JPH09109345A - Polyester film for diazo second copy of original - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent scratch resistance and excellent adhesive properties and to reduce the decrease in the adhesive properties even under high temperature and high humidity environment by providing a laminated layer film on one side surface of a polyester film, phase separating the laminated film in the thickness direction, and making the mixed phase of respective phases exist in a separate boundary. SOLUTION: A laminated film has a laminated membrane made of substantially one layer on at least one side surface of a polyester film. The laminated film is phase separated in the thickness direction, and the phase separate boundary is a polyester film for diazo second copy of original existing the mixed phase of the respective phases. The diazo film for the second copy of original has a diazo sensitive material layer laminated at the easy adhesive layer side of the easy adhesive film, and a normal blue or white colored mat layer laminated at the opposite side as a four-layer structure. The way of using includes the steps of superposing an original at the sensitive material layer side of the diazo film, inserting it into a dry diazo copier to be exposed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester film for a diazo second original drawing, and more particularly to a polyester film for a diazo second original drawing which is excellent in scratch resistance, adhesion, moisture resistance adhesion and the like.

[0002]

2. Description of the Related Art Currently, various polymers are widely used in various fields. Among them, polyesters, particularly polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate or poly-1,4-cyclohexanedimethylene terephthalate and polyesters mainly containing these have excellent physical and chemical properties, and fiber, It is widely used as a film or sheet and also as a molded product thereof.

In particular, since polyester films have excellent heat resistance, chemical resistance and mechanical properties, they are used in many applications such as magnetic recording materials, various photographic materials, packaging materials, electrical insulating materials and general industrial materials. It is used.

However, since polyester itself is generally inactive and poor in adhesiveness, when various coatings such as diazo photosensitive paint are applied to the film surface, in order to improve the adhesiveness with the coating, It is known that the film surface is subjected to a physical treatment such as corona discharge or plasma, a chemical treatment using a chemical such as an alkali or amine, and a method of coating an easily adhesive substance.

However, the physical or chemical surface treatment method does not provide sufficient adhesion, and depending on the method, the process becomes complicated and the cost increases.

On the other hand, the method of coating an easily adhesive substance can be carried out in the production process of the polyester film, is advantageous in terms of cost, and it is possible to select an adhesive substance which can be applied to various coatings. A laminate of acrylic resin, water-soluble and water-dispersible polyester on a polyester film as an easily adhesive substance has been proposed (Japanese Patent Publication No. 3-62551).

[0007]

However, the above-mentioned conventional technique has the following problems. That is, when an acrylic resin, a water-soluble or water-dispersible polyester is laminated, even if the desired adhesiveness is obtained, the scratch resistance of the coating film, the moisture resistance, etc. are inferior, so the adhesion with scratching,
There are problems such as poor adhesion under high temperature and high humidity environment. The present invention eliminates these drawbacks, scratch resistance, adhesion, excellent adhesive resistance to moisture, etc., and also provides a polyester film for diazo second original drawing with less deterioration in adhesion even under a high temperature and high humidity environment. is there.

[0008]

The present invention provides a laminated film in which a laminated film consisting essentially of one layer is provided on at least one side of a polyester film, and the laminated film is phase-separated in the thickness direction, and The phase-separated interface is mainly composed of a polyester film for diazo second original drawing, which is characterized by the presence of mixed phases of each phase.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Here, the constitution of a polyester film for a second original drawing, which is one of the uses for an easily adhesive diazo film, will be described. The structure of the diazo film for the second original drawing is a four-layer structure in which a diazo sensitive material layer is laminated on the easy adhesive layer side of the easy adhesive film, and a matte layer usually colored blue or white is laminated on the opposite side of the easy adhesive layer. It has a structure. As for usage, for example, when making a copy of a drawing or the like, the original is directly superposed on the photosensitive material layer side of the diazo film, inserted into a dry diazo copying machine, and exposed. The diazo compound in the photosensitive portion (blank part of the original) is decomposed by light to generate a photodegraded product, which does not develop color even in the development in the subsequent step. On the other hand, the diazo compound in the non-photosensitive area (the area where the light is blocked by lines or characters) produces an azo dye by the ammonia gas (alkali) development in the next step in the presence of the coupler, and the line or character area Is colored black.

The polyester film for the second original image is a map or film that requires high accuracy or long-term storage stability because of its high density, high resolution, durability, water resistance, heat resistance, retouchability, long-term storage stability, and antistatic property. Mainly used for reproduction of blueprints of aircraft, ships, automobiles, etc.

In order to be used as described above, the easy-adhesion layer of the polyester film for diazo second original drawing needs to firmly adhere the polyester base film and the diazo sensitive material layer. In general, a cellulose acetate-based and acrylic polymer, for example, when using an acrylic resin alone in the easy-adhesion layer, the adhesion with the diazo sensitive material layer is good, but the adhesion with the polyester base film is Is insufficient. On the other hand, when a polyester resin layer or a polyurethane resin layer is used as the easy-adhesion layer, the adhesion to the polyester base film is sufficient, but the adhesion to the diazo sensitive material layer is insufficient. Further, a graft polymer obtained by grafting an acrylic monomer on a polyester resin cannot obtain sufficient adhesion to any of them. In order to solve this contradictory phenomenon, the present inventors used two kinds of resins, for example, an acrylic resin and a polyester resin in combination, and controlled the coating conditions when the easy-adhesion layer was formed. It has been found that a so-called two-phase structure is adopted in which a phase-separated structure is adopted and a polyester resin is on the polyester base film side and an acrylic resin is on the gas phase side.

