JPH0844100A - Recording film - Google Patents

Abstract

PURPOSE:To ensure superior heat resistance, silicone oil absorbing property, ink absorbing property, toner fixability and printability by using a polyethylene 2,6-naphthalate film as a substrate film and forming a recording layer with colloidal silica and a water-soluble polymer. CONSTITUTION:When a recording layer is laminated on a substrate film to obtain a recording film, a polyethylene 2,6-naphthalate film is used as the substrate film and the recording layer is formed with colloidal silica and a water- soluble polymer. Polyester is a general name for polymers each having ester bonds as the principal bonds of the principal chain and especially pref. polyester is polyethylene 2,6-naphthalate. The colloidal silica has a rosary-like linked and/or branched shape and is, e.g. spherical colloidal silica having a rosary-like linked long chain structure or connected and branched colloidal silica.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to polyethylene 2,6-
The present invention relates to a recording film having a naphthalate film as a base material and a recording layer laminated thereon. In more detail, good color copying is possible with an electrophotographic copying machine, high image density, excellent color image sharpness, toner fixability, silicone oil absorbability, curl property, running property, and transparency. The present invention relates to a recording film that is optically excellent even up to a white base. Further, the present invention relates to a recording film having excellent recording properties with an inkjet printer and color recording / printability with a thermal transfer ribbon, a fabric ribbon, a carbon ribbon or the like. Furthermore, heat resistance, water resistance, abrasion resistance, paper feedability,
The present invention relates to a recording film having excellent handleability.

[0002]

2. Description of the Related Art In recent years, with the spread of OA, it has become possible to easily create and record documents and OHPs in an office, and meet the demand for a high-speed, excellent image quality and low noise color printer. As an example, a color electrophotographic copying machine has been put into practical use. In addition, a color image forming method such as an ink jet method or a thermal transfer method, and a conventional image recording method using a fabric or a carbon ribbon have been widely used. Currently, as a recording method of a color electrophotographic copying machine, a dry copying method in which four color toners (black, yellow, magenta, and cyan) are fixed by using a heat roller is generally used. Especially in a color copier, the temperature of the heat roller is higher than that in a monochrome copier. (1) A so-called offset phenomenon occurs in which toner is transferred to the heat roller, which makes it difficult to obtain a good image. Silicone oil is replenished to prevent this offset phenomenon.

(2) When the base material film is a polyethylene terephthalate film, heat shrinkage easily occurs, and wrinkles and curls easily occur.

Further, an ink jet printer uses an ink which is difficult to dry in order to prevent clogging of nozzles, and the components of this ink are generally those in which a binder, a dye, a solvent, an additive and the like are dissolved in water. Therefore, it is necessary to use a recording sheet having a good water absorption property, and a special paper having a good ink absorption property is usually used.

[0005]

In copying with a color electrophotographic copying machine, wrinkles and curls are liable to occur due to heat shrinkage by a heat roller, and the silicone oil in the recording layer of the copying base material remains. It is a problem above. In particular, when a polyethylene terephthalate film is used as a substrate, various recording films have been studied, but the fact is that none of them satisfy the characteristics yet. It is desired to improve.

On the other hand, when a sheet having low ink absorbency is used for copying with an ink jet printer, the ink may be insufficiently dried or may not be dried at all. Dirty and virtually unusable.

An object of the present invention is to improve color image recording and OH in which the above problems of the conventional recording film based on polyethylene terephthalate film are solved.
It is to provide a recording film for P. That is, the present invention solves these problems and is excellent in heat resistance, silicone oil absorbency, ink absorbency, toner fixability, printability, and water resistance, running property, and curl against heat during recording and printing. The purpose of the present invention is to provide a recording film having excellent properties, handleability and processability.

[0008]

In order to achieve the above object, the present invention has the following constitution, that is, a recording film obtained by laminating a recording layer (II) on a substrate film (I), A recording film, wherein the film (I) is a polyethylene 2,6-naphthalate film and the recording layer (II) is composed of colloidal silica and a water-soluble polymer.

The material of the base film of the present invention is preferably a polyethylene 2,6-naphthalate film. Polyester film is a generic term for polymer films having an ester bond as a main bonding chain, and particularly preferred polyesters are polyethylene 2,6-naphthalate and polyethylene α, β-bis (2-chlorophenoxy) ethane. 4,4′-dicarboxylate, polybutylene 2,6-naphthalate, and the like. Among them, polyethylene 2,6 is taken into consideration when quality and the like are comprehensively considered.
-Naphthalate (hereinafter sometimes abbreviated as PEN) is most preferable. In addition, known additives in the PEN, such as heat resistance stabilizer, oxidation resistance stabilizer, weather resistance stabilizer, ultraviolet absorber, organic lubricant, pigment, organic or inorganic fine particles, mold release agent, antistatic agent Agents and nucleating agents may be added.

The PEN film is unoriented, uniaxially oriented,
A biaxially oriented PEN film is preferable because it can be used in any of the biaxially oriented directions, but it is excellent in mechanical strength. The biaxially oriented PEN film is made by stretching an unstretched PEN sheet or film in the longitudinal direction and the width direction by so-called biaxial directions of 2.5 to 5 times, respectively, and is biaxial by wide-angle X-ray diffraction. It refers to those showing a pattern of orientation.

In addition to PEN alone, the PEN film has a composite structure, for example, polyethylene 2,6-
It may be a naphthalate / polyethylene terephthalate composite film, a polyethylene 2,6-naphthalate / polyethylene terephthalate / polyethylene 2,6-naphthalate composite film, or the like.

The thickness of the PEN film as the film support is not particularly limited, and is preferably 10 to 500 μm, more preferably 20 to 300 μm, and more preferably from the viewpoint of the stiffness required for the laminated film. 25
˜250 μm is desirable.

The support made of this PEN film preferably has a heat shrinkage ratio at 150 ° C. of 0.5% or less. By suppressing the heat shrinkage rate of the film support to a low level in this way, it is possible to suppress the occurrence of wrinkles and curls in the recording film due to heat shrinkage even when a high-temperature heat roller is used.

