JPH10180968A - Laminated polyester film for diazo - Google Patents

Abstract

(57) Abstract: A laminated film containing an acrylic resin and an oxazoline group-containing crosslinking agent as main components is provided on at least one surface of a polyester film, and in the laminated film, 100 parts by weight of the acrylic resin is used. On the other hand, a laminated polyester film for diazo, comprising an oxazoline group-containing cross-linking agent in an amount of 1 to 30 parts by weight in terms of solid content by weight. The laminated polyester film for diazo prepared according to the present invention can be obtained by using a laminated polyester film provided with a laminated film mainly composed of an acrylic resin and a specific amount of an oxazoline group-containing crosslinking agent. It has excellent adhesive properties under normal conditions, scratch resistance, etc., and also exhibits excellent effects on stability over time and adhesiveness after high-temperature treatment, and as a base film used for diazo films. It is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated polyester film for diazo, and more particularly, it has excellent adhesion to a diazo photosensitive material layer under normal conditions, scratch resistance, and the like, and further has stability over time and adhesion after high-temperature treatment. The present invention relates to a laminated polyester film for diazo having excellent properties.

[0002]

2. Description of the Related Art Biaxially oriented polyester films have excellent properties such as dimensional stability, mechanical properties, heat resistance, transparency, and electrical properties. It is widely used as a base film for many uses such as various photographic materials and graphic arts materials.

[0003] Among them, polyester films are widely used as base films in applications where durability, water resistance, heat resistance, flatness, accuracy, etc. are not satisfactory with paper or the like, for example, in diazo film applications.

[0004] Applications of the diazo film include a second original drawing, tint, proof, and printing. Above all, the diazo film for the second original drawing is mainly used for duplicating design drawings of maps, aircraft, ships, automobiles, etc., which require accuracy and long-term preservation. Also called a screen original screen or a screen for exclusive use of a net, very fine, round, square and other halftone dots are made with a diazo film.For example, the color, color tone, shade of color,
Adjustment of line blur etc. is performed.

[0005] Taking the diazo film for the second original drawing as an example,
The structure is such that a diazo sensitive material layer is laminated on one surface of a polyester film as a base material, and a mat layer colored blue or white is usually laminated on the other surface. In principle, for example, when making a copy of a drawing or the like, a document is superimposed as it is on the light-sensitive material layer side of the diazo film, inserted into a diazo copying machine, and exposed. In the light-sensitive material layer, the diazo compound in the photosensitive portion (corresponding to a blank portion of the document) is decomposed by light to generate a photo-decomposed product, and does not develop color even in the subsequent development. On the other hand, the diazo compound in the non-photosensitive portion (corresponding to the portion where light is shielded by a line or a character) generates an azo dye in a subsequent step of development (using ammonia gas) in the presence of a coupler,
Lines or characters are colored black. The basic principle is the same regardless of the diazo film used for any purpose.

By the way, since the diazo film is used as described above, the base polyester film and the diazo sensitive material layer need to be firmly bonded. Therefore,
In general, various types of easy-adhesion treatments are applied to the surface of the polyester film on the side where the diazo sensitive material layer is provided, and used.

For example, physical treatments such as corona discharge treatment, plasma treatment and ultraviolet irradiation treatment under various gas atmospheres on the polyester film surface, chemical treatments with alkali, trichloroacetic acid, amines, phenols and the like,
Alternatively, a treatment method using these in combination, a method of providing a primer layer, and the like have been performed.

However, the physical or chemical surface treatment method complicates the process, not only increases the cost, but also does not provide sufficient adhesiveness.

On the other hand, the method of providing a primer layer can be carried out in the process of producing a polyester film, is advantageous in terms of cost, and can select and coat an adhesive substance which can cope with various coatings. For this reason, a polyester film laminated with a water-soluble or water-dispersible polyester resin, acrylic resin, urethane resin or the like as an adhesive substance (Japanese Patent Laid-Open No. 55-158).
No. 25, JP-A-58-77861, JP-A-678 / 76
No. 0-248232, JP-A-62-204940, JP-A-1-108037, etc.) have been proposed.

[0010]

However, the above-mentioned prior art has the following problems.

When a water-soluble or water-dispersible polyester resin, an acrylic resin, or a urethane resin is laminated on a polyester film in order to impart adhesiveness to the diazo sensitive material layer, the adhesiveness under normal conditions is reduced. Even if it is obtained, there is a problem such as poor scratch resistance (hereinafter referred to as "scratch resistance") when scratched with a pencil or an ore needle such as diamond or sapphire.

Further, when laminating the above-mentioned resin to which a cross-linking agent such as melamine or epoxy is added, the adhesion and the scratch resistance under a normal condition are greatly improved, and are required in a general use condition. Characteristics.

