JPH04122643A - Polyester backing - Google Patents

Abstract

PURPOSE:To improve the bonding property and the flatness of a waterproof poly(vinylidene chloride) layer and polyester backing by having a layer formed of an addition polymer and an ethyleneimine type crosslinking agent between the poly(vinylidene chloride) layer and a polyester film. CONSTITUTION:There is a layer formed of an addition polyester and a crosslinking agent between a poly(vinylidene chloride) layer and a polyester film. Examples of addition polymers are a polymer containing ingredients which comprise butadiene, a polymer containing hydroxymethyl mathacrylate, a polymer containing glycidyl methacrylate and the like. Examples of crosslinking agents are a compound having an ethyleneimine group such as tetramethylene-1,4-bis hexamethylene-1,6-bis.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a plastic film having a waterproof polyvinylidene chloride layer and having excellent adhesion to a polyester support such as a core layer and excellent flatness.

[Background of the invention]

Because of its excellent water barrier properties, polyvinylidene chloride is often laminated onto a film substrate to increase the waterproofness of the entire film. In the case of supports such as photographic supports, a polyvinylidene chloride layer has been provided on a polyester support for a long time, as seen in Japanese Patent Publication No. 303437. However, the adhesion between polyester and polyvinylidene chloride cannot sufficiently meet the strict demands of recent years. For this reason, for example, JP-A-1-193731 discloses a technique for improving adhesion by providing an aqueous polyester layer, which is a condensation polymer, between a polyester and a polyvinylidene chloride layer.
In No. 84844, σ having a carboxyl group between the polyester and the polyvinylidene chloride layer.

A technique has been disclosed that improves adhesion by providing a layer containing a copolymer of β-unsaturated carboxylic acid and a specific curing agent. However, in order to obtain excellent film adhesion, this method requires a long heat treatment, which is not only disadvantageous industrially but also impairs the flatness of the polyester, which poses a problem in terms of commercial value.

[Purpose of the invention]

In order to solve the above-mentioned problems, the object of the present invention is to provide a polyester material laminated with a waterproof polyvinylidene chloride layer.
To provide a polyester support which has excellent adhesion between a vinyl II-F layer and a polyester support without impairing its flatness.

[Structure of the invention]

The above-mentioned object of the present invention is a polyester film in which layers containing polyvinylidene chloride are laminated, characterized in that a layer formed from an addition polymer and a crosslinking agent is provided between the polyvinylidene chloride layer and the polyester film. This is achieved by using a polyester support.

The present invention will be explained in detail below.

Examples of addition polymers in the present invention include copolymers of one or more vinyl monomers and the following monomers.

■Butadiene monomer lO ~ 90% ■ Monomer containing glycidyl group lO ~ 90% ■ Monomer containing hydroxyl group lO ~ 90% The monomer may be one type or multiple types, but two types The above is preferable.

Here, vinyl monomers include, for example, conjugated dienes such as butadiene and isoprene, non-conjugated dienes such as 1,4-pentadiene and 1,4-hexadiene, vinyl aromatics such as styrene and methylstyrene, methyl methacrylate, ethyl methacrylate, butyl Methacrylic esters such as methacrylate, glycidyl methacrylate, and hydroxymethyl methacrylate; acrylic esters such as methyl acrylate, ethyl acrylate, and butyl acrylate;
Examples include acid septamers such as acrylic acid, methacrylic acid, itaconic acid, and maleic acid.

Particularly preferred addition polymers include polymers containing a component consisting of butadiene, polymers containing hydroxymethyl methacrylate, polymers containing glycidyl methacrylate, and the like.

Examples of the ethyleneimine crosslinking agent used in the present invention include compounds having an ethyleneimine group such as tetramethylene-1,4-bis(ethyleneurea) and hexamethylene-1,6-bis(ethyleneurea). Special J
This is preferable.

The vinylidene chloride copolymer in the present invention refers to a copolymer containing vinylidene chloride, JP-A-51-135526
A copolymer of vinylidene chloride/acrylic acid ester/vinyl monomer having an alcohol in the side chain described in No. 2, a copolymer of vinylidene chloride/alkyl acrylate/acrylic acid described in U.S. Pat. Copolymer of vinylidene chloride/acrylonitrile/itaconic acid of U.S. Pat. No. 2,698.235, U.S. Pat.
Examples include a copolymer of vinylidene chloride/alkyl acrylate/itaconic acid described in No. 788.856. Specific examples of compounds include the following.