The polyester of the polyester film of the present invention is produced by esterification or transesterification of dicarboxylic acid or its ester-forming derivative with glycol and polycondensation reaction. The type of polyester is not particularly limited as long as it can be formed into a film. Suitable polyesters that can be formed into a film include those using an aromatic dicarboxylic acid as a dicarboxylic acid component, such as polyethylene terephthalate, polyethylene 2,6-naphthalate,
Examples thereof include polybutylene terephthalate, polyethylene α, β-bis (2-chlorophenoxy) ethane 4,4, -dicarboxylate, and the like. Among these, polyethylene terephthalate is most preferable in view of quality, economy and the like. Therefore, polyethylene terephthalate (hereinafter abbreviated as PET) will be described below as a typical example of polyester.

PET is 80 mol% or more, preferably 9
Although 0 mol% or more, more preferably 95 mol% or more, has ethylene terephthalate as a repeating unit,
Some other dicarboxylic acid components and diol components may be copolymerized. Known additives such as heat resistance stabilizer, oxidation resistance stabilizer, weather resistance stabilizer, ultraviolet absorber, organic lubricant, pigment, dye, organic or inorganic fine particles, filler, antistatic agent, etc. You may mix | blend a nucleating agent etc. The PET film described above has an intrinsic viscosity (measured in orthochlorophenol at 25 ° C.) of 0.4 to 1.2 dl / g, preferably 0.5 to 0.8 dl / g. It is suitable.

The polyester film in the present invention is preferably biaxially oriented from the viewpoint of mechanical and thermal characteristics in the state where the laminated film is provided. For example, polyester is dried, melt-extruded to form an unstretched sheet, and then biaxially stretched and heat-treated to produce a film. Biaxial stretching may be either longitudinal or transverse sequential stretching or biaxial simultaneous stretching, and the stretching ratio is not particularly limited, but usually 2 to 5 times both longitudinal and transverse are suitable. Alternatively, it may be stretched in the longitudinal direction or the transverse direction and then re-stretched in either the longitudinal direction or the transverse direction. The thickness of the polyester is not particularly limited, but 2 to 500 μm is preferably used.

In the laminated film provided on the surface of the polyester film of the present invention, the surface layer in the present invention is mainly composed of acrylic resin and the lower part thereof is composed of polyester resin in view of compatibility and adhesion with the diazo sensitive material layer. It is preferable to use it as a main constituent, and it is preferable that its interface is a mixture of acrylic resin and polyester resin.

The composition of the acrylic resin is not particularly limited, but those containing acrylonitrile in the component are preferably used from the viewpoint of scratch resistance and adhesion. The copolymerization amount of acrylonitrile is also not particularly limited, but it is 1 to 3 from the viewpoint of scratch resistance and adhesion.
It is 0% by weight, preferably 2 to 20% by weight, particularly preferably 3 to 15% by weight. If it is less than 1% by weight, the improving effect is small, and if it exceeds 30% by weight, scratch resistance and adhesion tend to be deteriorated.

Such an acrylic resin can be manufactured by a known method, and the following monomer components can be exemplified as the monomer component constituting the resin, but the monomer components are not particularly limited as long as they satisfy the above requirements. Absent. Monomers used for polymerization of the acrylic resin include alkyl acrylate and alkyl methacrylate (as the alkyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-
(Ethylhexyl group, lauryl group, stearyl group, cyclohexyl group, phenyl group, benzyl group, etc.) as a basic skeleton, and in order to impart a functional group, it is copolymerized with a monomer having the following functional group. That is, as the functional group, a carboxyl group, a methylol group, an acid anhydride group, a sulfonic acid group, an amide group or an alkylolated amide group,
Examples thereof include an amino group (including a substituted amino group), an alkylolated amino group, a hydroxyl group, an epoxy group, and the like, and salts or esterified products thereof may be copolymerized.

Examples of the compound having a carboxyl group and / or its salt or an acid anhydride group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, alkali metal salts of these carboxylic acids, and ammonium. Examples thereof include salts and anhydrides.

Examples of the compound having a sulfonic acid group and / or a salt thereof include vinyl sulfonic acid, styrene sulfonic acid, alkali metal salts and ammonium salts thereof.

Examples of the compound having an amide group or an alkylolated amide group include acrylamide, methacrylamide, N-methylmethacrylamide, methylolacrylamide, methylolmethacrylamide, ureido vinyl ether, β-ureidoisobutyl vinyl ether and ureidoethyl acrylate. And so on.

Examples of compounds having an amino group or an alkylated amino group and / or a salt thereof include diethylaminoethyl vinyl ether, 2-aminoethyl vinyl ether, 3-aminopropyl vinyl ether,
2-aminobutyl vinyl ether, dimethylaminoethyl methacrylate, dimethylaminoethyl vinyl ether, and their amino groups methylolated,
Examples thereof include those which are quaternized with an alkyl halide, dimethyl sulfate, sultone, and the like.