However, depending on the purpose of use and the user, there is a case where a heat treatment is applied after the diazo photosensitive material is applied, or a storage treatment is performed for several weeks to several months or more, followed by development processing before use. If the adhesiveness of the light-sensitive material layer after development processing after passing through such conditions is poor, the function as a diazo film cannot be sufficiently satisfied.

The present invention solves these drawbacks, and has excellent adhesion to a diazo sensitive material layer under normal conditions, excellent scratch resistance, and excellent stability over time and adhesion after high-temperature treatment. A laminated polyester film is provided.

[0015]

According to the present invention, there is provided a laminated polyester film for diazo according to the present invention, wherein at least one surface of the polyester film is provided with a laminated film mainly composed of an acrylic resin and an oxazoline group-containing crosslinking agent. And in the laminated film, an acrylic resin 10
It is characterized in that the oxazoline-based crosslinking agent is contained in an amount of 1 to 30 parts by weight based on 0 parts by weight based on the solid content.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION In the laminated polyester film for diazo of the present invention, polyester is a generic name of polymers having an ester bond as a main bonding chain of a main chain. Preferred polyesters are ethylene terephthalate and ethylene. At least one component selected from -2,6-naphthalate, butylene terephthalate, ethylene-α, β-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylate as a main component; Can be used. These components may be used alone or in combination of two or more.
It is particularly preferable to use a polyester containing ethylene terephthalate as a main constituent component when comprehensively judging economy and the like. In applications where heat acts on the substrate, for example, for diazo applications, or when the resin is shrunk during curing or drying, such as an ultraviolet curable resin, polyethylene-2,6-naphthalate having excellent heat resistance and rigidity is used. Is more preferred.

Further, these polyesters may further contain some other dicarboxylic acid component or diol component, preferably
0 mol% or less may be copolymerized.

The polyester further contains various additives such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, Antistatic agents, nucleating agents and the like may be added to such an extent that their properties are not deteriorated.

The intrinsic viscosity of the above-mentioned polyester (25 ° C.)
Measured in o-chlorophenol) is 0.4-1.2.
dl / g is preferable, and more preferably 0.5 to 0.8 d
Those in the range of 1 / g are suitable for practicing the present invention.

The polyester film using the above polyester is preferably biaxially oriented when the laminated film is provided. The biaxially oriented polyester film generally means an unstretched polyester sheet or film in the longitudinal direction and the width direction.
It is stretched about 5 to 5 times, and then heat-treated to complete crystal orientation, and indicates a biaxially oriented pattern by wide-angle X-ray diffraction. The biaxial stretching may be longitudinal or transverse sequential stretching or biaxial simultaneous stretching. Also,
After stretching in the longitudinal and transverse directions, the film may be further stretched in any of the longitudinal and transverse directions.

The thickness of the polyester film is not particularly limited and may be appropriately selected depending on the intended purpose.
0 μm, preferably 10 to 200 μm. Further, the obtained films can be used by being bonded by various methods.

In the laminated polyester film for diazo according to the present invention, the acrylic resin used as a constituent component of the laminated film may be one containing acrylonitrile as a monomer component constituting the acrylic resin in terms of adhesiveness and scratch resistance. preferable.

The amount of acrylonitrile to be copolymerized is not particularly limited, but from the viewpoints of adhesion and scratch resistance, it is not limited to 0.1.
It is preferably from 5 to 20% by weight, more preferably from 1 to 15% by weight, most preferably from 3 to 10% by weight. If it is less than 0.5% by weight, the improvement effect is small, and if it is less than 20% by weight.
On the other hand, when the ratio exceeds 2, the adhesiveness under normal conditions and the scratch resistance tend to decrease.

The monomer components other than acrylonitrile constituting the acrylic resin include, for example, alkyl acrylate and alkyl methacrylate (the alkyl group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group). , T-butyl group, 2-
Hydroxy such as ethylhexyl, lauryl, stearyl, cyclohexyl, phenyl, benzyl, and phenylethyl), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. Group-containing monomer, acrylamide,
Methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-phenylacrylamide Amide group-containing monomers such as N,
Amino group-containing monomers such as N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; acrylic acid, methacrylic acid and salts thereof (lithium salt, sodium salt, potassium salt) And the like, and a monomer containing a carboxyl group or a salt thereof, and the like, and these are copolymerized using one or two or more kinds. Furthermore,
These can be used in combination with other types of monomers described below.

