JPS63113532A - Diazo film and its production - Google Patents

Abstract

PURPOSE:To improve the adhesiveness of a diazo photosensitive layer and polyester film by providing a primer layer essentially consisting of an aq. vinylidene chloride resin on one face of the polyester film and further providing the diazo photosensitive layer thereon. CONSTITUTION:An aq. primer liquid essentially consisting of the aq. vinylidene chloride resin is coated on at least one face of the polyester film before completion of crystal orientation, then the film is subjected to drying, stretching and heat treatment, by which the primer coated biaxially stretched polyester film completed with the crystal orientation of the polyester is formed. The diazo photosensitive layer is further provided on the primer layer of such film. The polyester is the linear satd. polyester synthesized of an arom. dibasic acid or the ester formable deriv. thereof and diol or the ester formable deriv. Thereof. The aq. vinylidene chloride resin in a resin which can be dissolved or uniformly dispersed into a water medium and is a copolymer of a vinylidene chloride monomer and a monomer which can be copolymerized therewith. The vinylidene chloride monomer component is preferably incorporated into the copolymer at >=80mol%.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a diazo film and a method for producing the same, and more particularly to a diazo film in which a highly durable diazo photosensitive layer is provided on a polyester film, and a method for producing the same. .

<Prior Art> It is known to melt-extrude thermoplastic polyesters, such as polyethylene terephthalate or its copolymers, polyethylene naphthalate or its copolymers, or blends of these with small proportions of other resins, to form films. be. It is also known that the resulting biaxially stretched and heat-set polyester film has better heat resistance, gas barrier properties, electrical properties, and chemical resistance than films made of other resins. However, since the surface is highly crystal oriented, the surface cohesiveness is high, such as paints, etc.
Poor adhesion of adhesives, inks, etc.

Therefore, physical treatment (
(e.g. corona treatment, ultraviolet treatment, plasma treatment, etc.), E
B treatment, flame treatment, or chemical treatment (for example, treatment with alkali, aqueous amine solution, trichloroacetic acid, phenols, or other chemicals) are known. However, these methods have practical disadvantages such as deterioration of adhesive strength over time and contamination of the working environment due to volatilization of chemicals.

Another known method is to provide a primer layer by applying an easily adhesive coating agent to the surface of the film in a process other than step 21 for ordinary polyester films. However, with this method, organic solvents are usually used as coating solvents, and the coating atmosphere is not sufficiently clean, resulting in frequent surface defects of processed products due to dust adhesion, or environmental deterioration due to the solvent. safety.

There are hygiene issues.

Therefore, if this primer treatment is performed during the polyester film forming process using a water-based coating agent, the film will be film-forming in a clean environment without dust adhesion, and since it is a water-based solvent, there will be no risk of explosion or environmental deterioration. It is advantageous in terms of performance, economy, and safety.

Because of these advantages, it has been proposed to use water-soluble or water-dispersible polyester resins or acrylic resins as primers (Japanese Patent Laid-Open No. 54-4301).
No. 7, Special Publication No. 1977-10243, Japanese Patent Publication No. 1977-197
No. 86, JP-A-52-19787, etc.). However, the above-mentioned resin has a drawback that it has poor adhesion to the diazo photosensitive layer, and part of the photosensitive layer peels off during long-term storage.

<Object of the Invention> The object of the present invention is to improve the adhesion between the diazo photosensitive layer and the polyester film by providing an aqueous vinylidene chloride primer layer on the polyester film, and to provide a diazo film with long-term storage stability, and its preferable The purpose is to provide a manufacturing method.

<Structure/Effects of the Invention> According to the invention, the objects of the present invention are as follows: (1) A primer layer mainly composed of an aqueous vinylidene chloride resin is provided on at least one side of a polyester film, and a diazo-sensitized layer is further applied on this primer layer. An aqueous primer solution containing an aqueous vinylidene chloride resin as a main component is applied to at least one side of the diazo film formed by providing the layer and the ('2J) polyester film before crystal orientation is completed, and then dried.
This is achieved by a method for producing a diazo film, which is characterized by forming a primer-coated biaxially oriented polyester film that has been subjected to stretching and heat treatment to complete the crystal orientation of the polyester, and further providing a diazo photosensitive layer on the primer layer of this film. Ru.

In the present invention, the polyester constituting the polyester film is a linear saturated polyester synthesized from an aromatic dibasic acid or its ester-forming derivative and a diol or its ester-forming derivative. Specific examples of such polyesters include polyethylene terephthalate,
Polyethylene isophthalate, polybutylene terephthalate.

Examples include poly(1,4-cyclohexylene dimethylene terephthalate) and polyethylene-2,6-naphthalene dicarboxylate, and also include copolymers thereof or blends of these with small proportions of other resins.