Examples of the compound having a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β
-Hydroxypropyl methacrylate, β-hydroxyvinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate and the like.

Examples of the compound having an epoxy group include glycidyl acrylate and glycidyl methacrylate.

In addition to the above, the following compounds may be used in combination. That is, with methacrylonitrile, styrenes, butyl vinyl ether, maleic acid mono- or dialkyl esters, itaconic acid mono- or dialkyl esters, methyl vinyl ketone, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl pyridine, vinyl pyrrolidone, vinyl trisalkoxysilane, etc. Of course, the present invention is not limited to these.

Monomers and other compounds having these crosslinkable functional groups may be copolymerized with the monomers that form the basic skeleton at an arbitrary ratio, and two or more kinds of monomers may be copolymerized. As a specific example of the preferable ratio, the ratio of the monomer having a crosslinkable functional group to the monomer serving as the basic skeleton is usually 1 to
It is about 30% by weight.

The glass transition temperature of the acrylic resin used in the present invention is not particularly limited, but is preferably 0 ° C. or higher and 80 ° C. or lower, and more preferably 10 ° C. or higher and 50 ° C. or lower. When an acrylic resin having a low glass transition temperature is used, the adhesion and scratch resistance under high temperature and high humidity tend to be poor. On the contrary, when it is too high, cracking may occur during stretching, which is not preferable. The glass transition temperature of the acrylic resin can be arbitrarily set depending on the monomer to be used. For example, in order to obtain a polymer having a high glass transition temperature, the copolymerization amount of methyl methacrylate is increased, and to obtain a resin having a low glass transition temperature, Copolymerization of chain alkyl acrylates is effective. Further, when the molecular weight of the acrylic resin is 100,000 or more, the toughness of the easily adhesive layer is increased, which is particularly preferable.

The above-mentioned acrylic resin is preferably one that can be dissolved, emulsified or suspended in water from the viewpoint of environmental pollution and explosion-proof, and such a copolymer is a monomer having a hydrophilic group (acrylic acid, methacrylic acid, acrylamide, It can be prepared by a known method such as copolymerization with vinyl sulfonic acid and its salt), emulsion polymerization using a surfactant, suspension polymerization, soap-free polymerization without a surfactant.

As an example of a preferable acrylic resin composition in the present invention, an acrylic copolymer having methyl methacrylate, butyl acrylate or ethyl acrylate copolymer as a basic skeleton and a small amount of acrylic acid, acrylonitrile or glycidyl methacrylate, acrylamide and the like is copolymerized. An example is coalescence.

In the present invention, it is important that a polyester resin layer is provided below the acrylic resin layer.

The polyester resin is also not particularly limited, but an aqueous polyester resin having no sulfonate group in the molecule is preferably used from the viewpoint of scratch resistance, adhesion and moisture resistance adhesion. The glass transition temperature of the aqueous polyester resin is 20 ° C or higher and lower than 90 ° C, preferably 40 ° C or higher and lower than 80 ° C. Glass transition temperature is 2
If the temperature is lower than 0 ° C, the adhesiveness will be inferior to the humidity resistance.
The above is not preferable because the film-forming property becomes inferior. The acid value of the aqueous polyester resin is 20 KOHmg /
g or more, preferably 40 KOHmg / g or more is preferably used from the viewpoint of scratch resistance and adhesion. The lamination ratio of acrylic resin layer / polyester resin layer is 90/10
The range of 10/90 is preferable in terms of scratch resistance.

As an example of a preferable composition of the polyester resin in the present invention, a copolyester such as tereric acid or isophthalic acid as a dicarboxylic acid component and ethylene glycol, neopentyl glycol or 1,4-butanediol as a diol component may be mentioned. You can Further, in order to increase the concentration of carboxylic acid in the polyester resin, it is preferable to use a dicarboxylic acid having three or more functional groups, and trimellitic acid, trimellitic anhydride, etc. are preferably used. In particular, in order to make the polyester resin containing no sulfonate group aqueous, a method of increasing the carboxylic acid concentration and ammonium-forming the portion is used.

In the present invention, addition of a cross-linking agent to the above acrylic resin and polyester resin is effective for more clearly causing phase separation, and is preferable in terms of scratch resistance and adhesion. The cross-linking agent in the present invention is not particularly limited, it is a functional group present in the resin constituting the laminated film, for example, a hydroxyl group, a carboxyl group, a amide group and the like that can be cross-linked, as a representative example. Is a methylolated or alkylolated urea-based, melamine-based, acrylamide-based, polyamide-based resin, epoxy compound, isocyanate compound,
Examples thereof include an aziridine compound, various silane coupling agents, and various titanate coupling agents. In the present invention, methylolated melamine is preferably used in terms of scratch resistance, adhesiveness, and the like.

The amount of the crosslinking agent added is 0.5 to 30% by weight, preferably 2 to 20% by weight, based on the solid content weight ratio in the easy-adhesion layer so that the effect of the present invention can be exhibited more significantly. The range of 3 to 10 wt% is preferable. If the cross-linking agent is less than 0.5% by weight or more than 30% by weight, scratch resistance tends to decrease, which is not preferable. Further, another crosslinking agent may be used in combination as long as the effect of the present invention is not impaired.