Examples of other types of monomers include epoxy group-containing monomers such as allyl glycidyl ether and sulfones such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (lithium salt, sodium salt, potassium salt, ammonium salt, etc.). Monomers containing acid groups or salts thereof, crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (lithium salts, sodium salts,
Monomers containing a carboxyl group or a salt thereof, such as potassium salts and ammonium salts), maleic anhydride,
Monomers containing acid anhydrides such as itaconic anhydride, vinyl isocyanate, allyl isocyanate, styrene, vinyl methyl ether, vinyl ethyl ether, vinyl trisalkoxysilane, alkyl maleic acid monoester, alkyl fumaric acid monoester, methacrylonitrile, Alkyl itaconic acid monoester, vinylidene chloride, vinyl acetate, vinyl chloride and the like can be used.

As the acrylic resin that can be used in the present invention, a modified acrylic copolymer, for example, a block copolymer or a graft copolymer modified with polyester, urethane, epoxy or the like is also possible.

The glass transition point (hereinafter referred to as “Tg”) of the acrylic resin used in the present invention is not particularly limited, but is preferably 10 to 50 ° C., more preferably 20 to 40 ° C. When an acrylic resin having a low Tg is used, the adhesiveness after high-temperature treatment tends to be poor,
Conversely, if it is too high, a crack may occur during stretching,
Adhesion and scratch resistance tend to be poor. The molecular weight of the acrylic resin is preferably 100,000 or more, and more preferably 300,000 or more, from the viewpoint of adhesiveness.

Preferred acrylic resins used in the present invention include acrylonitrile, methyl methacrylate, ethyl acrylate, n-butyl acrylate,
2-hydroxyethyl acrylate, acrylamide,
And copolymers selected from N-methylolacrylamide, glycidyl methacrylate, acrylic acid, and the like.

In producing the laminated polyester film for diazo of the present invention, an aqueous laminated film forming coating solution is applied to the polyester film before the completion of the crystal orientation, and is stretched in at least one direction and heat-treated. However, the method is capable of heat treatment at high temperature,
It is particularly preferable because the crosslink density can be improved and a more uniform and thin laminated film can be obtained. In the case of forming a laminated film by the above method, an acrylic resin which is soluble, emulsified, or suspended in water is preferable in terms of environmental pollution and explosion-proof properties. Such an aqueous acrylic resin may be copolymerized with a monomer having a hydrophilic group (such as acrylic acid, methacrylic acid, acrylamide, vinyl sulfonic acid, or a salt thereof), emulsion-polymerized using a reactive emulsifier or a surfactant, and suspended. It can be prepared by a method such as turbid polymerization or soap-free polymerization.

In the laminated film according to the present invention, by applying an oxazoline group-containing cross-linking agent to the above-mentioned acrylic resin, heat treatment can be carried out after application of the diazo photosensitive material layer, in addition to adhesion and scratch resistance under normal conditions. Adhesiveness after application (hereinafter referred to as “adhesion after high-temperature treatment”), or adhesiveness when developed after storage for several weeks to several months or more (hereinafter “adhesion after heat treatment”). (Referred to as “aging stability”).

The oxazoline group-containing crosslinking agent used in the present invention is not particularly limited as long as it has an oxazoline group as a functional group. Those comprising a copolymer are preferred.

Examples of the oxazoline group-containing crosslinking agent include those described in JP-A-2-60941 and JP-A-2-9953.
7, JP-A-2-115238, JP-B-63
A copolymer described in, for example, -48884 or a derivative thereof can be used.

Specifically, the following general formula

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently hydrogen, halogen, alkyl, aralkyl, phenyl or substituted phenyl group, and R ₅ is a noncyclic organic group having an addition-polymerizable unsaturated bond. Can be used. A copolymer obtained by copolymerizing the addition-polymerizable oxazoline represented by the formula (1) and at least one other monomer can be used.

Examples of the addition-polymerizable oxazoline include 2-vinyl-2-oxazoline and 2-vinyl-4-methyl-2.
-Oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-
Isopropenyl-4-methyl-2-oxazoline, 2-
Isopropenyl-5-ethyl-2-oxazoline and the like can be used, and one or a mixture of two or more thereof can also be used. Among them, 2-isopropenyl-2-oxazoline is preferable because it is easily available industrially.

In the oxazoline group-containing crosslinking agent, the at least one other monomer used for the addition-polymerizable oxazoline is not particularly limited as long as it is a monomer copolymerizable with the addition-polymerizable oxazoline. Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate,
Acrylic acid esters such as methacrylic acid-2-ethylhexyl or methacrylic acid esters, acrylic acid,
Unsaturated carboxylic acids such as methacrylic acid, itaconic acid and maleic acid, unsaturated nitriles such as acrylonitrile and methacrylonitrile, unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide and N-methylolmethacrylamide, acetic acid vinyl,
Vinyl esters such as vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; olefins such as ethylene and propylene; halogen-containing α-, β-unsaturated monomers such as vinyl chloride, vinylidene chloride and vinyl fluoride; Α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene can be used, and one or a mixture of two or more thereof can also be used.

