixture was melt-kneaded to obtain a master pellet.
• the amount of particles was adjusted to 1% by mass.
• PET-H A polyester resin (PET-G) was obtained in the same manner as PET-A, except that the amount of potassium hydroxide, magnesium acetate and phosphoric acid added was changed so that M / P was 1.5. .
• the intrinsic viscosity of the polyester resin (PET-H) was 0.62 dl / g, the cyclic trimer content was 0.43% by weight, and the glass transition temperature Tg was 80.degree.
• PET-I A polyester resin (PET-I) was obtained in the same manner as PET-A except that the additive of magnesium acetate tetrahydrate and phosphoric acid was changed to M / P of 2.0. .
• the intrinsic viscosity of the polyester resin (PET-I) was 0.63 dl / g, the cyclic trimer content was 0.43% by weight, and the glass transition temperature Tg was 80.degree.
• PET-J A polyester resin (PET-I) was obtained in the same manner as PET-A except that the additive of magnesium acetate tetrahydrate and phosphoric acid was changed to M / P of 5.4. .
• the intrinsic viscosity of the polyester resin (PET-J) was 0.65 dl / g, the cyclic trimer content was 0.43% by weight, and the glass transition temperature Tg was 80.degree.
• PET-K A polyester resin (PET-I) was obtained in the same manner as PET-A except that the additive of magnesium acetate tetrahydrate and phosphoric acid was changed to M / P of 6.0. .
• the intrinsic viscosity of the polyester resin (PET-K) was 0.67 dl / g, the cyclic trimer content was 0.43% by weight, and the glass transition temperature Tg was 80.degree.
• PET-L PET-A and silica particles having an average particle diameter of 0.5 ⁇ m were mixed, and the mixture was melt-kneaded to obtain a master pellet.
• the amount of particles was made to be 0.5% by mass.
• [Used coating liquid] (Coating agent A) Under nitrogen gas atmosphere, 40 molar parts of 2,6-naphthalenedicarboxylic acid as dicarboxylic acid component, 50 molar parts of terephthalic acid, 10 molar parts of sodium 5-sulfoisophthalate, 95 molar parts of ethylene glycol as glycol component, 5 molar parts of diethylene glycol Is added to a transesterification reactor, 100 parts by mass of tetrabutyltitanate (catalyst) is added to 1,000,000 parts by mass of all dicarboxylic acid components, and esterification reaction is performed at 160 to 240 ° C. for 5 hours, The distillate was removed.
• Coating agent B In a stainless steel reaction vessel, 75 parts by mass of methyl methacrylate, 20 parts by mass of hydroxyethyl methacrylate, urethane acrylate oligomer (Kegami Kogyo Co., Ltd. product, Art resin (registered trademark) UN-3320 HA, number of acryloyl groups is 6) 5 parts by mass and 2 parts by mass of sodium dodecylbenzene sulfonate as an emulsifying agent were added and stirred to prepare a liquid mixture 1. Next, a reactor equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel was prepared.
• the prepared thermoplastic resins A and B were each dried in vacuum at 160 ° C. for 4 hours, and then supplied to an extruder for melt extrusion at 285 ° C. After filtering with a filter with an average opening of 5 ⁇ m obtained by sintering and pressing stainless steel fibers and then with a filter with a sintered stainless steel powder with an average opening of 14 ⁇ m, the mass ratio of A / B becomes 2:48 with a gear pump.
• the film was gripped by a clip, was introduced into an oven, and was heated at a temperature of 110 ° C. and a hot air flow of 20 m / min. Subsequently, the film was continuously introduced into a stretching step, and stretched 3.7 times in the width direction while heating with hot air at a temperature of 100 ° C. and a wind speed of 15 m / min.
• the obtained biaxially oriented film is continuously subjected to a heat treatment for 15 seconds with hot air at a temperature of 230 ° C.
• the film was wound up to obtain a laminated film having a thickness of 50 ⁇ m.
• the laminated film obtained here had few flaws and defects and was excellent in transparency. Moreover, the haze rise after heating was also small, and it could be suitably used as a surface protection film for conductive films and a transparent conductive substrate film.
• Examples 3 and 4 Comparative Example 1
• the procedure was performed in the same manner as in Example 1 except that the mass ratio of A: B was set to 3:47, 4:46, and 5:45, respectively, and the thickness of the A layer was increased by changing the rotation speed of the gear pump.