In the present invention, the substrate film may be an optically transparent one, or if necessary, depending on the purpose.
A film colored in white or the like may be used.

As the white base film used in the present invention, it is possible to use one which is whitened by containing white inorganic particles in polyester. The white inorganic particles refer to known non-colored inorganic particles such as calcium carbonate, amorphous zeolite particles, titanium oxide, calcium phosphate, calcium sulfate, barium sulfate, silica, alumina, kaolin, talc and clay. . In addition to such inorganic particles, it is also possible to use fine particles deposited by the reaction of the catalyst residue and the phosphorus compound in the polyester polymerization reaction system.

In the present invention, the specific gravity of the base film is
Although not particularly limited, when a laminated film having a low specific gravity and excellent whiteness is desired, a specific gravity of 1.3 or less is preferable, and 1.2 or less is more preferably used. Since the base film is made of a PEN film, in order to suppress the specific gravity thereof to 1.3 or less, for example, a special device as described below is required.

First, when an incompatible polymer is dispersed and mixed in a PEN film, voids are formed around the incompatible polymer, especially when the PEN is stretched into a film, and the specific gravity can be suppressed to a low level at the same time. , The film is whitened by numerous voids. The PEN film as the substrate film thus obtained has a lower specific gravity than the ordinary PEN film and has excellent whiteness and cushioning properties. The shape factor of the incompatible polymer to be dispersed and mixed in the film is preferably 1 to 4. The average equivalent spherical diameter of voids in the film formed of the incompatible polymer is 1 to 10 μm.
It is preferred that

The incompatible polymer is not particularly limited as long as it is a polymer incompatible with PEN, but is preferably methylbutene polymer, methylpentene polymer,
It is a polymer having a melting point of 200 ° C. or higher selected from styrene-based polymers, fluorine-based polymers, cellulose acetate polymers, and cellulose propionate polymers.

In order to keep the specific gravity of the base film low, the PEN film may be mixed with the above-mentioned incompatible polymer or separately from the incompatible polymer only for the purpose of lowering the specific gravity. It is also effective to include a low specific gravity agent. The low specific gravity agent is a compound having an effect of reducing the specific gravity by adding it to PEN, and the effect is recognized only in a specific compound. For example, the specific gravity reducing agent can be selected from polyalkylene glycols, ethylene oxide / propylene oxide copolymers, alkylbenzene sulfonates, alkyl sulfonates and modified products thereof, and copolymers thereof with polyesters.

In the PEN film of the present invention, at least one outermost layer is a polyester layer (III) in which inert particles are contained to form uniform unevenness on the surface, or the polyester layer is not dependent on the particles. The polyester layer (IV) in which desired fine protrusions are formed on the surface by utilizing the crystallization of is excellent in runnability and slipperiness, and is further improved in processability and handleability, which is preferable.

In, the thickness of the outermost layer (t μm)
And the average particle diameter (dμm) of the particles are in the range of 0.1 ≦ t / d ≦ 10, the particle content is 0.1 to 50% by weight, and the thickness of the outermost layer is 0.1. It is preferable that a polyester layer having a thickness of 0 to 1 to 3 μm and containing PEN as a main component is laminated. Whether t / d is larger or smaller than the above range,
It is not preferable because the running property and the slip property are easily deteriorated. When the content of the particles is less than 0.1% by weight, running properties and slipperiness are apt to be deteriorated, while when it exceeds 50% by weight, the film strength is apt to decrease.
Each is not preferable. The thickness of the outermost layer is 0.01 μm
If it is less than 3, the running property and slipperiness are likely to be deteriorated, while if it exceeds 3 μm, the film strength is likely to be deteriorated, which are not preferable.
The outermost layer has ethylene naphthalate as a main constituent,
It is preferable that PEN is 80% by weight or more, but P
It may be a blend of EN and another polyester, or a copolymer of PEN and another polyester. Further, within the range that does not impair the object of the present invention,
Different polymers may be blended, or organic additives such as antioxidants, heat stabilizers, lubricants and UV absorbers may be added to the extent that they are usually added. The inert particles are not particularly limited, but colloidal silica,
The average particle size of calcium carbonate, titanium dioxide, alumina, and a crosslinked polymer (for example, crosslinked polystyrene) is preferably 0.1 to 10 times, more preferably 0.5 to 5 times, more preferably the thickness of the outermost layer. It is desirable that the range is 1.1 to 3 times. If it is smaller or larger than the above range, the running property tends to deteriorate, which is not preferable. The size of the inactive particles is such that the average particle diameter (diameter) in the outermost layer is 0.005.
0.5 μm is preferable, more preferably 0.02 to
When the thickness is in the range of 0.45 μm, the running property and the like are better, and it is desirable.