In the present invention, acrylonitrile is also used as a copolymerizable monomer of the oxazoline group-containing crosslinking agent.
Preferably from 0.5 to 10 parts by weight, more preferably from 1 to 5 parts by weight.
Those obtained by copolymerization by weight are preferred in terms of affinity with the acrylic resin used, a crosslinking effect, and adhesiveness with the diazo sensitive material layer.

In order to obtain an oxazoline group-containing crosslinking agent using addition-polymerizable oxazoline and at least one other monomer, polymerization may be carried out by an emulsion polymerization method, a solution polymerization method or the like.

For example, in the emulsion polymerization method, a polymerization catalyst, water,
Various methods such as a method in which a surfactant and a monomer are mixed at a time and polymerization, or a monomer dropping method, a multi-stage polymerization method, a pre-emulsion method and the like can be used. Polymerization catalysts include, for example, benzoyl peroxide, t-butyl hydroperoxide, azobisisobutyronitrile, hydrogen peroxide, potassium persulfate, ammonium persulfate, 2,2 ′
-A radical polymerization initiator such as azobis (2-amidinopropane) dihydrochloride can be used. As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a reactive surfactant, or the like can be used. The polymerization temperature is usually 0 to 100 ° C, preferably 50 to 80 ° C, and the polymerization time is usually 1 to 10 ° C.
Time.

In the solution polymerization method, usable solvents include toluene, hexane, methyl ethyl ketone, ethyl cellosolve, methyl cellosolve, ethyl acetate, isopropyl alcohol, propylene glycol monomethyl ether, and the like. Can also be used. Examples of the polymerization initiator used include azobisisobutyronitrile and benzoyl peroxide. The polymerization temperature is from 20 to 200C, preferably from 40 to 120C.

In obtaining an oxazoline group-containing cross-linking agent using an addition-polymerizable oxazoline and another monomer,
The amount of addition-polymerizable oxazoline used is 0.5
There is no particular limitation as long as it is in the range of ８０80% by weight or more. If the amount of the addition-polymerizable oxazoline is less than 0.5% by weight, the crosslinking effect due to the oxazoline group is small, and the adhesiveness tends to be poor. If it exceeds 80% by weight, the affinity with other resins used in combination and the crosslinking agent It tends to be poor in its own polymerizability.

The oxazoline group-containing cross-linking agent thus obtained is obtained, for example, in the form of an aqueous dispersion by an emulsion polymerization method and in the form of an organic solvent liquid by a solution polymerization method. It can be used as a coating liquid for forming a laminated film. In addition, a solution obtained by a solution polymerization method can also be used as a pseudo-aqueous coating liquid by a method such as addition of water as long as it is an aqueous organic solvent. In particular, when the resin obtained in this manner is used in a mixture with another resin, for example, an aqueous resin, the acrylic resin used in the present invention is better than the aqueous dispersion obtained by the emulsion polymerization method. Is preferred because the affinity of the compound becomes higher and the crosslinking effect becomes remarkably higher.

In the laminated film according to the present invention, the oxazoline group-containing crosslinking agent is added to 100 parts by weight of the acrylic resin in terms of adhesion under normal conditions, scratch resistance, stability over time, and adhesion after high-temperature treatment. Must be contained in an amount of 1 to 30 parts by weight, preferably 2 to 25 parts by weight,
More preferably, it is 5 to 20 parts by weight. When the amount of the oxazoline group-containing crosslinking agent is less than 1 part by weight or more than 30 parts by weight, the stability over time and the adhesiveness after high-temperature heat treatment are inferior.

The laminated film according to the present invention comprises the above-mentioned acrylic resin and the oxazoline group-containing crosslinking agent as main constituents. The main constituents in the present invention are as follows. It means that it occupies more than%. In particular, in the present invention, the ratio of the two components is preferably 80% by weight or more, more preferably 90% by weight or more.

In the laminated film, other resins such as an acrylic resin other than the above-mentioned acrylic resin, a polyester resin, a urethane resin, a polyolefin resin, and the like, as long as the effects of the present invention are not impaired. A polycarbonate resin, an epoxy resin, a silicone resin, a urea resin, a phenol resin, a vinyl chloride resin, a fluorine resin, a rubber resin, or the like may be blended.

Further, various additives such as a crosslinking agent other than the oxazoline group-containing crosslinking agent used in the present invention, an antioxidant,
Heat stabilizers, weather stabilizers, ultraviolet absorbers, organic lubricants, pigments, dyes, organic or inorganic fine particles, fillers, antistatic agents, nucleating agents, and the like may be added.

In particular, those obtained by adding inorganic particles to the laminated film are more preferable because the lubricity and blocking resistance are improved.

