DE2128388A1 - Improved adhesion of layers to polyester film - Google Patents

Description

AGi ¹ A-GEVAERT AG LEVERKUSEN

Improved adhesion of layers to polyester film.

Priority: Great Britain, June 9, 1970, An.No. 27 979/70.

January 21, 1971, An.Nr. 2879/71

This invention relates to a method of improving adhesion of layers containing polymeric binders on untreated polyester film, as defined below, especially untreated polyethylene terephthalate film, and on the kept upgraded materials.

The term "untreated polyester film" is used here Polyester film meant that does not have any chemical and / or physical pretreatment to enable or facilitate has been subjected to the coating of this polyester film with a hydrophilic layer. Examples of such treatments are the application of intermediate and / or adhesive layers, the treatment of the polyester surface with solvents or Swelling agents for the polyester, and exposure to a high voltage electrical corona discharge.

usually when layers containing polymeric binders on polyester films, especially on polyethylene terephthalate films are to be applied, it is necessary to first provide this carrier with a known adhesive layer or the To pretreat the surface of the support according to known techniques. For example, the polyester film base can be provided with an adhesive layer which are a copolymer of at least • one of the chlorine-containing monomers vinylidene chloride and vinyl chloride contains. This adhesive layer has been described in French patent specification 1,582,378. Good results, is also obtained when the surface of the adhesive layer is subjected to a high-voltage direct current corona discharge as described in Belgian patent 74-2769. Occasionally can be an electrical corona discharge treatment

GV.525 109861/18 51

.the polyester film carrier itself is sufficient.

The surface of the polyester film carrier can also be: .Pj " treated with a solution of a swelling agent for the polyester *, as described in Belgian patent 751A-5 will.

It has now been found that layers containing polymeric binders can be applied directly to untreated polyester film backing, and that these layers can be applied to the Polyester surface both when dry and when wet can adhere without the need for special auxiliary layers or the need to pretreat the polyester film surfaces.

According to the invention there is a method for improving the adhesion of polymeric binder-containing layers on the untreated polyester film as defined above, provided which method thorough mixing of the polymeric binders prior to their. Apply to the untreated polyester film with at least 25% by weight, based on the polymeric binder, of at least a dye that has a carboxyl group in its molecule contains at least one hydroxyl group, amino group, halogen atom or a second carboxyl group, or of at least one Dye containing two or more hydroxyl groups.

The method according to the invention can be applied to all materials "where a colored or light filter layer is applied directly to an untreated polyester surface, especially on . an untreated polyethylene terephthalate film base. Such colored or light filter layers are present in light-sensitive photographic materials, for example in photographic materials where an antihalation layer is applied to the back of the polyester support has been. Other photographic applications include an antihalation layer s in which the colored layer zxtfischen the polyester support and the light-sensitive layer or the light-sensitive layers is present. Polyester films provided with a colored layer can also be used in non-light-sensitive photographic materials find use, e.g. in light filters for darkroom lighting, in

GV.525-1098B1 / 1851

BATH ORIGINAL

? arl "t-c" -reratur-ü2 :: v.'andlungsfilter and color correction filters for .lic color photography, and as a light filter in manufacture -.cn negative and positive color separations for graphic work. From outside photography, the polyester films are one of those like or UV absorbing layer, useful in sunglasses], and especially in transparent gardin-'η for Showcase to protect the exhibited products in front of the i: r. Harmful UV radiation present in sunlight.

The inventive dyes belong to almost all known classes of dyes, such as the classes of the triphenyl methane type

CCCH

(C "H _C ) ₅ lI - ^^ - C 2 5 2 > c - M ^ ,

COO "

ei / - "I

\ y COOH

COOH

-NH- _V _

COOH

COOH

Kr. 3 ■ "

^C00 "* BAD OBIGINAL

GV.525 109S51 / 1651

Kr. 4

COOH

H ₃ CO-.

-NH,

coo "

COOH-Cl

COOH

Cl

CH,

-OH

COOH

coo "X ^ fN = Nf

COOH

108861 / 18S1

212838S

ITr. 8th

COOH

COO

ITr. 9

cooH

\ p> -N *

I _

COO

- the classes of Oxono! dyes, e.g.:

¹⁰

Oh

Oh

Il

IJ

¹ V

C0 HO-C ^V C0

ι ι »Ι ι

H_C- (CH) -NC = CH-CHsCH-C. N- (CH_) ^ 3 2 3 \ _c / N ^ 2 3

it

ITr. 11

HOOC

OC ^N C0

N.

HO-c ^'V CO

^{; l} J) ϊ

C = CH-CH = CH-CH = CH-C _V K-

GV. 525

109851/1851

2Tr. 12th

I-COOH

A 1

\ ^ CO WO-C * ^N CO

t II I

I _n ^ C = CH-CH = CH-C TI-CH-CH

CfT "V--

■ «Il

O O

■ ■. ■ d-

· HOOC-H-C, 110 CH-COOH

² IS - ι ι ² ■ -

N C ^ C H

»O"s' ^ c = ch-ch = ch-ch = ch-c ". * So ^ * ^ -c 'V_n'

HOOC-H C ° ° CH ₀ -COOH

- the classes of azo dyes, e.g.

SOH

Ϊ ■. .- ■ -

II J ₁ - ^

HO-C ^ ^X N y

Ii il ⁷

HO "S- <? ~~ \ -N = NC-C-COOH. HN = C

- the classes of the rierostyi-ylverMridun ^ en, e.g.