In the above, most or all of the surface protrusions are formed by crystallization of polyester, and the number of protrusions is 5 × 10 ³ / mm ² or more, and the number of protrusions and the surface are formed. It is preferable that the number of protrusions / the number of particles (N _R ), which is the ratio to the number of particles contained in the surface layer, is 5 or more. When N _R is less than 5, the proportion of protrusions formed by the contained particles increases, and the proportion of protrusions that are easily broken due to void formation accompanying particle addition increases, so that it becomes difficult to obtain desirable scratch resistance, Not preferable. The formation of surface protrusions utilizing the crystallization of polyester as described above is performed as follows. In producing a biaxially stretched film containing polyester as a main component, heat treatment is applied to at least one surface of the unstretched film,
Thereafter, the unstretched film is biaxially stretched to form desired surface protrusions. By first subjecting the unstretched film to heat treatment, crystallization of the surface of the unstretched film is promoted, and a large number of fine crystals are generated. This unstretched film is biaxially stretched, the film is biaxially oriented and the target strength of the film itself is achieved, and due to the difference in hardness between the crystal and the other part, the fine crystals cause A uniform fine surface protrusion is formed. Here, regarding whether or not the surface protrusions are made of polyester fine crystals, under the target protrusion,
Etching with an appropriate solvent in the film thickness direction,
When the substance that forms the protrusions remains as an insoluble substance, the particles are added from the outside or the particles are precipitated inside (X). When substantially nothing remains as an insoluble substance, it can be estimated that the substance that forms the protrusion is fine crystals (Y). As the above-mentioned solvent, for example, a mixed solvent of phenol / carbon tetrachloride (weight ratio: 6/4) is preferably used. The frequency of X and the frequency of Y when the visual field is set to about 1 mm ² are obtained by this method, and it is preferable that the value of X / (X + Y) is 70% or more. In the present invention, the type of polyester is not particularly limited, but the crystallization parameter ΔTcg is preferably 70 ° C. or lower, more preferably 65 ° C. or lower, and further preferably 55 ° C.
It is desirable that the temperature is ℃ or less. Crystallization parameter ΔT
When cg is larger than 70 ° C., it is difficult to obtain the surface protrusion targeted by the present invention, which is not preferable. The polyester is not particularly limited as long as it satisfies the above conditions, but is particularly preferable when at least one structural unit selected from ethylene rephthalate and ethylene 2,6-naphthalate units is a main constituent component. In order to form the target surface protrusions, the film containing polyester as a main component is crystallized by heat treatment before biaxial stretching as described above, but is present in the unstretched film before biaxial stretching. The diameter r of the spherulites is preferably in the range of 0.03 to 0.45 μm. More preferably 0.10
It is in the range of 0.30 μm. By controlling in such a range, the scratch resistance of the film surface after biaxial stretching becomes excellent. The polyester film of the present invention may be used alone as a biaxially oriented film containing polyester as a main component, or may be used as a laminated film laminated on at least one side of a film containing PEN as a main component.

When the PEN film is a film which has been subjected to surface treatment by a known method, that is, corona discharge treatment (in air, nitrogen, carbon dioxide, etc.) or easy adhesion treatment, the adhesion to the coating layer, It can be used more preferably because the water resistance and chemical resistance are improved. For the easy-adhesion treatment, various known methods can be used, and those obtained by coating various known easy-adhesive agents on the film during the film production process or after uniaxially or biaxially stretching can be preferably used.

The film made of PEN used in the present invention contains an acrylic resin, a polyester resin dissolved or emulsified and suspended in water and / or an organic solvent in order to improve the adhesion between the recording layer and PEN. An undercoat of polyurethane resin or the like can be preferably used.
In particular, a product obtained by undercoating a reaction product of a vinyl-based copolymer having a hydroxyl group and a partial ester group of phosphoric acid and a polyisocyanate compound (described in JP-B-58-35145), or a polyester resin containing a hydrophilic group and an acrylic resin. Undercoating a composition consisting of a copolymer grafted with a compound and a cross-linking agent, undercoating a composition obtained by mixing these with a polyurethane resin, a recording layer and a film comprising a polyalkylene naphthalate It is preferable as a film having improved adhesiveness and excellent durability such as resistance to moist heat and resistance to boiling water.

In the recording film of the present invention, a recording layer containing colloidal silica and a water-soluble polymer as main components is provided on at least one surface of the base film.

The colloidal silica used in the present invention is
It has a bead-like connected and / or branched shape, and specific examples thereof include those having a long chain structure in which spherical colloidal silica is connected in a beaded shape, and those in which the connected silica is branched. it can. The colloidal silica is one in which primary particles of spherical silica are bound to each other by interposing metal ions having a valence of 2 or more, and preferably at least 3 or more, more preferably 5 or more,
More preferably, 7 or more particles are connected, and further, particles in which beads connected in a bead shape are branched are also included.

Further, colloidal silica and other inorganic particles,
For example, it may be a composite or mixed particle of alumina, ceria, titania, or the like, or may be a particle in which these particles are interposed and linked. The intervening metal ion is preferably a divalent or higher valent metal ion, such as Ca ⁺² , Zn ⁺² ,
Mg ⁺² , Ba ⁺² , Al ⁺³ , Ti ⁺⁴ and the like. Especially Ca
When it is ⁺² , it is suitable for producing colloidal silica which is connected and / or branched in a beaded shape.

The primary particle size of colloidal silica is 5 to
100 nm is preferable, and more preferably 7 to 50 n.
m, more preferably 8 to 30 nm is preferable from the viewpoint of increasing the silicone oil absorbency and ink absorbency of the recording layer.

Further, regarding the silicone oil absorbency and ink absorbency of the recording layer, silica particles are connected in a beaded shape and //
Alternatively, the number becomes larger when branched, and the larger the number of linked silica primary particles is, the more preferable, but usually 3 to 100.
The number is preferably from 5 to 50, more preferably from 7 to 30. When the number is less than 3, the silicone oil absorbency and the ink absorbency are insufficiently expressed, and when the number is more than 100, the silica particles tend to thicken and the dispersibility deteriorates, which is not preferable.

The pH of the colloidal silica used in the present invention is preferably acidic, preferably 2 to 6, and more preferably 2 to 4. If it exceeds this range, the viscosity of the coating liquid tends to increase when mixed with a water-soluble polymer, and the workability is deteriorated, which is not preferable.

The water-soluble polymer in the present invention refers to a polymer that is soluble in water at room temperature. Examples thereof include starches such as oxidized starch, etherified starch and dextrin, and cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose. Casein, gelatin, polyvinyl alcohol and derivatives thereof, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid or esters thereof, salts and copolymers thereof, vinyl-based polymers such as polyhydroxyethyl methacrylate and copolymers thereof, or Examples include functional group-modified polymers such as carboxyl groups of these various polymers.

The water-soluble polymer preferably used in the present invention is polyvinyl alcohol and its derivatives, and the degree of saponification of vinyl acetate units is usually preferably 70 mol% or more, more preferably 80 mol% or more.