The polyester film of the present invention is obtained by melt-extruding such a linear saturated polyester resin, forming it into a film by a conventional method, and subjecting it to orientation crystallization and heat treatment crystallization. This polyester film is crystal oriented to such an extent that the heat of crystal fusion measured by a differential scanning thermal omega meter in a nitrogen stream [at a heating rate of 10°C/min] is usually 4 cal/g or more. is preferred.

In the present invention, a polyester film before crystal orientation is completed means an unstretched film obtained by thermally melting the polymer and forming it into a film as it is; A uniaxially stretched film that is oriented in either one of the following directions; Furthermore, a film that is oriented by stretching at a low magnification in both the vertical and horizontal directions (finally re-stretched in the vertical or horizontal direction to complete oriented crystallization) (biaxially stretched film before stretching), etc.

In the present invention, the aqueous vinylidene chloride resin is one that can be dissolved or uniformly dispersed in an aqueous medium, and in this case, a small amount of an organic solvent may be used. This solubility or dispersibility can be judged by whether or not a stable aqueous primer coating solution can be prepared.

The aqueous vinylidene chloride resin is a copolymer of nylidene chloride monomer and a heptamer copolymerizable with this monomer. The vinylidene chloride monomer component is preferably at least 50 mol%, more preferably at least 80 mol%, particularly from 80 to 95 mol%. Examples of copolymerizable monomers include vinyl chloride, ethylene, propylene, vinyl acetate, fumaric acid, itaconic acid and esters thereof, acrylonitrile, butadiene, acrylic monomers [for example, (meth)
Acrylic acid, (meth)acrylamide, hydroxyalkyl (meth)acrylate (e.g. 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, etc.), alkyl (meth)acrylate (For example, metal (meth)acrylate, ethyl (meth)acrylate, etc.). Among these, monomers having a hydrophilic group are preferred, and acrylic monomers are particularly preferred.

In order to impart hydrophilicity to vinylidene chloride resin, it is recommended to introduce functional groups such as hydroxyl groups, amide groups, carboxyl groups, or their salts (e.g., sodium salts, potassium salts, ammonium salts, tertiary amine salts, etc.). preferable.

The aqueous vinylidene chloride resin can be produced by a known method such as emulsion polymerization, and can be easily obtained commercially as an aqueous solution or dispersion.

In the present invention, the aqueous primer liquid is a coating liquid containing the above-mentioned aqueous vinyl chloride resin as a main resin component, and the resin component is dissolved or finely dispersed. The aqueous primer liquid contains an anionic surfactant, a cationic surfactant,
A necessary amount of a surfactant such as a nonionic surfactant can be added and used. Such surfactants are preferably those that can lower the surface tension of the aqueous coating solution to 40 dyne/cm or less and promote wetting to the polyester film, such as polyoxyethylene alkylphenyl ethers and polyoxyethylene fatty acid esters.

Sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl sulfate, alkyl sulfonate, alkyl sulfosuccinate.

Examples include quaternary ammonium chloride salts and alkylamine hydrochlorides. Further, other additives such as antistatic agents, ultraviolet absorbers, pigments, organic fillers, inorganic fillers, lubricants, and antiblocking agents may be mixed in without detracting from the effects of the present invention.

The amount of antiblocking agent to be used is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, based on the total weight of the primer layer.

Application of water-based primer solution to polyester film is as follows:
It may be carried out in a normal coating process, that is, in a process of coating a biaxially stretched and heat-set polyester film separately from the film manufacturing process.

However, this process tends to trap dirt, dust, etc., and it is desirable to apply the coating in a clean atmosphere for advanced products such as magnetic tapes and floppy disks. From this point of view, coating during the polyester film manufacturing process is preferable. In particular, it is preferable to apply an aqueous primer coating liquid to one or both sides of the polyester film before the crystal orientation is completed during this step. In this case, the solid content concentration of the aqueous primer coating liquid is usually 30% by weight or less, more preferably 10% by weight or less. Application 0 is 0.5 to 20 rJ per running film 1711, and further 1 to 10!7
is preferred.

Any known coating method can be used as the coating method.

For example, a roll coating method, a gravure yaw method, a roll plush method, a spray coating method, an air knife coating method, an impregnation method, a curtain coating method, etc. may be applied alone or in combination.

The polyester film coated with the aqueous primer solution and before crystal orientation is dried and stretched.

This leads to processes such as heat fixation. For example, a longitudinally-axially stretched polyester film coated with an aqueous primer solution is guided through a stenter, then laterally stretched and heat-set. During this time, the coating solution dries and forms a continuous film on the film. Drying is preferably carried out before or during stretching.

Oriented crystallization conditions of polyester film, e.g. stretching,
Conditions such as heat fixation can be carried out under conditions conventionally accumulated in the industry.

In the present invention, a diazo photosensitive layer is provided on the primer layer of the thus obtained primer-coated two-wheel stretched polyester film. The diazo photosensitive layer is usually composed of baingu, a diazo compound, a photosensitive agent as a coupling component, and other additives such as a coupling inhibitor and an antioxidant.