The effect of the cross-linking agent in the present invention plays a role of effectively exhibiting phase separation and more firmly adhering and bonding the easy-adhesion layer and the base film and the easy-adhesion layer and the diazo sensitive material layer. There is.

In the easy-adhesion layer, known additives such as heat-resistant stabilizers, oxidation-resistant stabilizers, weather-resistant stabilizers, ultraviolet absorbers, flame retardants, pigments, dyes, etc. are added within a range that does not impair the effects of the present invention. Fatty acid ester, organic lubricant such as wax or antifoaming agent such as polysiloxy acid may be blended, and further clay, mica, titanium oxide, calcium carbonate, kaolin, wet and dry silica, for the purpose of imparting lubricity. Inorganic particles such as colloidal silica, calcium phosphate, barium sulfate, and alumina, as well as acrylic acids,
You may mix | blend the organic particle etc. which have styrene etc. as a structural component. The average particle size of these inorganic or organic particles is 0.
01 to 1 μm is preferable, and the addition amount is usually 30% by weight.
Less than is preferred.

The thickness of the easy-adhesion layer in the present invention is 0.0
The range of 05 to 3 μm, preferably 0.03 to 1 μm, and more preferably 0.05 to 0.5 μm is preferable. If the thickness of the easy-adhesion layer is too thick, the coating film itself tends to be cleaved, while if it is too thin, scratch resistance, adhesion, etc. tend to deteriorate. As a method of coating on the base film, a known coating method such as a reverse coating method, a gravure coating method, a rod coating method or a die coating method can be used.

In the present invention, in a laminated film in which a laminated film substantially consisting of one layer is provided on at least one surface of a polyester film, the laminated film is phase-separated in the thickness direction, and the phase-separated interfaces are A laminated film characterized by the presence of mixed phases, particularly a coating film in which the surface layer of the laminated film has an acrylic resin as a main constituent, and the portion close to the polyester film substrate has a polyester resin as a main constituent. Therefore, it is preferable that each mixed layer exists at the interface between the acrylic resin and the polyester resin.

In order to obtain the phase-separated structure in the present invention, for example, a cross-linking agent is mixed in a coating material obtained by mixing a polyester resin and an acrylic resin, and a coating method is applied to a base film under specific conditions, followed by drying and stretching. A method of obtaining the laminated film constitution of the present invention by doing so.

The above-mentioned specific conditions mean that the coating material is applied at the following ambient temperature, then dried and stretched. First, it means drying after the glass transition point (Tg) of the base polyester resin or lower, then immediately raising the temperature to Tg or higher, drying again at a temperature near Tg (however, Tg or higher), and then stretching. In summary, at least two water-soluble or water-dispersible resins having different cohesive energies are mixed on at least one side of a polyester film before completion of crystal orientation, coated, dried, and then stretched at least uniaxially. In the laminated film, the surface of the base film was subjected to corona discharge treatment before coating, and the wetting tension of the surface was 45 dy.
n / cm or more, preferably 47 dyn / cm or more, more preferably 50 dyn / cm or more, and characterized by being rapidly dried after application and before the stretching, and then stretched. is there.

Next, a polyethylene terephthalate (hereinafter abbreviated as PET) film will be described as an example of the base film for the method for producing the laminated film of the present invention, but the present invention is not limited to this.

Polyester resin pellets (intrinsic viscosity 0.62 dl / g) constituting the laminated film were vacuum dried according to a conventional method, and then melt-extruded at about 280 ° C., and the sheet-like melt was subjected to electrostatic application (7 kV) casting. Surface temperature of about 25 ℃
An unstretched PET film is prepared by cooling and solidifying on a cast drum. This unstretched film is heated from 80 ° C to 100
The film is stretched 2.5 to 5 times in the machine direction between the rolls heated to ℃. At least one side of this film was subjected to a corona discharge treatment in air to have a wetting tension of the surface of 45 dyn / cm.
As described above, a coating agent for forming a laminated film is applied to the treated surface. The coated film is guided to a drying zone heated to 140 ° C. while holding it with a clip to dry the water, and then it is stretched 3.5 times in the width direction while being heated to 120 ° C. while being held with a clip. A heat treatment is performed in a heat treatment zone of 160 to 230 ° C. for 1 to 10 seconds to complete the crystal orientation of the polyester film. If necessary, a relaxation treatment of 3 to 12% may be performed during this heat treatment. Biaxial stretching may be either longitudinal or transverse sequential stretching or simultaneous biaxial stretching. After longitudinal or transverse stretching, it may be re-stretched in either longitudinal or transverse direction. The thickness of the polyester is not particularly limited, but 2 to 200 μm is preferably used. The coating liquid used in this case is preferably an aqueous system from the viewpoint of environmental pollution and explosion proof.

The film substrate may also contain at least one selected from acrylic, polyester and melamine. In this case, there are effects such that the easy-adhesion layer and the base film have improved slipperiness and adhesiveness. When acryl, polyester or melamine is contained, the amount of addition thereof is preferably 5 ppm or more and less than 20% by weight in terms of slipperiness and adhesiveness. of course,
The acrylic, polyester and melamine may be a coating composition provided on a base film (including recycled pellets of the easily adhesive film of the present invention).