All numbers in parentheses represent weight ratios.

Copolymer of vinylidene chloride: methyl acrylate: hydroxyethyl acrylate (83:12:2) Copolymer of vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (82:10:8) Vinylidene chloride: hydroxydiethyl methacrylate Vinylidene chloride: butyl Acrylate: Acrylic acid (94:4:
2) copolymer vinyldene chloride:butyl acrylate:itaconic acid (7
5:20:5) copolymer vinylidene chloride; methyl acrylate: etaconic acid (
90:8:2) copolymer vinylidene chloride: methyl acrylate: methacrylic acid (93:4:3) vinylidene chloride: itafonic acid monoethyl ester (96
:4) copolymer of vinylidene chloride:acrylonitrile:acrylic acid (96
:3.5:1.5) copolymer vinylidene chloride:methyl acrylate:acrylic # (90:5:5) copolymer vinylidene chloride:ethyl acrylate:acrylic acid (9
2:5:2) copolymer vinylidene chloride:methyl acrylate:3-chloro-2
- Copolymer of hydroxypropyl acrylate (84:9=7) Copolymer of tanol acrylamide (85:10:5) Vinylidene chloride: Methyl acrylate: Acrylic acid (9
Copolymer vinylidene chloride: methyl acrylate: itaconic acid (9:1:l)
7:1:2) copolymer vinylidene chloride:acrylonitrile:acrylic acid (99
:0.5:0.5) Copolymer of vinylidene chloride:ethyl acrylate:acrylic acid (98:1:1)Hinylidene chloride:methyl acrylate:acrylic acid (6
5:34+1) copolymer vinylidene chloride: methyl acrylate: itaconic acid (7
Copolymer vinylidene chloride:acrylonitrile:acrylic acid (70:29:1)
:29:I) copolymer vinylidene chloride:ethyl acrylate:acrylic acid (6
8:31:1) copolymer.For details on the polyester in the present invention,
A polyester whose main components are aromatic dibasic acids and glycol. Typical dibasic acids include terephthalic acid, isophthalic acid, p-β-oquinethoxybenzoic acid, cypheylsulfonic acid, and difenoquine. Examples of glycol include ethanedicarboxylic acid, adipic acid, sebanic acid, acelaic acid, pentasodium sulfoisophthalic acid, diphenylene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, etc. Glycols include ethylene glycol, propylene glycol, butanediol, Pentylene gellicol, ■, 4-cyclohexanediol, l, 4-
Examples include cyclohexane dimetatool, 1,4-bisoxysudoxybenzene, bisphenol A1 diethylene glycol, and polyethylene glycol. These polyester films can be produced using a known biaxial stretching method, such as that described in JP-A No. 52-54428.

Various treatments can be applied to create a strong bond between the polyester and its top layer.

For example, surface treatment with chemicals, mechanical treatment, corona discharge treatment,
Flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment,
Surface activation treatments such as active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment can be performed. In addition to this, it is also possible to use known means for preventing charging. For example, there is a method in which a fluorine-based surfactant, various conductive polymers, inorganic oxides, organic antistatic agents, etc. are contained in the undercoat layer.

Although the support of the present invention can be used for various purposes, it is particularly suitable for use as a support for materials that involve wet processing, such as silver halide photographic light-sensitive materials, by taking advantage of its water barrier property. I can do it. In the case of applications involving such wet processing, the effect of increasing dimensional stability can be expected.

When using the support of the present invention, there are no particular limitations on the silver halide photographic light-sensitive material, and it can be prepared and processed using various techniques known in the light-sensitive material industry.

〔Example〕

EXAMPLES Hereinafter, the effects of the present invention will be illustrated by Examples, but the present invention is not limited to these Examples.