In this case, as the inorganic particles to be added, silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, calcium carbonate and the like can be used. The inorganic particles used have an average particle size of 0.0
1-5 μm is preferable, and more preferably 0.05-3 μm
m, most preferably 0.08 to 2 μm, and the mixing ratio with respect to the resin in the laminated film is not particularly limited, but is preferably 0.05 to 8 parts by weight, more preferably 0.1 to 3 parts by weight in terms of solid content weight ratio. Parts by weight.

The use of a cross-linking agent other than the oxazoline group-containing cross-linking agent used in the present invention is preferred because the adhesion and the scratch resistance under normal conditions are further improved. The crosslinking agent used is not particularly limited, but may be any one capable of performing a crosslinking reaction with a functional group present in the acrylic resin used in the present invention, for example, a hydroxyl group, a carboxyl group, an amide group, and the like. Examples include methylolated or alkylolated urea-based, melamine-based, acrylamide-based, polyamide-based resins, epoxy compounds, isocyanate compounds, aziridine compounds, various silane coupling agents, various titanate coupling agents, and the like. Among them, it is most preferable to add a melamine-based crosslinking agent.

The thickness of the laminated film is not particularly limited, but is usually preferably in the range of 0.01 to 5 μm, more preferably 0.02 to 2 μm, and most preferably 0.05 μm to 0.2 μm.
5 μm. If the thickness of the laminated film is too small, poor adhesion may occur.

Various coating methods such as a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a die coating method, a spray coating method and the like can be used as a method of coating on the substrate film.

In the present invention, before applying the coating liquid for forming a laminated film, the surface of the base film is subjected to a corona discharge treatment or the like so that the surface has a wetting tension of preferably 47 mN / m or more, more preferably 50 mN / m or more. / M or more can be preferably used because the adhesion of the laminated film to the base film can be improved.

Next, the method for producing the laminated polyester film for diazo of the present invention will be described with reference to polyethylene terephthalate (hereinafter referred to as “PET”) as a base film, but the present invention is not limited thereto. .

The laminated polyester film for diazo according to the present invention, which is excellent in adhesiveness under normal conditions and scratch resistance as well as excellent in stability over time and adhesiveness after high-temperature treatment, has at least one surface of a polyester film. It can be manufactured by providing a laminated film composed of an acrylic resin and an oxazoline group-containing crosslinking agent.

More specifically, the intrinsic viscosity is 0.5 to 0.8.
dl / g PET pellets are sufficiently dried in a vacuum, fed to an extruder, extruded in a sheet at 260 to 300 ° C., and cast at a surface temperature of 10 using an electrostatic application casting method.
It is wound around a mirror casting drum at 〜60 ° C. and solidified by cooling to prepare an unstretched PET sheet. This unstretched film is stretched 2.5 to 5 times in the longitudinal direction (the direction of film movement) with a roll heated to 70 to 120 ° C. to obtain a uniaxially stretched PET film. At least one surface of the film is subjected to a corona discharge treatment, and the wettability of the surface is reduced to 4%.
7 mN / m or more, and a coating liquid for forming a laminated film having a predetermined concentration is applied to the treated surface. After coating, the film edge is gripped with a clip and guided to a hot air zone heated to 70 to 150 ° C., dried, and then stretched 2.5 to 5 times in the width direction. Subsequently, it is led to a heat treatment zone of 160 to 250 ° C,
A heat treatment is performed for 1 to 30 seconds to complete the crystal orientation.
During this heat treatment step, a relaxation treatment of 1 to 12% may be performed in the width direction or the longitudinal direction as necessary. The biaxial stretching may be any of longitudinal and transverse sequential stretching or simultaneous biaxial stretching, and after longitudinal and transverse stretching, may be re-stretched in either the longitudinal or transverse direction or in both directions. Further, the thickness of the polyester film is not particularly limited, but 2 to 50
0 μm is preferably used. In this case, the coating solution to be used is preferably an aqueous solution in view of environmental pollution and explosion-proof properties.

In the above example, the base film on which the laminated film is provided may contain at least one selected from an acrylic resin, an oxazoline group-containing crosslinking agent, and a reaction product thereof. In this case, there are effects that the adhesiveness between the laminated film and the base film is improved, and the lubricity of the laminated polyester film is improved.
When an acrylic resin, an oxazoline group-containing cross-linking agent, and a reaction product thereof are contained, the total amount of the additives is preferably 5 ppm or more and less than 20% by weight in terms of easy adhesion and smoothness. . Of course, acrylic resin,
The oxazoline group-containing crosslinking agent and the reaction product thereof may be a coating composition (including regenerated pellets of the laminated polyester film for diazo of the present invention) provided on the base film.

[0056]

[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) Thickness of Coating Layer Using a transmission electron microscope HU-12 manufactured by Hitachi, Ltd., the thickness was determined from a photograph obtained by observing a cross section of a biaxially oriented polyester film provided with a laminated film. Thickness is 30 within the field of view
The average value was used.