The diazo sensitive material layer is applied to the easily adhesive layer side of the thus obtained laminated film.

[0044]

[Method for measuring characteristics and method for evaluating effects] The method for measuring characteristics and the method for evaluating effects in the present invention are as follows.

(1) Adhesiveness A coating layer was provided by coating the surface of the film with a bar coater so that the thickness of the diazo sensitive material coating composition after drying was 6 μm. After coating, it is dried at 100 ° C for 2 minutes, and after drying, it is developed with a dry diazo copying machine "RICOPY" SM2300F (manufactured by Ricoh Co., Ltd.), and a 1 mm width cross-cut (cross-cut) is made on the unexposed area (coloring area). Insert, attach cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) and press it firmly by hand, then 18
It was peeled off rapidly in the 0 degree direction. At this time, the residual area ratio of the coating layer remaining on the film surface side was measured, and those that did not peel at all were marked as [◎], and the residual area ratio of 90% or more was marked as [○], and those that did not meet all were marked as [X]. did.

(2) Moisture resistance and adhesion 40 times the film provided with the coating layer prepared in the above (1).
Leave for 15 hours in an atmosphere of ℃ × 90% RH, take out, dry diazo copier "RICOPY" SM2300F
(Developed by Ricoh Co., Ltd.) and 1 in unexposed area (colored area)
A cross cut (cross-cut) was put in a width of mm, cellophane adhesive tape (manufactured by Nichiban Co., Ltd.) was attached, and after strongly pressure-bonded by hand, it was rapidly peeled in a direction of 180 degrees. At this time, the residual area ratio of the coating layer remaining on the film surface side was measured, and those that did not peel at all were marked with [◎], and the residual area ratio of 90% or greater was marked with [○].
And, all that were less than that were marked as [x].

(3) Scratch resistance The diazo light-sensitive material coating material was applied on the film surface using a bar coater so that the thickness after drying was 6 μm to form a coating layer. After coating, the coating was dried at 100 ° C. for 2 minutes, and then dried and developed with a dry diazo copying machine “RICOPY” SM2300F (manufactured by Ricoh Co., Ltd.). A sapphire needle with a tip of 0.1 mmφ is applied at a right angle to this unexposed area (coloring area) using a surface quality measuring instrument “HEIDON” -14DR manufactured by Shinto Kagaku Co., Ltd., and sapphire is moved at a sample moving speed of 100 mm / min. The load applied to the needle was changed, and the load at which the surface of the previously unexposed portion (coloring portion) started to be damaged was determined as an index of scratch resistance according to the following criteria. The load at which the surface starts to be damaged is correlated with the pencil hardness.

◯: 120 g or more Δ: 80 or more and less than 120 g ×: less than 80 g

(4) Glass transition temperature Various resins were measured using a differential scanning calorimeter ("Robot" DSC, RDSC 220 type manufactured by Seiko Denshi Kogyo Co., Ltd.).
After holding at 300 ° C. for 5 minutes, the sample was rapidly cooled with liquid nitrogen and then measured at a temperature rising rate of 20 ° C./minute.

(5) Cross-sectional morphology of easy-adhesion layer, phase-separated structure The cross-sectional morphology and phase-separated structure of the easy-adhesion layer were obtained by cutting the cross-section of the easy-adhesive film into ultrathin sections, and then Ru O4 stained Os O4 stained ultrathin section method. By TEM (transmission electron microscope)
Photographs were taken, the phase separation state of the easy-adhesion layer was confirmed from the cross-sectional photographs, and the thickness of each polymer was measured. In addition, the polymer type was determined by the density difference by the staining method, and the unclear portion was defined as the polymer mixed layer.

Observation method Apparatus: Transmission electron microscope (H-7100 manufactured by Hitachi Ltd.)
FA type) Measurement conditions: Accelerating voltage 100kV Sample preparation: Frozen ultrathin section method

[0052]

EXAMPLES Next, the present invention will be explained based on examples, but the present invention is not necessarily limited to these.

Example 1 PET pellets containing 0.015% by weight of colloidal silica having an average particle size of 0.4 μm and 0.005% by weight of the same colloidal silica having an average particle size of 1.5 μm (intrinsic viscosity 0.62 dI / g ) Is sufficiently vacuum-dried, supplied to an extruder, melt-extruded at 280 ° C., filtered through a 10 μm-cut metal sintered filter, and then extruded into a sheet from a T-shaped die, which is cooled at 30 ° C. It was wrapped around and cooled and solidified. In order to improve the adhesion between the sheet and the cooling drum during this period, a wire electrode was arranged on the sheet side and a DC voltage of 6 kV was applied. The unstretched PET film thus obtained was heated to 95 ° C. and stretched 3.5 times in the longitudinal direction to obtain a uniaxially stretched film. A coating for forming an easy-adhesion layer in which one surface of this film is subjected to corona discharge treatment in an air atmosphere so that the base film has a wetting tension of 52 dyn / cm and the treated surface has the following compounding ratio (solid content ratio). Was prepared and applied by a gravure coating method. The coating thickness was such that the easy adhesion layer had a thickness of 0.1 μm after biaxial stretching. After introducing the uniaxially stretched film coated with the coating agent into the tenter and drying the water in the preheating step at 140 ° C,
While being heated to 120 ° C, it is stretched 3.5 times in the width direction while gripping with a clip, and then heat treated at 230 ° C for 5 seconds,
A laminated polyester having a laminated thickness of 0.1 μm and a film thickness of 50 μm was obtained. As a result of TEM observation of the cross section of the obtained laminated film, the laminated film was phase-separated in the thickness direction, and a mixed phase of these resins was present.