Example 1 The following first layer coating solution was applied to both sides of a biaxially oriented polyethylene terephthalate support having a thickness of 100μ that had been subjected to corona discharge treatment. After drying at 140° and 2 seconds, the second layer coating solution was applied to both sides. It was applied and dried at 140°C for 1 minute. The composition of the coating liquid is as follows: First layer of undercoat (liquid A): 4 g of copolymer latex (solid content: 50%) consisting of butadiene 38 wt%, styrene 54 vt%, acrylic acid 5 wt%, itaconic acid 3 wt%.
Hexamethylene-1,6-bisethyleneurea 30
Finish with mg water to 100 mff, 20 per m″
Apply at a rate of 1 IIa.

(Liquid B) Copolymer latex (solid content 30%) consisting of hydroxyethyl methacrylate 25wt% butyl acrylate 35wt% styrene 40wt% 10g hexamethylene-1,6-bisethyleneurea 30o+
g Finish with water to make 100 m4, and 20 m (l) per 1 m2.
Apply at the rate of

(Liquid C) Copolymer latex (solid content 30%) consisting of glycidyl methacrylate 40wt% butyl acrylate 4Qwt% styrene 20wt% 10
gHexamethylene-1,6-bisethyleneurea 3
Finish with 0mg water to give 100-ρ, 2D per layer 2
Apply at a ratio of IIIρ.

(Liquid H): Copolymer latex (30% solids) consisting of ethyl acrylate 45wt% methyl methacrylate 50wt% methacrylamide 5wt% 10
g2. 4-dichloro-6-hydroquine-3-triazine Na salt 5% aqueous solution Finish with 1.5 cc water to 100
Apply TI11 at a rate of 20m4 (7) per 1 and 2.

(Liquid H) Water-soluble PoI) Varnish-r wD-5ize (
30%) 12.3g (manufactured by Eastman Chemical) 2.4-dichloro-6-hydroxy-S triazine Na
5% salt aqueous solution 1.5cc α-sulfosuccinic acid di(2-
Ethylhexyl)ester sodium salt (5%) 0.
Finish with 2cc water to make 100I, 15n per 1m2
Apply at a rate of +ff.

(Liquid H): Solution A with hexamethylene-1,6-bisethyleneurea removed (Liquid G): Solution H with hexamethylene-1,6-bisethyleneurea removed (Liquid H) Liquid 20, excluding hexamethylene-1,6-bisethyleneurea (Liquid ■) = Liquid D, excluding 2,4-dichloro, 6-hydroxyl, and 3°5-triazine. Layer A co-electrical latex (solid content 48%) consisting of vinylidene chloride 9Qwt%, methyl acrylate 5vt% and acrylic acid 5wt% is finished with 30g water to give 100IIQ and applied at a rate of 10mff per m2.

These coating liquids were combined to prepare polyester supports as shown in Table 1, and the adhesiveness was evaluated by the following method.

Method for evaluating the surface contact of the prepared sample: Scratch the surface of the prepared sample with a cutter, firmly stick cellophane adhesive tape on it, and then peel off the adhesive tape sharply at an angle of about 90° to check the peeling state of the film. It was observed and graded as follows.

l: No peeling at all: Peeling area lO~20%: Peeling area 20~50%: Peeling area 50% or more Table 1 As is clear from the above results, there is no added weight between the polyester film and the polyvinylidene chloride layer. The adhesion properties are extremely improved by having a layer consisting of a combination of urethaneimine and a utylenimine crosslinking agent.

- Sample 5 using a condensation polymer has improved adhesion compared to the sample without the first layer, but inferior adhesion compared to the present invention.

2,4-dichloro-6-hydroquine-3- as a curing agent
No. 5 using triazine sodium salt had a smaller adhesion improvement effect than those without, but No. 2, No. 3 using ethyleneimine curing agent.

Samples No. 4 had an extremely large improvement effect compared to samples that were not used. Moreover, this improvement effect becomes even greater when a polymer having a glyc/dyl group or a hydroxyl group is used in combination.