The degree of polymerization of polyvinyl alcohol is usually preferably 1000 to 3000, more preferably 1
Those in the range of 500 to 2500 are used.

Colloidal silica and water-soluble polymer have a weight ratio of colloidal silica / water-soluble polymer of 1/1 to 10 /.
1 is preferable, further preferably 2/1 to 8/1, and more preferably 3/1 to 5/1. When the colloidal silica / water-soluble polymer is less than 1/1, the water resistance of the recording layer formed is poor, and when it exceeds 10/1, the strength of the recording layer formed is lowered, and the coating property is further deteriorated. However, it is difficult to form a uniform layer, which is not preferable.

The surface resistance of the recording layer in the present invention is 10
It is preferably ⁸ to 10 ¹³ Ω / □. More preferably, it is 10 ⁸ to 10 ¹² Ω / □. If the surface resistance value of the recording layer is lower than 10 ⁸ Ω / □, the charging property is lowered and the transferability of the toner is poor, and if the surface resistance value of the recording layer is higher than 10 ¹³ Ω / □, the toner scatters or runs. It is not preferable because of poor quality.

In the present invention, inorganic and / or organic particles may be dispersed in order to enhance the recording characteristics of the recording layer. Examples of the inorganic particles include silica, clay, talc, diatomaceous earth, calcium carbonate, barium sulfate, aluminum silicate, synthetic zeolite, alumina, zinc oxide, and mica other than those used as the main component of the present invention. As the organic particles, for example, polymethylmethacrylate, polystyrene and their copolymers, polyvinyl chloride, polyethylene, polypropylene, polyvinylidene chloride, plastic pigments such as polycarbonate can be preferably used, but are not limited thereto. There is no.

In the recording layer of the recording sheet of the present invention,
Known additives such as a defoaming agent, a coating property improving agent, a thickening agent, an antistatic agent, an antioxidant, an ultraviolet absorber, a dye and the like may be contained within the range of not impairing the characteristics of the present invention.

The coating thickness of the recording layer is not particularly limited,
1 to 50 μm is preferable, and more preferably 3 to 50 μm.
m. If it is thinner than this, the silicone oil absorbency and ink absorbency are poor, and if it is thicker than this, the strength of the recording layer is lowered and the workability is deteriorated, which is not preferable.

In the present invention, an antistatic agent is applied to the surface of the film opposite to the recording layer or a coating agent containing inorganic or organic fine particles is applied in order to improve the running property and double running property of the recording sheet. May be.

The coating method of the recording layer is not particularly limited, and known methods such as gravure coating method, reverse coating method, kiss coating method, die coating method and bar coating method can be applied. At this time, not only the coatability is improved by applying a known surface treatment such as a corona treatment in air or other atmosphere on the film as necessary before coating, or a primer treatment, The recording layer can be more firmly formed on the film. The coating agent concentration, coating film drying conditions, etc. are not particularly limited, but it is desirable that the coating film drying conditions be carried out within a range that does not adversely affect various characteristics of the substrate.

Since the recording film of the present invention is superior in heat resistance as compared with the one using a polyethylene terephthalate film as a support, it can be coated and dried at a high temperature at a high speed during coating and is also excellent in high-speed processability. ing.

[0042]

Since the present invention is constructed as described above, it is excellent in heat resistance, silicone oil absorption and ink absorption,
In addition, it has excellent toner fixability and printability, and also has excellent water resistance, runnability, curl resistance to heat during recording and printing, slippage, and runnability. A recording film which is excellent in handleability and can be dried at a high temperature at the time of coating, and is also excellent in high-speed processability and the like is obtained.

[0043]

[Measurement of Physical Properties and Evaluation of Effects] The characteristic values of the present invention are based on the following measurement methods and evaluation criteria.

(1) Surface Roughness According to JIS-B0601-1976, a cutoff of 0.
25 mm, measuring length 4 mm, center line average roughness Ra (μm)
And the maximum roughness Rt (μm) were determined.

(2) Average Spherical Equivalent Diameter of Voids in Film Formed by Incompatible Polymer The cross section of the film cut in the machine direction or the vertical direction in the film forming process is magnified 1000 to 5000 times with a scanning electron microscope. Take a magnified photo of at least one of the specified thickness ranges
An image analyzer was applied to 00 or more voids, and the diameter distribution of circles corresponding to the void areas was determined. The volume average diameter of this distribution is defined as the average spherical equivalent diameter of the void.

(3) Specific gravity 25 using a carbon tetrachloride-n-heptane density gradient tube
Values in ° C were used.

(4) Heat Shrinkage The film is 10 mm wide and 300 mm long in the longitudinal or width direction.
After cutting into 200 mm, marking at 200 mm intervals and fixing to a support plate under constant tension (5 g), the original length a (mm) of the marking interval is measured. Next, a load is applied using a clip of 3 g, the treatment is performed for 30 minutes while rotating in a hot air oven at 150 ° C., and the marking interval b (mm) is measured in the same manner as the measurement of the original length. The heat shrinkage rate was calculated by the following formula, and the average value of 5 was used.

Thermal shrinkage (%) = (ab) / a

(5) Optical Density The transmission density is measured using an optical densitometer (TR927, manufactured by Macbeth Co.). The thickness of the film and the optical density were plotted to determine the optical density corresponding to each thickness.

(6) Whiteness U manufactured by Shimadzu Corporation according to JIS-L-1015
When V-260 was used and the reflectances at wavelengths of 450 nm and 550 nm were B% and G%, respectively, the whiteness was expressed as 4B-3G.

(7) Stretchability When the film was formed continuously for 24 hours, no film breakage was evaluated as "good" and two or more times as "breakaged".

(8) Cushion ratio (%) Dial gauge NO. 2109-10
The standard gauge head 900030 is used for the dial gauge stand NO. Using the 7001DGS-M, the thickness is calculated from the film thicknesses d ₅₀ and d ₅₀₀ of the respective films when a load of 50 g and 500 g is applied to the dial gauge pressing portion by the following formula.