[Easy Adhesive Layer Forming Coating] (A) MMA / BA / AA / AN Copolymer Acrylic Emulsion Mixing Ratio 50 parts by Weight 65/35/2/5% by Weight MMA: Methyl Methacrylate BA: Butyl Acrylate AA: Acrylic Acid AN: Acrylonitrile

(B) IPA / DEG / NPG Copolyester 50 parts by weight 50/20/30 mol% Ammonium salt type aqueous dispersion comprising the above acid component and glycol component IPA: Isophthalic acid DEG: Diethylene glycol NPG: Neopentyl glycol

(C) Methylolated melamine 5 parts by weight

Ethylene glycol monomethyl ether (methyl cellosolve) is used as a solvent on the surface provided with the laminated film.
A diazo sensitive material layer containing as a main component was provided. The results are shown in Table 1. The adhesiveness and scratch resistance of the diazo sensitive material coating layer provided on the laminated film side were extremely good, and the adhesiveness did not decrease even in a high temperature and high humidity environment.

Example 2 An aqueous coating composition for forming a laminated film was prepared in the same manner as in Example 1 except that the component ratios of (A) and (B) in Example 1 were changed as follows. Then, a laminated polyester film having a laminated thickness of 0.1 μm and a thickness of 50 μm was obtained. As a result of TEM observation of the cross section of the obtained laminated film, the laminated film was phase-separated in the thickness direction, and a mixed phase of these resins was present. The evaluation results of this laminated polyester film are shown in Table 1. The adhesiveness and scratch resistance of the diazo sensitive material coating layer provided on the laminated film side are extremely good, and the adhesiveness is lowered even in a high temperature and high humidity environment. There was no

(A) MMA / BA / AA / AN Copolymer Acrylic Emulsion 80% by Weight 65/35/2/5% by Weight

(B) IPA / DEG / NPG copolymerized polyester 20 parts by weight 50/20/30 mol% Ammonium salt type aqueous dispersion comprising the above acid component and glycol component

(C) 5 parts by weight of methylolated melamine

Example 3 An aqueous coating composition for forming a laminated film was prepared in the same manner as in Example 1 except that the component ratios of (A) and (B) in Example 1 were changed as follows. Then, a laminated polyester film having a laminated thickness of 0.1 μm and a thickness of 50 μm was obtained. As a result of TEM observation of the cross section of the obtained laminated film, the laminated film was phase-separated in the thickness direction, and a mixed phase of these resins was present. The evaluation results of this laminated polyester film are shown in Table 1. The adhesiveness and scratch resistance of the diazo sensitive material coating layer provided on the laminated film side were extremely good, and the adhesiveness did not decrease even under a high temperature and high humidity environment.

(A) MMA / BA / AA / AN Copolymer Acrylic Emulsion Mixing Ratio 20 parts by Weight 65/35/2/5% by Weight

(B) IPA / DEG / NPG copolymerized polyester 80 parts by weight 50/20/30 mol% Ammonium salt type aqueous dispersion comprising the above acid component and glycol component

(C) Methylolated melamine 10 parts by weight

Example 4 An aqueous coating composition for forming a laminated film was prepared in the same manner as in Example 1 except that the composition of the laminated film was changed to a combination of acrylic and urethane, and the laminated thickness was 0.1 μm. A laminated polyester film having a thickness of 50 μm was obtained.
As a result of TEM observation of the cross section of the obtained laminated film, the laminated film was phase-separated in the thickness direction, and a mixed phase of these resins was present. The evaluation results of this laminated polyester film are shown in Table 1. The adhesiveness and scratch resistance of the diazo sensitive material coating layer provided on the side of the easily adhesive layer were extremely good, and the adhesiveness did not deteriorate even in a high temperature and high humidity environment.

(A) MMA / BA / AA / AN Copolymer Acrylic Emulsion Blending Ratio 50 parts by weight 65/35/2/5% by weight

(B) Polyurethane “Hydran” HW-350 50 parts by weight (manufactured by Dainippon Ink and Chemicals, Inc.)

(C) Methylolated melamine 5 parts by weight

Example 5 The same as Example 1 except that as the base film, the laminated polyester film of Example 1 was crushed into pellets instead of the polyethylene terephthalate used in Example 1 and 10 parts by weight was added. And stack thickness 0.1μ
Thus, a laminated polyester film having a thickness of 50 μm and having m was obtained. That is, 10 parts by weight of a mixture of 50 parts by weight of acrylic copolymer resin, 50 parts by weight of copolymerized polyester resin, and 5 parts by weight of methylolated melamine was used as a mixture with polyethylene terephthalate. The composition of the easy-adhesion layer applied to the base film was exactly the same as in Example 1. As a result of TEM observation of the cross section of this laminated polyester film, it had a phase-separated structure and a mixed phase was also present.
Adhesion of the diazo sensitive material coating layer provided on the side of the easily adhesive layer,
The evaluation results of scratch resistance are shown in Table 1. The results are extremely good, and there was no deterioration in adhesion even in a high temperature and high humidity environment.