• the mass ratio of A: B was set to 3:47, 4:46, and 5:45, respectively
• the thickness of the A layer was increased by changing the rotation speed of the gear pump.
• the mass ratio of A: B was set to 3:47, 4:46, and 5:45, respectively
• the thickness of the A layer was increased by changing the rotation speed of the gear pump.
• the internal haze increased. It is considered that this is because the inclusion of coarse particles inside the layer facilitates the formation of voids.
• the flaws on the surface tended to decrease.
• Example 8 The process was performed in the same manner as in Example 1 except that PET-B was used as the resin B. As a result, although the surface roughness and the haze did not change, they became smaller than the haze example 1 after the heat resistance test, and became a film having higher heat resistance.
• Example 9 The process was performed in the same manner as in Example 1 except that PET-C was used as the resin B. As a result, although the surface roughness and the haze did not change, the haze after the heat resistance test became large.
• Example 6 The procedure of Example 1 was repeated except that the mass ratio of A: B was changed to 0.5: 49.5 by changing the rotational speed of the gear pump. As a result, it became a film with many defects. When the scratch surface was observed with a laser microscope, a trace that particles were dropped was confirmed.
• the same procedure was performed as in Example 1 except for the above. As a result, it was found that although the haze was somewhat high, the film was excellent in transportability under vacuum and a film with few scratches.
• Example 12 The conditions were the same as in Example 1 except that the resin of layer B was changed to PET-H. A film which was transparent and excellent in heat resistance as compared to Example 1 was obtained. However, the castability at the time of film forming was bad, and it became a film with the bad thickness nonuniformity in the width direction.
• Example 13 The conditions were the same as in Example 1 except that the resin of layer B was changed to PET-I. A film which was transparent and excellent in heat resistance as compared to Example 1 was obtained. However, although the castability at the time of film forming was bad and it improved rather than Example 14, it became a film with the bad thickness nonuniformity in the width direction.
• Example 14 The conditions were the same as in Example 1 except that the resin of layer B was changed to PET-J in Example 1. As compared with Example 1, the catalyst residue in PET was large, resulting in a film with a large internal haze. A transparent and heat resistant film was obtained.
• Example 7 The conditions were the same as in Example 1 except that the resin of layer B was changed to PET-K. As compared with Example 1, the internal haze was further increased due to the large amount of catalyst residue in PET, and the heat resistant haze was further deteriorated.
• Example 8 The conditions were the same as in Example 1 except that the resin of layer B was changed to PET-L. As compared with Example 1, since the particles were contained in the inner layer, the film had a high internal haze. In addition, since Tcc was 149 ° C., the crystallinity was high, and the haze increase after heating was large.
• Example 1 In Example 1, it implemented on the conditions similar to Example 1 except having coated the coating agent A. The coating is subjected to corona discharge treatment in air on both sides of the film after obtaining a uniaxially stretched film to make the surface tension of the film 55 mN / m, and the coating material A is used with a bar coater on both sides of the uniaxially stretched film It applied. In addition, the thing of diameter 13 mm and wire diameter 0.1 mm (# 4) was used for the metalling wire bar. The obtained film was highly transparent but slightly lower in heat resistance as compared to the formulation with coating.
• Example 2 The procedure of Example 12 was repeated, except that the coating agent was changed to coating agent B. As a result, a film having an acrylic layer with a coating thickness of 100 nm was obtained. The obtained film had high transparency and the best heat resistance. On the other hand, as the film thickness was increased, the surface roughness decreased, and as a result, the generation of scratches was a little worse.
• thermoplastic resin A As the thermoplastic resin A, only PET-A was used, and the same procedure as in Example 1 was performed except that the coating agent A was coated to impart lubricity. The coating is subjected to corona discharge treatment in air on both sides of the film after obtaining a uniaxially stretched film to make the surface tension of the film 55 mN / m, and the coating material A is used with a bar coater on both sides of the uniaxially stretched film It applied. In addition, the thing of diameter 13 mm and wire diameter 0.1 mm (# 4) was used for the metalling wire bar. As a result, although it was a film with the highest transparency, it turned out that it becomes a film with many flaws.

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