(2) Adhesiveness The following diazo sensitive material paint was applied using a bar coater on the laminated film surface of the laminated polyester film for diazo of the present invention so as to have a thickness of 6 μm after drying. 2
After drying for a minute, a diazo sensitive material layer was provided. Since the diazo film coated with the diazo sensitive material layer is photosensitive, it is stored in a state where light is blocked.

This is called a dry diazo copier “RICOP”
Developed with Y "SM2300F (manufactured by Ricoh Co., Ltd.), put 100 cross-cuts of 1 mm ^{2 in} the unexposed area (colored area), adhered cellophane tape (manufactured by Nichiban Co., Ltd.), and Was reciprocated three times under a load of 19.6 N, pressed, and then peeled in the 90-degree direction, and evaluated on a four-point scale based on the number of remaining diazo photosensitive material layers (A: 100,
○: 80 to 99, Δ: 50 to 79, ×: 0 to 49). In addition, (◎) and (）) were evaluated as having good adhesiveness.

"Diazo Sensitive Material Coating" Resin content:-Cellulose acetate butyrate resin 60% by weight-Acrylic resin (acrylic copolymer of ethyl methacrylate / methyl methacrylate / acrylic acid at a solid content weight ratio of 85/10/5) Resin) 40% by weight Solvent component: ・ Ethylene glycol monomethyl ether 70% by weight ・ Toluene 20% by weight ・ Isopropyl alcohol 10% by weight A mixture of the above resin component and the solvent component in a weight ratio of 25/75 is used as a binder. The diazonium salt was added as a solid content weight ratio of 7 parts by weight to 100 parts by weight of the binder, and used as a diazo sensitive material paint.

(3) Scratch resistance The diazo film provided with the diazo photosensitive material layer prepared in the above (2) was dried with a dry diazo copier "RICOPY" SM230.
The image was developed with 0F (manufactured by Ricoh Co., Ltd.). The unexposed area (colored area) is applied to a surface property measuring device “HEIDO” manufactured by Shinto Kagaku Co., Ltd.
Using a N ″ -14DR, a sapphire needle with a tip of 0.1 mmφ was applied at a right angle, and the sample moving speed was 100 mm.
/ Min, the load applied to the sapphire needle was changed, and the load at which the unexposed portion (colored portion) surface of the developed diazo film began to be damaged was used as an index of scratch resistance. Note that 12
0 g or more has good scratch resistance, and 80 g
This is a practically usable level.

(4) Stability over time The diazo film provided with the diazo photosensitive material layer prepared in the above (2) is stored under normal conditions (23 ° C., 65% RH) for one month. RICOPY ”SM23
Developed with 00F (manufactured by Ricoh Co., Ltd.). The developed diazo film was evaluated in the same manner as in (2) and (3) above.

(5) Adhesion after high-temperature treatment The diazo film provided with the diazo photosensitive material layer prepared in the above (2) was heat-treated in a hot-air oven at 125 ° C. for 5 minutes to obtain a dry diazo copier “RICOPY”. "SM230
The image was developed with 0F (manufactured by Ricoh Co., Ltd.). The developed diazo film was evaluated in the same manner as in (2) and (3) above.

(6) Glass transition point (Tg) “Robot” DSC (differential scanning calorimeter) RDC220 manufactured by Seiko Denshi Kogyo Co., Ltd.
The measurement was performed with an SC5200 disk station connected. The measurement conditions of DSC are as follows. That is, sample 1
After adjusting 0 mg to an aluminum pan, it is set in a DSC device (reference: an aluminum pan of the same type without a sample), heated at a temperature of 300 ° C. for 5 minutes, and then quenched in liquid nitrogen. This sample is
The temperature is raised at 0 ° C./min, and the glass transition point (Tg) is detected from the DSC chart.

[0065]

Next, the present invention will be described with reference to examples, but is not necessarily limited thereto.

Example 1 PET pellets containing 0.015% by weight of colloidal silica having an average particle diameter of 0.4 μm and 0.005% by weight of colloidal silica having an average particle diameter of 1.5 μm (intrinsic viscosity: 0.62 dl / g) ) Is sufficiently dried in a vacuum, fed to an extruder, melted at 280 ° C., filtered through a 10 μm-cut metal sintering filter, extruded into a sheet shape from a T-shaped die, and subjected to an electrostatic application casting method. Surface temperature 25 ° C
And then cooled and solidified. This unstretched sheet was heated to 95 ° C. and stretched 3.2 times in the longitudinal direction to obtain a uniaxially stretched film. One surface of this film was subjected to corona discharge treatment in air, the wet tension of the substrate film was set to 52 mN / m, and the following coating solution for forming a laminated film was applied to the treated surface by a bar coating method. The thickness of the laminated film was set to 0.1 μm after the completion of the crystal orientation.