Example 6 The substrate film was replaced with polyethylene terephthalate,
Example 1 except that polyethylene 2,6-naphthalate was used.
A laminated film of the present invention was obtained in the same manner as. That is, ethylene glycol and dimethyl naphthalene 2,6-dicarboxylate are transesterified and then polycondensed to obtain an intrinsic viscosity of 0.6.
7 polyethylene 2,6-naphthalate (2,6-PE
N) Chips were manufactured. The transesterification reaction conditions use calcium acetate as a catalyst at 200 to 230 ° C. for 7 hours, and the polycondensation reaction uses antimony trioxide at 280 to 3
It was 3 hours at 00 ° C. This chip has an average particle size of 0.2
After containing 0.2% by weight of silicon dioxide of μm, it was sufficiently dried, fed to an extruder and melted at 300 ° C.
After passing through a m-cut sintered metal filter, the mixture was extruded in a sheet form from a T-shaped die and wound around a cooling drum having a surface temperature of 30 ° C. to be cooled and solidified. In order to improve the adhesion between the sheet and the surface of the cooling drum during this time, a wire electrode was arranged on the sheet side, and a DC voltage of 6000 V was applied. 3. The unstretched 2,6-PEN film thus obtained was lengthwise between rolls heated to 140 ° C.
It was stretched 0 times to obtain a uniaxially stretched film. After subjecting one side of this film to corona discharge treatment in an air atmosphere to have a surface wetting tension of 48 dyn / cm, the treated surface was biaxially stretched with the same aqueous resin layer as used in Example 1 by a gravure coating method. To have a thickness of 0.1 μm.
Guide the coated uniaxially stretched film into the tenter and
After being dried at a temperature of 130 ° C., it was stretched 4.0 times in the width direction at a temperature of 130 ° C., and then heat-treated at 215 ° C. for 5 seconds to give a laminated polyester film having a laminated thickness of 0.1 μm and a thickness of 50 μm. Obtained. As a result of TEM observation of the cross section of the obtained laminated film, the laminated film was phase-separated in the thickness direction, and a mixed phase of these resins was present. The adhesiveness and scratch resistance of the diazo sensitive material coating layer provided on the laminated film side were extremely good, and the adhesiveness did not decrease even under a high temperature and high humidity environment.

Comparative Example 1 0.015% of colloidal silica having an average particle size of 0.4 μm
And PET pellets containing 0.005% of colloidal silica having an average particle size of 1.5 μm (an intrinsic viscosity of 0.6
2dI / g) was sufficiently dried in vacuum, then supplied to an extruder, melt-extruded at 280 ° C., filtered through a 10 μm cut metal sintered filter, and then extruded into a sheet from a T-shaped die, which was heated at 30 ° C. It was wound around the cooling drum of and cooled and solidified. In order to improve the adhesion between the sheet and the cooling drum during this period, a wire electrode is placed on the sheet side to provide 6 KV.
DC voltage was applied. Unstretched PET thus obtained
The film was heated to 95 ° C. and stretched 3.5 times in the longitudinal direction to obtain a uniaxially stretched film. A corona discharge treatment was applied to one surface of this film in an air atmosphere, and a water-based resin layer-forming coating material containing an acrylic copolymer resin alone was prepared on the treated surface and applied by a gravure coating method. The coating thickness was such that the laminated film had a thickness of 0.1 μm after biaxial stretching.

(A) MMA / BA / AA / AN Copolymer Acrylic Emulsion Mixing Ratio 100 parts by weight 65/35/2/5% by weight

The uniaxially stretched film coated with this laminated film coating agent was introduced into a preheating zone heated to 140 ° C. to dry the water, and then continuously gripped by a clip in a heating zone of 130 ° C. in the width direction. Stretched 3.5 times, then heat-treated in a heating zone at 225 ° C. for 5 seconds to obtain a laminated thickness of 0.1 μm.
A laminated polyester film having a thickness of 50 μm was obtained. As a matter of course, this laminated film did not exhibit a phase separation structure.

The evaluation results of this laminated polyester film are shown in Table 1. The adhesiveness and scratch resistance of the diazo sensitive material coating layer provided on the laminated film side were inferior, and the adhesiveness was deteriorated in a high temperature and high humidity environment.

Comparative Example 2 A laminated film having a thickness of 0.1 μm was formed in the same manner as in Example 1 except that the composition of the laminated film was changed as follows.
A μm laminated polyester film was obtained. The evaluation results of this laminated polyester film are shown in Table 1. The scratch resistance was inferior. As a result of TEM observation of the cross section of this laminated film, a phase-separated structure and a mixed phase were not recognized.

(A) MMA / BA / AA / AN Copolymer Acrylic Emulsion Blending Ratio 65 parts by weight 65/35/2/5% by weight

(B) 35 parts by weight of methylolated melamine

Comparative Example 3 A laminated polyester film having a thickness of 50 μm and having a laminated thickness of 0.1 μm was obtained in the same manner as in Example 1 except that the composition was changed as follows. T of this laminated film
As a result of cross-sectional observation by EM, a phase-separated structure and a mixed phase were not recognized. The evaluation results of this laminated polyester film are shown in Table 1. It was inferior in scratch resistance and adhesion in a high temperature and high humidity environment.