Cushion rate = [(d ₅₀ −d ₅₀₀ ) / d ₅₀ ] × 100

(9) Shape Factor As in the case of obtaining the average equivalent spherical diameter of voids, the shape of the incompatible polymer on the film surface was applied to an image analyzer to show the average ratio of 100 major axis / minor axis.

(10) Young's modulus According to JIS-Z-1702, the tensile strength was measured at 25 ° C. and 65% RH using an “Instron” type tensile tester.

(11) Crystallization parameter ΔTcg Perkin-Elmer DSC-II (differential scanning calorimeter)
It measured using. The measurement conditions of DSC are as follows. That is, 10 mg of a sample is set in a DSC device,
After melting at a temperature of 300 ° C. for 5 minutes, it is rapidly cooled in liquid nitrogen. The temperature of this quenched sample is raised at 10 ° C./min, and the glass transition point Tg is detected. The temperature was further raised, and the crystallization exothermic peak from the glass state was taken as the cold crystallization temperature Tcc. The temperature was further raised and the heat of fusion was determined from the melting peak. Here, the difference between Tcc and Tg (Tcc-Tg) is defined as the crystallization parameter ΔTcg.

(12) Number of projections on film surface 2 Detector type scanning electron microscope (ESM-3200,
Elionix Co., Ltd.) and cross-section measurement device (PMS-1,
In Elionix Co., Ltd., the height measurement value of the protrusion when the flat surface of the film surface is set to 0 and the measured height of the protrusion is measured by an image processing apparatus (IBAS2000, Carl Zeiss Co., Ltd.).
, And reconstruct the film surface protrusion image on the image processing device. Next, the highest value among the individual projections obtained by binarizing the projections in this surface projection image is taken as the height of the projection, and this is calculated for each projection. This measurement was repeated 500 times at different places, and those having a height of 20 nm or more were used as protrusions to determine the number of protrusions. The magnification of the scanning electron microscope is selected to be 1000 to 8000 times. In some cases, the number information such as a peak count obtained by a high-precision optical interference type three-dimensional surface analysis device (TOPO-3D manufactured by WYKO, objective lens: 40 to 200 times, use of a high resolution camera is effective) is given above. SE
You may read and use it as the value of M. Also, in order to capture the protrusions in three dimensions, tilt the film by 82.5 ° and set the magnification to 1
The number of protrusions is 1 m from the average value of 100 fields of view taken by taking a photograph with an electron microscope (SEM) at a magnification of 10,000 to 500,000 times.
You may convert it per m ² .

(13) Number of Particles Contained in Surface Layer In the present invention, the surface layer means a portion from the film surface to a depth of 3D. Here, 3D means the average particle diameter D × 3 of the particles contained in the film. The cross section of the film is observed by a transmission electron microscope (TEM), and 3D is observed from the surface.
The number of particles present in the part up to 3000 to 100
Observation was carried out at a magnification of 000 for 500 fields of view, and the average number of particles converted per 1 mm ² was obtained.

(14) Average Particle Size of Particles in Film The polymer is removed from the film by a plasma low temperature ashing method to expose the particles. As for the processing condition, the polymer is incinerated, but Grain selects the condition that it is not damaged as much as possible. The particles are observed with a scanning electron microscope (SEM), and the particle image is processed with an image analyzer. The magnification of the SEM is approximately 2000 to 10,000 times, and the visual field in one measurement is appropriately selected from approximately 10 to 50 μm on each side. The volume average diameter f is obtained by the following equation from the particle diameter and its volume fraction when the number of particles is 500 or more by changing the observation location.

F = Σf _i · Nv _i where f _i is the particle size and Nv _i is the volume fraction. When the particles are organic particles or the like and are significantly damaged by the plasma low temperature ashing method, the following method may be used.

A transmission electron microscope (TE
M) is used and observation is performed at a magnification of 3000 to 100000 times.
The TEM section thickness is about 1000 angstroms,
The observation was performed for 500 fields or more in different places, and the volume average diameter f was obtained from the above formula.

(15) Scratch resistance The surface was rubbed with steel wool # 0000 and the degree of scratching was evaluated according to the following criteria.

◯: Almost no scratch even with light rubbing ×: Scratch with light rubbing

(16) Average diameter of spherulites The cross section of the film is observed by an optical or electron microscope, and the measurement is repeated until 100 spherulites in total can be observed, and the obtained values are averaged to obtain spherulites. The average diameter was used.

(17) Molecular Orientation The infrared polarization ATR method is used. As the device, an FT-IR (IFS-113V) manufactured by Bruker, to which an auxiliary device for polarization ATR measurement (manufactured by Bio-Rad Digilab) is attached is used. This ATR device has a square Inte with a symmetrical edge and a thickness of 3 mm and a side of 25 mm.
A rnal Reflection Element is attached, and absorption measurement is performed in two directions parallel and perpendicular to the stretching direction.

Taking the incident direction of light in the film length direction,
The spectrum of the coated surface and that of the uncoated surface are measured using polarized light perpendicular to the entrance slope, and are designated as S _MC and S _MP , respectively. In addition, the incident direction of light is set to the film width direction, and the spectrum of the coated surface and the uncoated surface is measured using polarized light perpendicular to the incident surface, and they are S _TC and S _TP , respectively. However, when the non-coated surface does not exist, the coated surface is wiped with various solvents, water, etc., and then the substrate surface is measured.

The difference spectrum between the coated surface and the non-coated surface is obtained by the following procedure. As the internal reference band when calculating the difference spectrum, the absorption band of the base film observed in the wave number region close to the absorption band of the coat layer required for analysis is selected.

A coefficient is determined so that the absorbance of the internal reference absorption band is 0, and a difference spectrum obtained by subtracting the spectrum of the uncoated surface from the spectrum of the coated surface is obtained for each polarization component.