[Laminated Film Forming Coating Solution] Acrylic resin: methyl methacrylate 65% by weight butyl acrylate 28% by weight acrylonitrile 5% by weight acrylic acid 2% by weight Acrylic resin copolymer emulsion copolymerized with the above composition (Tg: 35 ° C.) )

Oxazoline group-containing cross-linking agent: methyl methacrylate 60% by weight butyl acrylate 20% by weight styrene 5% by weight 2-isopropenyl-2-oxazoline 15% by weight Water of the oxazoline group-containing resin composition copolymerized with the above composition / Propylene glycol monomethyl ether mixed solution

A coating liquid for forming a laminated film was prepared by adding 3 parts by weight of an oxazoline group-containing crosslinking agent to 100 parts by weight of the above acrylic resin.

The coated uniaxially stretched film was guided to a preheating zone while being gripped with clips, dried at an ambient temperature of 110 ° C., and then continuously stretched 3.4 times in the width direction in a 125 ° C. heating zone. Furthermore, heat treatment is performed in a heating zone at 230 ° C., and the laminated PET for diazo is completed in the crystal orientation.
A film was obtained. At this time, the thickness of the base PET film was 50 μm. The results are shown in Table 1.

Example 2 Example 1 was repeated except that the amount of the oxazoline group-containing crosslinking agent used was 10 parts by weight in the coating liquid for forming a laminated film of Example 1.
In the same manner as in the above, a laminated PET film for diazo was obtained. The results are shown in Table 1.

Example 3 The same procedure as in Example 2 was carried out except that the thickness of the laminated film was set to 0.3 μm.
An ET film was obtained. The results are shown in Table 1.

Example 4 Example 1 was repeated except that the amount of the oxazoline group-containing crosslinking agent was 25 parts by weight in the coating liquid for forming a laminated film of Example 1.
In the same manner as in the above, a laminated PET film for diazo was obtained. The results are shown in Table 1.

Comparative Example 1 A laminated PET film for diazo was obtained in the same manner as in Example 1 except that the coating liquid for forming a laminated film of Example 1 was used without adding an oxazoline group-containing crosslinking agent. The results are shown in Table 1.

Comparative Example 2 A laminated PET film for diazo was prepared in the same manner as in Example 1 except that the amount of the oxazoline group-containing crosslinking agent was 0.5 part by weight in the coating liquid for forming a laminated film of Example 1. Obtained. The results are shown in Table 1.

Comparative Example 3 The procedure of Example 1 was repeated except that the amount of the oxazoline group-containing crosslinking agent used was 35 parts by weight in the coating liquid for forming a laminated film of Example 1.
In the same manner as in the above, a laminated PET film for diazo was obtained. The results are shown in Table 1.

Example 5 A laminated PET film for diazo was prepared in the same manner as in Example 1 except that the acrylic resin shown in Example 1 was replaced with the following acrylic resin, and the amount of the oxazoline group-containing crosslinking agent was changed to 5 parts by weight. I got The results are shown in Table 1.

Acrylic resin: methyl methacrylate 70% by weight butyl acrylate 28% by weight acrylic acid 2% by weight Acrylic resin copolymer emulsion copolymerized with the above composition (Tg: 38 ° C.)

Example 6 A laminated PET for diazo was prepared in the same manner as in Example 5 except that the acrylic resin shown in Example 5 was replaced with the following acrylic resin.
A film was obtained. The results are shown in Table 1.

Acrylic resin: methyl methacrylate 50% by weight butyl acrylate 28% by weight acrylonitrile 20% by weight acrylic acid 2% by weight Acrylic resin copolymer emulsion copolymerized with the above composition (Tg: 25 ° C.)

Example 7 A laminated PET for diazo was prepared in the same manner as in Example 1 except that the acrylic resin of Example 1 was replaced with the following acrylic resin, and the amount of the oxazoline group-containing crosslinking agent was changed to 10 parts by weight.
A film was obtained. The results are shown in Table 1.

Acrylic resin: methyl methacrylate 60% by weight ethyl acrylate 35% by weight acrylonitrile 2% by weight acrylic acid 3% by weight Acrylic resin copolymer emulsion copolymerized with the above composition (Tg: 43 ° C.)

Example 8 A laminated PET for diazo was prepared in the same manner as in Example 1 except that the acrylic resin of Example 1 was replaced with the following acrylic resin, and the amount of the oxazoline group-containing crosslinking agent was changed to 10 parts by weight.
A film was obtained. The results are shown in Table 1.

Acrylic resin: methyl methacrylate 45% by weight butyl acrylate 48% by weight acrylonitrile 5% by weight acrylic acid 2% by weight Acrylic resin copolymer emulsion copolymerized with the above composition (Tg: 5 ° C.)