(A) MMA / BA / AA / AN Copolymer Acrylic Emulsion Mixing Ratio 99.5 Parts by Weight 65/35/2/5% by Weight

(B) Methylolated melamine 0.5 part by weight

Comparative Example 4 A laminated polyester film having a thickness of 50 μm provided with a laminated film thickness of 0.1 μm was obtained in the same manner as in Example 1 except that the composition was changed as follows. As a result of TEM observation of the cross section of this laminated film, a phase-separated structure and a mixed phase were not recognized. The evaluation results of this laminated polyester film are shown in Table 1. The scratch resistance, the adhesiveness, and the adhesiveness in a high temperature and high humidity environment were poor.

(A) IPA / DEG / NPG Copolyester Blending Ratio 100 parts by weight 50/20/30 mol% Ammonium salt type aqueous dispersion comprising the above acid component and glycol component

Comparative Example 5 The surface of a polyester base film was subjected to corona discharge treatment in an air atmosphere to have a wetting tension of 48 dyn / cm, and the same copolyester resin 50 as used in Example 1 was used. After coating and drying the equivalent amount of 50 parts by weight, 50 parts by weight of the same copolymer acrylic resin as used in Example 1 was applied to the surface of the polyester resin coating film, and the same procedure as in Comparative Example 1 was performed. 50 μm with total laminated film thickness 0.1 μm after drying and heat treatment
m of laminated polyester film was obtained. That is, two-stage coating was performed. As a result of TEM observation of the cross section of the obtained laminated film, the laminated film was phase-separated in the thickness direction, but a mixed phase of these resins was completely present. There wasn't. The evaluation results of this laminated polyester film are shown in Table 1.
However, the scratch resistance, the adhesion, and the adhesion in a high temperature and high humidity environment were inferior.

First-stage coat MMA / BA / AA / AN copolymer acrylic emulsion blending ratio 50 parts by weight 65/35/2/5% by weight

Second-stage coat IPA / DEG / NPG copolymerized polyester 50 parts by weight 50/20/30 mol% Ammonium salt type aqueous dispersion comprising the above acid component and glycol component

Example 7 A laminated polyester film having a laminated thickness of 0.1 μm and a film thickness of 50 μm was obtained in exactly the same manner as in Example 1 except that the methylolated melamine was removed from the coating composition used in Example 1. . As a result of TEM observation of the cross section of the obtained laminated film, although not clear as compared with the case where methylolated melamine was added, the laminated film was phase-separated in the thickness direction and a mixed phase was also present.

The characteristics of the obtained film are shown in Table 1.
Both scratch resistance and adhesion were acceptable levels.

[0089]

[Table 1]

[0090]

INDUSTRIAL APPLICABILITY The present invention is a laminated film in which an easy-adhesion layer made of an acrylic resin and a polyester resin is provided on at least one side of a polyester film, which has excellent adhesion in a high temperature and high humidity environment and is scratch resistant. It has properties and is preferably used for a base film used for a diazo second original film.

Claims (10)

[Claims] 1. A laminated film in which a laminated film consisting essentially of one layer is provided on at least one surface of a polyester film, the laminated film being phase-separated in the thickness direction, and the phase-separated interface is A polyester film for a diazo second original drawing, which has a mixed phase. 2. The polyester film for a diazo second original drawing according to claim 1, wherein the surface layer of the laminated film has an acrylic resin as a main constituent and the lower part has a polyester resin as a main constituent. 3. The laminated thickness ratio of a layer containing an acrylic resin as a main constituent and a layer containing a polyester resin as a main constituent in the laminated film is in the range of 90/10 to 10/90. The polyester film for diazo second original drawing according to claim 1 or 2. 4. A cross-linking agent is contained in the laminated film in an amount of 0.5 to 30% by weight.
The polyester film for a diazo second original drawing according to any one of claims 1 to 3, wherein the polyester film contains the polyester film. 5. The polyester for diazo second original diagram according to any one of claims 1 to 4, wherein the polyester resin in the laminated film is an aqueous polyester resin having no sulfonate group in the molecule. the film. 6. The glass transition temperature of the polyester resin in the laminated film is 20 ° C. or higher and lower than 90 ° C., and the acid value is 20K.
OHmg / g or more, The polyester film for diazo second original drawings in any one of Claims 1-5 characterized by the above-mentioned. 7. The polyester film for diazo second original drawing according to claim 1, wherein the acrylic resin in the laminated film is copolymerized with acrylonitrile. 8. The polyester film for a second diazo original drawing according to claim 1, wherein the laminated film has a thickness of 0.005 to 3 μm. 9. The polyester for the second original drawing of diazo according to claim 1, wherein the polyester film is made of a polymer containing polyethylene terephthalate or polyethylene 2,6 naphthalate as a main constituent. the film. 10. The diazo second according to claim 1, wherein the polyester film comprises a composition containing at least one selected from acrylic resin, polyester resin and melamine. Polyester film for original drawings.