[Equation 1] And

The points at two predetermined wave numbers on the difference spectrum thus obtained are connected to form a baseline,
The height from the baseline to the peak of the absorption band is the coating layer absorption band

[Equation 2] And

The degree of orientation (P) is calculated from the absorbance of the coating layer thus obtained by the following equation.

[0071]

(Equation 3) (18) Identification of hydrophilic group-containing polyester by ESCA method Measurement by ESCA method (X-ray photoelectron spectroscopy) was performed under the following conditions.

Apparatus: Shimadzu ESCA750 Excitation X-ray: Mg, Kα1.2 ray (1253.6 eV) Energy correction: The binding energy value of the C _1S main peak was adjusted to 284.6 eV.

Photoelectron escape angle (θ): 90 ° Identification was carried out at a depth within 100 angstroms from the surface of the crosslinked modified layer by the above method, and the atomic area was determined from the S _2P / C _1S peak area ratio attributed to the hydrophilic group. The number ratio was determined, and when the value was 0.001 or less, it was set as the detection limit or less.

From the chemical states of the detected elements, C _1S and O
The presence or absence of polyester was identified by the proportion of _1S peak components and the peak shape, especially the presence or absence of π-π ^* satellite due to the presence of benzene ring due to polyester.
As a result, the S _2P / C _1S atomic number ratio and the case where polyester was not detected were marked with “◯”, and the case where both or either were detected was marked with “X”.

(19) Electrophotographic recording characteristics Full color electrostatic copying machine Pixel D manufactured by Canon Inc.
A full color test pattern was printed using io, the printing quality, silicone oil absorbency, running property and curl property were evaluated, and the recording property was judged as follows. The printing quality was evaluated by visual observation with a magnifying glass, the silicone oil absorption was evaluated 30 minutes after printing, and the absorption of silicone oil was evaluated by touching with a finger, and the curl was measured 30 minutes after printing on an A4 size recording film. At 20 ° C. and 60% RH, the recording layer was allowed to stand still on a horizontal plate, and the maximum value of the floating distances from the four corner plates was measured and evaluated.

Print quality ◎: Very good ○: Good Δ: Slightly inferior ×: Toner flow, repellency, bleeding, etc.

Silicone oil absorbency ○: Good Δ: Slightly inferior ×: Almost no silicone oil is absorbed

Travelability: Evaluation was made by comprehensively judging occurrence of heavy running, paper jam, and alignment in the storage tray. Good ones were marked with ◯, and bad ones were marked with x.

Curlability ◯: Good (less than 3 mm) Δ: Slightly inferior (3 mm or more, less than 15 mm) X: Poor (15 mm or more)

(20) Inkjet recording property 98 note personal computer manufactured by NEC Corporation
Bubble Jet Printer BJC- manufactured by Canon Inc.
820J was connected, a character pattern was inkjet-recorded, image quality and ink absorbency were evaluated, and the printability was determined as follows. The image quality was evaluated by visual observation using a magnifying glass, and the ink absorbency was evaluated by the degree of contamination of the recording layer with the ink when the recorded portion was rubbed once with a finger immediately after recording.

Image quality ⊚: Very good (dots are uniform and clear) ◯: Good Δ: Slightly inferior ×: Dot flow, repelling, bleeding, etc.

Ink absorbency ⊚: Very good (the recording layer is not soiled at all) ◯: Good Δ: Slightly inferior ×: Ink is removed and the recording layer is soiled

(21) Fabric ribbon recording property 98 note personal computer manufactured by NEC Corporation
The serial printer "PC-PR201U" is connected to e and the character pattern is printed on the fabric ribbon "OAR-N".
Printing was performed using F2 ″ (manufactured by Pilot Co., Ltd.), the printing quality and ink absorbency were evaluated, and the recording property was judged as follows. The image quality was evaluated by visual observation using a magnifying glass. The ink absorbency was evaluated by the degree of contamination of the recording layer with the ink when the recording portion was rubbed once with a finger immediately after recording.

◯: Both print quality and ink absorbency are good. Δ: Print quality and ink absorbency are slightly inferior. X: Print quality and ink absorbency are both poor.

(22) Water resistance of recording layer: Water was applied to a cotton swab, and the recording layer was lightly rubbed for evaluation.

⊚: Very good (no loss of recording part even after rubbing 50 times) ○: Good (no loss of recording part after rubbing 30 times) Δ: Slightly inferior (loss of recording part after rubbing 10 to 30 times) X): Poor (falls off less than 10 times)

(23) pH pH meter (manufactured by HORIBA Ltd., pH METE
It was measured using R F-14).

(24) Surface resistance value ULTRA HIGH RESISTANCE MET
Using ER (ADVANTEST R8340), voltage: 100V, Charge: 5 seconds, 20 ° C., 6
It was measured in an environment of 0% RH.

(25) Haze Integrating sphere type light transmitting device (Japan Precision Optics Co., Ltd. HT.
R. JIS K-6 using meter SEP-H-2)
714 according to the measurement.

[0090]

EXAMPLES The present invention will now be described by way of examples, which should not be construed as limiting the invention.

Example 1 Polyethylene 2,6-naphthalate homopolymer chip produced by a conventional method (intrinsic viscosity [η] = 0.7)
After being sufficiently dried in vacuum, it is supplied to an extruder, melt-extruded at 295 ° C., filtered through a 10 μm-cut metal sintered filter, and then extruded into a sheet from a T-shaped die, and cooled at a surface temperature of 25 ° C. It was wound around a drum and electrostatically cooled and solidified.
In order to improve the adhesion between the sheet and the surface of the cooling drum during this period, a wire electrode is arranged on the sheet side, and 6000
A DC voltage of V was applied. The thus obtained unstretched polyethylene 2,6-naphthalate film was stretched 3.5 times in the longitudinal direction by a roll group heated to 120 ° C and cooled to 25 ° C. Further, the drawn film is guided to a tenter 1
Stretched 3.3 times in the width direction in an atmosphere kept at 25 ° C,
Heat setting was performed at 225 ° C. to obtain a film having a thickness of 100 μm. After the corona discharge treatment was performed on the surface of the film thus obtained, the recording layer having the following composition was used as the recording layer on the corona discharge treated surface, and the coating was dried by a reverse coater so that the thickness after drying was 30 μm. A recording sheet of the present invention was obtained. The properties of the recording sheet thus obtained are as shown in Tables 1 and 2, and the recording properties were good, and the water resistance and curl were excellent. When projected by an overhead projector, the image was clear and was good as an overhead projector sheet.