Examples of the diazo compound include benzenediazo compounds, 〇- or P-aminobenzenediazo compounds, and P-amine ester benzenediazo compounds.

Examples include mercaptobenzenediazo compounds.

An example of a coupling component is phenol.

Resorcin, α- or β-naphthol, R acid, HM
, GM, pyrazolone derivatives and the like. Examples of the coupling inhibitor include phosphoric acid, citric acid, oxalic acid, boric acid, oxypyridine, and oxybenzotriazole. Examples of antioxidants include thiourea, salicylic acid, and pyrogal. Other additives include methylene blue as a color tone modifier, and ZN CJ12 as a dispersant or special auxiliary agent. As the binder, cellulose binders with excellent transparency, such as cellulose acetate butyralate, cellulose acetate propionate, etc., and polyester binders are preferably used.

The proportions of these components to be used may be any conventionally known proportions. These components, for example, methanol.

Dissolved in a single or mixed solvent such as methyl ethyl ketone (MEK), ethyl acetate, butyl acetate, toluene, Celsolve, diacetone alcohol, cyclohexane, etc.
The resulting coating liquid is applied onto the primer layer by a known coating method such as a reverse coating method, and then heated at 80 to 150°C.
A diazo film can be obtained by drying at a temperature of from several tens of seconds to several minutes.

The thickness of the photosensitive layer after drying is preferably 2 to 5 μm.

In this way, a diazo film with excellent long-term storage stability can be easily obtained.

<Example> The present invention will be further explained below with reference to Examples.

Note that "part" in the examples means "heavy product".

Moreover, each characteristic of the film was measured by the following method.

1. Scotch tape NQ on the diazo photosensitive layer of the adhesive diazo film
600 (manufactured by 3M) with a width of 19.4 mm and a length of 15 cm, adhere it to avoid bubbles, and then apply JISC27 on top of it.
01 (1975) to bring it into close contact with each other, and then cut it out to the tape width. This sample was rapidly peeled off with the polyester film facing upward, and the peeling status of the diazo photosensitive layer was observed.

Most of the diazo photosensitive layer has been transferred to the adhesive tape, but half of the X diazo photosensitive layer remains on the polyester film △The entire diazo photosensitive layer remains on the polyester film 02. Primer coating treatment of blocking polyester film After matching the sides, cut into 10cm x 15cm squares and heat them at 55℃.
6KFI/ctd for 17 hours in an atmosphere of X88%RH
Then, the peel strength of this 10α width is measured. The peeling speed at this time was 100 m/min.

Examples 1 to 3 and Comparative Examples 1 to 3 Intrinsic viscosity measured in O-chlorophenol at 25°C 0
．． 65 polyethylene terephthalate (containing lubricant) 2
It was extruded onto a rotating cooling drum maintained at 0°C to a thickness of 9.
An unstretched film of 50 μm was obtained, and then 3.
After stretching 5 times, the aqueous primer solution shown in Table 1 was applied to both sides of the uniaxially stretched film by a kiss coating method. Subsequently, it was stretched 3.9 times in the transverse direction at 105°C, and further stretched at 210°C.
A double-sided primer-coated polyester film having a thickness of 75 μm was obtained. The average coating ω at this time was 50 Rg/rd in terms of solid content.

On the primer layer of this film, a diazo photosensitive solution having the following composition was coated to a dry layer thickness of 3 μm, and dried at 100° C. for 2 minutes to obtain a diazo film.

<Diazo photosensitive liquid> Binder cellulose acetate butyrate 80 parts Diazo compound Daito Kagaku DH-3008F4 4 parts Coupling agent Daito Kagaku Qrounder D 6 parts ZnCUz O, 1 part Thiourea 0.1 part P-chlorobenzenesulfonic acid 0, Part 1 M E K
200 part 1 ~ Ruen
Table 1 shows the adhesion and blocking properties of the diazo film containing 100 parts of cyclohexanone and 200 parts of 1q.

Table 1 shows that the diazo film of the present invention has excellent adhesion between the polyester film and the diazo photosensitive layer and can withstand long-term storage, while the film of the comparative example has poor adhesion.
It is clear that the diazo photosensitive layer may peel off from the end face due to expansion and contraction due to temperature and temperature changes during storage.

Claims (2)

[Claims] (1) Providing a primer layer mainly composed of aqueous vinylidene chloride resin on at least one side of the polyester film,
A diazo film is further provided with a diazo photosensitive layer on top of this. (2) An aqueous primer solution containing an aqueous vinylidene chloride resin as a main component was applied to at least one side of the polyester film before crystal orientation was completed, and then drying, stretching, and heat treatment were performed to complete the crystal orientation of the polyester. A method for producing a diazo film, which comprises a primer-coated biaxially stretched polyester film, and further providing a diazo photosensitive layer on the primer layer of the film.