Example 2 On top of Sample 1-10 prepared in Example 1, methyl methacrylate-ethyl acrylate-methacrylic acid (5
5/36.6/8.4) Copolymer latex was coated and dried to form a layer of 0.2 μm in thickness. 2 of the obtained samples
These samples numbered 01 to 210 were printed using cellophane ink based on nitrocellulose,
This printed surface was scratched with a cutter, and then cellophane adhesive tape was strongly pasted on top of it, and then the adhesive tape was suddenly peeled off at an angle of approximately 90°, and the state of peeling of the film was observed. Adhesion results similar to Example 1 were obtained.

Example 3 On top of Samples 1 to IO prepared in Example 1, the following coating solution was further applied and dried so that the gelatin content was 3 g/m''.

・Gelatin 5g・p
- Sodium totisylbenyadisulfonate 50mg ・Ceratin hardener (l-oxy-3,5-dichloro-S triazone sodium salt 1% aqueous solution) 5cc ・Water
Specimens 301 to 310 are samples of 95 cc of coating liquid. The following silver halide emulsion layer and protective layer were provided on one side of these samples, and a backing layer was provided on the other side.

(Preparation of Emulsion I) Grains containing 10-' mol of rhodium per mol of silver were prepared by the controlled double jet method in an acidic atmosphere at pH 3.0. Particle growth was achieved by adding benzyladenine to 1 c of 1% aqueous gelatin solution to polyethylene glycol 1100 II 1/l 112 sodium dodecylbenzenesulfonate 100 mg/m" and hydroquinone 200 mg/m"
Phenidone 100 mg/m2 Sodium styrene sulfonate-maleic acid polymer (M
v=250,000) 200 mg/m" Gallic acid butyl ester 500 mg/m"5
-Methylbenzotriazole 2-mercaptobenzimidazole-5-sulfonic acid
30 mg/m2 inert ossein gelatin (isoelectric point 4.9) 1.5 g
/+" 1-(p-acetylamidophenyl)-5 mercaptotetrazole 30 mg/m" Silver amount
2.8 g/m" gelatin coating amount 2.0 g/m" Tetrazolium compound (emulsion layer protective film I) The coating was prepared and coated as an emulsion layer protective film so as to have the following coating amount.

Fluorinated dioctyl sulfosuccinate ester 300 m
g/m2 Matting agent Nijirica (particle size 8 μm) 20 mg/m
2// (particle size 3 pm) 10 + mg
/+”Lithium nitrate salt 30 tags
/rm” acid-treated gelatin (isoelectric point 7.0) 1.
2 g/a+2 colloidal silica 50
mglo” Sodium styrene sulfonate-maleic acid copolymer 100 a+
g/+'' Mordant Dye 03Na (Backing Layer) A backing layer containing a backing dye having the following composition was coated on the support opposite to the emulsion layer.

The gelatin layer contains glyoxal and l-oxy-3,5-
Hardened with cyclos-triazine sodium salt.

(Backing layer) Hydroquine 100 mg/m2 Funinidone 30 mg/ll
12 latex polymer dibutyl acrylate butyl acrylate styrene copolymer 0.5 g7m2 styrene-maleic acid copolymer 100 mg/+o2 citric acid
40 mg/m2 Benzotriazole 100 mg/m2 Sodium styrene sulfonate maleic acid copolymer
200 wag/ln2 lithium nitrate salt
30 mg/m2 backing dye (a
), (b), (c) Ossein gelatin
2.0 g/m2 Spherical polymethyl methacrylate (average particle size 5 μm) 20 mg/m” (
a) (b) (c) CH, SO, H 5 O, Na o 3 Na 500 mg/m” The silver halide photosensitive material thus produced was evaluated for film formation in the same manner as in Example 2. also,
It has been found that the presence of a layer of the addition polymer and curing agent of the present invention between the polyester film and the polyvinylidene chloride layer provides excellent emulsion layer or backing layer adhesion.

〔Effect of the invention〕

According to the present invention, it was possible to provide a polyester support with excellent waterproof properties. That is, in a film in which a vinylidene chloride layer is laminated on a polyester support, it was possible to provide a polyester support that has excellent adhesion between both layers and does not impair flatness.

Claims (1)

[Claims] A polyester film in which layers containing polyvinylidene chloride are laminated, the polyester support having a layer formed from an addition polymer and an ethyleneimine crosslinking agent between the polyvinylidene chloride layer and the polyester film. body.