[Coating Composition] Polyvinyl alcohol (PVA-H-24 manufactured by Denki Kagaku Co., Ltd. Saponification degree: 95.5
%, Degree of polymerization: 2400) and acidic beaded colloidal silica (“Snowtex” OUP pH manufactured by Nissan Chemical Industries, Ltd.)
2.9) is dissolved in water so that the solid content ratio becomes 1/5,
A paint having a solid content of 15% was used.

Example 2 In Example 1, polyvinyl alcohol (Kuraray Co., Ltd.) was used.
PVA-CM318 manufactured by PVA-CM318 A recording sheet of the present invention was obtained in the same manner except that the saponification degree: 88.0% and the polymerization degree: 1800) were used. The properties of the recording sheet thus obtained are as shown in Tables 1 and 2, and the recording properties were good, and the water resistance and curl were excellent. When projected with an overhead projector, the image was clear and good as an overhead projector sheet.

Example 3 In Example 1, polyvinyl alcohol (PVA-W-24 manufactured by Denki Kagaku Co., Ltd., saponification degree: 78.0%,
A recording sheet of the present invention was obtained in the same manner except that the degree of polymerization: 2400) was used. The properties of the recording sheet thus obtained are as shown in Tables 1 and 2, and the recording properties were good, and the water resistance and curl were excellent. When projected with an overhead projector, the image was clear and good as an overhead projector sheet.

Example 4 Polyvinyl alcohol (PVA-K-24E manufactured by Denki Kagaku Co., Ltd., saponification degree: 98.0) in Example 1
%, Degree of polymerization: 2400) and acidic beaded colloidal silica (“Snowtex” OUP pH manufactured by Nissan Chemical Industries, Ltd.)
A recording sheet of the present invention was obtained in the same manner except that the one dissolved in water-isopropyl alcohol solvent was used so that the solid content ratio of 2.9) was 1/5. The properties of the recording sheet thus obtained are as shown in Tables 1 and 2, and the recording properties were good, and the water resistance and curl were excellent. When projected with an overhead projector, the image was clear and good as an overhead projector sheet.

Example 5 Polyethylene 2,6-naphthalate (Intrinsic viscosity [η] =
0.7) 94% by weight, poly-4-methylpentene-1
(Mitsui Petrochemical Co., Ltd.) TPX-D820) 5% by weight,
A raw material that had been pelletized in advance at a ratio of 1% by weight of polyethylene glycol having a molecular weight of 4000 was supplied to the extruder A, melted at 295 ° C. by a conventional method, and introduced into the center of the T-die three-layer die.

On the other hand, 86% by weight of polyethylene 2,6-naphthalate was added to calcium carbonate (average particle size 0.8 μm).
The raw material added with 14% by weight of m) was supplied to the extruder B, melted at 295 ° C. by a conventional method and laminated on both surface layers of the T-die three-layer die, and the melt sheet was kept at a surface temperature of 25 ° C. On the cooling drum, it was contact-cooled and solidified by the electrostatic charge method. Then, the cast sheet was subjected to a conventional method at 120 ° C. in the longitudinal direction.
It is stretched 3.5 times using a group of rolls heated to
Cooled to ° C. Further, the stretched film was introduced into a tenter, stretched 3.2 times in the width direction in an atmosphere heated to 125 ° C., and heat-set at 225 ° C. to obtain a film having a thickness of 100 μm. The thickness of each film layer is 6 μm on the surface layer,
The central layer had a structure of 88 μm.

Then, after subjecting the film surface to corona discharge treatment, a recording sheet of the present invention was similarly obtained using the coating material of Example 4. The properties of the recording sheet thus obtained are as shown in Tables 1 and 2, and the recording properties were good, and the water resistance and curl were excellent.

Example 6 In Example 1, polyethylene glycol (molecular weight 3
00) and acidic beaded colloidal silica (Nissan Chemical Co., Ltd.)
A recording sheet of the present invention was obtained in the same manner, except that "Snowtex" OUP (manufactured by OUP, pH: 2.9) was dissolved in a water-isopropyl alcohol solvent so that the solid content ratio was 1/4. The properties of the recording sheet thus obtained are as shown in Tables 1 and 2, and the recording properties were good, and the water resistance and curl were excellent. When projected with an overhead projector, the image was clear and good as an overhead projector sheet.

Example 7 In Example 5, basic beaded colloidal silica (“Snowtex” UP pH: 10. manufactured by Nissan Kagaku Co., Ltd.) was used.
A recording sheet of the present invention was obtained in the same manner except that 3) was used. The properties of the recording sheet thus obtained are as shown in Tables 1 and 2, and the recording properties were good, and the water resistance and curl were excellent. When projected with an overhead projector, the image was clear and good as an overhead projector sheet.

Comparative Example 1 Using a polyethylene terephthalate homopolymer chip (intrinsic viscosity: [η] = 0.6, melting point: 259 ° C.) produced by a conventional method, a thickness of 100 μm was obtained by a conventional method.
A biaxially stretched polyethylene terephthalate film having m and a specific gravity of 1.4 was obtained. A recording sheet of the present invention was obtained in the same manner as in Example 1 except that the polyethylene terephthalate film thus obtained was used. The properties of the recording sheet thus obtained are as shown in Tables 1 and 2, and the recording properties were good and the water resistance was excellent, but the curling property was poor.