Comparative Example 4 The laminated PE for diazo was prepared in the same manner as in Example 1 except that the acrylic resin of Example 1 was replaced with the polyester resin shown below, and the amount of the oxazoline group-containing crosslinking agent was changed to 5 parts by weight.
A T film was obtained. The results are shown in Table 2.

Polyester resin: Acid component 56 mol% of terephthalic acid 18 mol% of isophthalic acid 20 mol% of trimellitic acid 6 mol% of diol component Ethylene glycol 30 mol% Neopentyl glycol 36 mol% 1,4-butanediol 34 Mol% Ammonium salt type aqueous dispersion of polyester resin (Tg: 20 ° C.) comprising the above acid component and diol component

Example 9 A laminated PE for diazo was prepared in the same manner as in Example 1 except that the oxazoline group-containing crosslinking agent of Example 1 was replaced with the following oxazoline group-containing crosslinking agent, and the amount added was 10 parts by weight.
A T film was obtained. The results are shown in Table 2.

Oxazoline group-containing crosslinking agent: styrene 60% by weight butyl acrylate 30% by weight 2-isopropenyl-2-oxazoline 10% by weight Water / propylene glycol monomethyl ether mixture of oxazoline group-containing resin composition copolymerized with the above composition solution

Comparative Example 5 An oxazoline group-containing crosslinking agent of Example 1 was replaced with a methylolated melamine crosslinking agent (“Symel” 350 manufactured by Mitsui Cyanamid Co., Ltd.), and the added amount was changed to 10 parts by weight. In the same manner as in Example 1, a laminated PET film for diazo was obtained. The results are shown in Table 2.

Example 10 In the coating liquid for forming a laminated film of Example 2, a methylolated melamine crosslinking agent (“Nikalac” manufactured by Sanwa Chemical Co., Ltd.) was added.
MW-12LF) was used in the same manner as in Example 2 except that 2 parts by weight of MW-12LF) was used to obtain a laminated PET film for diazo. The results are shown in Table 2.

Example 11 In Example 2, the polyester film was changed from polyethylene terephthalate film to polyethylene-2,6-
Except that the film was changed to a naphthalate (hereinafter abbreviated as “PEN”) film, the laminate P for diazo was used in the same manner as in Example 2.
An EN film was obtained. The results are shown in Table 2.

Example 12 The same as Example 1 except that the laminated PET film obtained in Example 1 was pulverized and pelletized, and 15% by weight was added to polyethylene terephthalate and melt-extruded as a base film. To obtain a hard coat film. The results are shown in Table 2.

[0093]

[Table 1]

[Table 2]

[0094]

As described above, the laminated polyester film for diazo of the present invention is formed by using a laminated polyester film provided with a laminated film mainly composed of an acrylic resin and a specific amount of an oxazoline group-containing crosslinking agent. Excellent adhesion under normal conditions, scratch resistance, etc.
It exhibits excellent effects on stability over time and adhesiveness after high-temperature treatment, and is preferably used as a base film used for a diazo film.

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Claims (7)

[Claims] 1. A laminated film mainly comprising an acrylic resin and an oxazoline group-containing crosslinking agent is provided on at least one surface of a polyester film, and the laminated film has an oxazoline group-containing compound based on 100 parts by weight of the acrylic resin. A laminated polyester film for diazo, characterized in that a cross-linking agent is contained in an amount of 1 to 30 parts by weight in terms of solid content by weight. 2. The laminated polyester film for diazo according to claim 1, wherein the acrylic resin in the laminated film contains acrylonitrile. 3. The laminated polyester film for diazo according to claim 1, wherein the glass transition point of the acrylic resin in the laminated film is 10 to 50 ° C. 4. The laminated polyester film for diazo according to claim 1, wherein acrylonitrile is contained in the acrylic resin in the laminated film in an amount of 0.5 to 20% by weight. 5. The polyester film is a polyethylene terephthalate film or polyethylene-2,6-
2. The film according to claim 1, wherein the film is a naphthalate film.
The laminated polyester film for diazo according to any one of claims 4 to 4. 6. A polyester film comprising a composition containing a total of 5 ppm or more and less than 20% by weight of at least one of an acrylic resin, an oxazoline group-containing crosslinking agent, and a reaction product thereof. The laminated polyester film for diazo according to any one of claims 1 to 5. 7. When providing a laminated film, a coating liquid for forming a laminated film containing an acrylic resin and an oxazoline group-containing crosslinking agent as main components is applied to at least one surface of the polyester film before the completion of the crystal orientation, and then applied in at least one direction. And stretching and heat-treating the sheet.
The laminated polyester film for diazo according to any one of the above.