Comparative Example 2 Acid beaded colloidal silica in Example 1 (“Snowtex” OUP pH: 2.9 manufactured by Nissan Chemical Industries, Ltd.)
A recording sheet was obtained in the same manner except that was not used. The properties of the recording sheet are as shown in Tables 1 and 2 and were inferior in silicone oil absorbability, running property and water resistance of the recording layer.

Comparative Example 3 In Example 1, polyvinyl alcohol (PVA-H-24 manufactured by Denki Kagaku Co., Ltd. saponification degree: 95.5%,
Polymerization degree: 2400) and acidic beaded colloidal silica (“Snowtex” OUP manufactured by Nissan Chemical Industries, Ltd.) pH: 2.
A recording sheet was obtained in the same manner except that the solid content ratio of 9) was 1/3. The properties of the recording sheet are as shown in Tables 1 and 2 and were inferior to the silicone oil absorbability, the ink jet recording property and the fabric ribbon recording property.

Example 8 Instead of polyethylene 2,6-naphthalate and calcium carbonate used in both surface layers of Example 7, an average particle size of 0.
PEN containing 15% by weight of 3 μm colloidal silica
And a recording sheet was obtained in the same manner as in Example 1 except that the thickness of both surface layers was 0.5 μm. The characteristics of the obtained recording sheet are as shown in Tables 1 and 2,
The recording property was good, and the water resistance and curling property were also excellent. In addition, it has excellent runnability and slipperiness, and is easy to handle.
It was also excellent in processability.

Example 9 PEN used in Example 1 was used as a central layer and ΔTcg was 30.
Polyester film having PEN at both temperatures of 180 ° C. for both outermost layers was dried under reduced pressure at 180 ° C. for 3 hours (400 Pa).
And feed each to two extruders and melt at 295 ° C.
These polymers are combined and laminated in a rectangular confluent block (feed block) for three layers, and by an electrostatically applied casting method, they are wound around a casting drum with a refrigerant temperature of 30 ° C., cooled and solidified, and an unstretched three-layer structure is formed. I got a film. At this time, the discharge amount of each extruder was adjusted to adjust the thickness of the outermost layer. The surface of the unstretched film which was not in contact with the drum was heat-treated at 190 ° C. for 5 seconds using a known radiation heater. After the heat treatment, the film was stretched 3.4 times in the longitudinal direction at a temperature of 90 ° C., further stretched 3.5 times in the width direction at 100 ° C. at a stretching rate of 2000% / min using a stenter, and further stretched at a constant length of 2 times.
Heat treatment was performed at 10 ° C. for 5 seconds to obtain a biaxially oriented PEN film (specific gravity: 1.0) having a total thickness of 100 μm (the outermost layers were 0.2 μm each). The number of surface protrusions of this film was 200,000 / mm ² , and N _R was 45. A recording sheet of the present invention was obtained in the same manner by using this film as a support film and using the coating material of Example 1. The properties of the recording sheet thus obtained are as shown in Tables 1 and 2, and have good recording properties, excellent water resistance, curl property, running property, slip property, handleability,
It was also excellent in processability.

[0106]

[Table 1]

[Table 2]

[0107]

Since the present invention is constructed as described above,
Excellent heat resistance, silicone oil absorption, ink absorption, toner fixability, printability, and water resistance.
Runnability, curl to heat during recording and printing, slipperiness,
A recording film that has excellent running properties, is less likely to be scratched during processing such as slitting and cutting, has excellent processability and handleability, and can be dried at high temperature during coating, and has excellent high-speed processability. Is. Therefore, it is possible to obtain a recording film having excellent handleability during recording, printing, and processing, which hardly causes curling due to heat as a recording sheet for monochrome and color electrophotographic copying machines, and recording for inkjet printers. It can be preferably used in applications such as sheets, fabric ribbon receivers, carbon ink receivers, and oil-based offset printing and flexographic printing. Further, the recording sheet of the present invention can be applied as other inks such as sublimation type thermal ink receivers and wet toner receivers by utilizing its excellent ink absorbability. Further, the transparent recording layer can be applied to OHP applications.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B41J 31/00 A B41M 5/00 B 5/38

Claims (10)

[Claims] 1. A recording layer (I) is formed on a base film (I).
A recording film obtained by laminating I), wherein the base film (I) is a polyethylene 2,6-naphthalate film and the recording layer (II) is composed of colloidal silica and a water-soluble polymer. the film. 2. The laminated film according to claim 1, wherein the colloidal silica has a beaded shape connected and / or branched. 3. The recording film according to claim 1, wherein the colloidal silica has an acidic pH. 4. The recording film according to claim 1, wherein the water-soluble polymer is polyvinyl alcohol. 5. The recording film according to claim 4, wherein the polyvinyl alcohol has a saponification degree of 70 mol% or more and a polymerization degree of 1000 to 3000. 6. The base film (I) is polyethylene 2,
The recording film according to claim 1, which is a 6-naphthalate / polyethylene terephthalate composite film or a polyethylene 2,6-naphthalate / polyethylene terephthalate / polyethylene 2,6-naphthalate composite film. 7. The recording film according to claim 1, wherein the base film (I) is a white polyethylene 2,6-naphthalate film. 8. The base film (I) has an apparent specific gravity of 0. Four
The recording film according to claim 1, wherein the recording film is a white polyethylene 2,6-naphthalate film having a thickness of 1.3 or less. 9. A base film (I) is a film layer (III) containing at least one surface of a thermoplastic resin (a) as a main component, and the base film (I) is contained in the film layer (III). The average particle size of the inert particles is the film layer (III)
0.1 to 10 times the thickness, the content of the inert particles is 0.1
˜50% by weight and the thickness of the film layer (III) is
The recording film according to claim 1, wherein the recording film has a thickness of 0.005 to 3 μm. 10. The substrate film (I) is characterized in that at least one side thereof is a polyester layer (IV) having protrusions formed by utilizing crystallization of polyester itself, essentially not containing particles. The recording film according to claim 1.