ITr. -15 - ■ - ■ -. ■ - -. . . _ .. ■■:., J-

HCOOC. ^ CHy-COOH y ^C ^ r

CCH ^ 3M . iCi-fr HiI-G ^

^N CH-COpH .V.cV

_CrV . ₅ 25 109851/1851

The polymeric binders for the polyester film backing colored layer to be applied can lead to different polymer classes belong. If the colored layer as an antihalation layer to be used in a photographic light-sensitive material are alkali-soluble polymers preferred. These layers dissolve easily, or they can, in alkaline photographic developing baths after processing them in highly alkaline pre-baths and before entering the first developing bath with rinsing water easily remove.

Suitable alkali-soluble polymers are, for example:

- partially or fully sulfonated polystyrene

- Co (styrene / maleic acid)

- partially or fully nitrated Co (styrene / maleic acid)

- Coi vinyl acetate / maleic acid) (50/50 mol%)

- CoiStyrene / acrylic acid) (70:30% by weight)

- CoiStyrene / kethacrylic acid) (30:70% by weight)

- Coin-butyl acrylate / kethacrylic acid) (70:30 % by weight)

- Coi ethyl acrylate / acrylic acid) (80:20 wt. #)

- Ethyl acrylate / methyl methacrylate / methacrylic acid) (15:50:35

Weight £)

- Co (n-butyl acrylate / ethyl methacrylate-alethacrylic acid) (67: 3: 30

- Coin-butyl acrylate / methacrylate / methacrylic acid) (35:30:35

Weight%)

- Coimethyl acrylate / methyl methacrylate / acrylic acid) (79: 1: 20% by weight)

- Co (2-ethylhexyl acrylate / methyl methacrylate-alethacrylic acid)

(30:30:40 wt. #)

- Co (ethyl acrylate / n-butyl methacrylate / methacrylic acid) (78: 2: 20

Weight%)

- Co (DtyrolAlonoisobutyLnia] .eate / maleic acid) (41: 57: 2

Typically, these polymers are water-insoluble in its acid Fora, but they dissolve readily in alkaline photographic developers such that the LiclithofJschute-Zusamnensetzung from photographic FilotrHger is removed and leaving a pnotographiecher FIIA.

In applications in which the colored layer does not have to be removed from the carrier, as in the case of light filters, can other polymeric binders such as styrene polymers or methyl methacrylate polymers or their copolymers with other ethylenically unsaturated monomers can be used.

The fact that the adhesion of the polymer layer to the polyester film support is attributable to the presence of the dye can be easily detected · If one of a polymer ■ Binder-formed layer in which a water-soluble dye having a substituent as described above is dispersed contains, is applied to a polyester film, the dye can be released from the layer with water. It was very surprising to find out that the layer, which adhered very well to the polyester film before the aqueous treatment, was light could be separated from it after the water-soluble dye contained therein had been dissolved away

The thickness of the colored layer and the amount of that contained in it dye depends on the intended use of the Material from · If the colored layer is used as an antihalation layer, it is between 0.2 and 3 microns thick and the amount of dye added is chosen such that the resulting layer has an optical density from about 0.5 to 3.

The colored layer can be removed from the solution by known methods can be applied to the polyester film support, for example by spraying, by roller application, with a squeegee or an air brush, or by a brushing process.

The examples described below relate in particular on colored layers, which on polyethylene terephthalate filne were applied. However, the invention is not limited to the use of polyester films made from Reaction derived from terephthalic acid and ethylene glycol. In the manufacture of high molecular weight polyesters, others can Glycols partially or wholly replace the ethylene glycol, e.g. Beopentyl glycol and 1,4-di (hydroxymethyl) cyclohexane. The terephthalic acid can also be partly or wholly by other dibasic

^GY ' ³²³ 10 9 8 51/18 5 1

• ν "-

Acids such as isophthalic acid, sebacic acid and adipic acid can be replaced.

The following examples illustrate the invention. The one in it dyes mentioned are replaced by those given in the list above Lobsters called

example 1

30 g of one of the following polymeric binders are combined or without 15 S of triphenylmethane dye # 5 in 1 liter Dissolved ethanol. 1 ml of 35% strength by weight aqueous is added to this solution .Solution of hydrochloric acid added to the dye to dissolve completely.

The polymeric binders used are the following:

(a) Co (styrene / maleic acid) (50:50 Hol%) 00 CoCVinylacetate / Iialeinic acid) (50:50 Mol #)

(c) Co (styrene / acrylic acid) (70:30 wt.%)

(d) Co (styrene / methacrylic acid) (30:70% by weight)

(e) Co (ITitrostyrene / maleic acid) (50:50 mol%) (all Styrene units are nitrided)

(f) Co (n-butyl acrylate / methacrylic acid) (70:30

With each of the prepared solutions, 48 m2 will be biaxially oriented Polyethylene terephthalate film is coated, and the layers are then dried by evaporation of the solvent.

The layers containing the triphenyl methine dye adhere very good on the polyester film base · However, the layers that do not contain triphenylmethane dye come off very easily from their wearer.

Example 2

. Two solutions are prepared, each containing 20 g of Co (vinyl acetate / Maleic acid) (50:50 mol%) dissolved in a mixture of 200 ml

'Methanol, 200 ml of ethanol, 600 ml of acetone and 1 ml of 35 wt aqueous solution of hydrochloric acid. In one of these Solutions are also 10 g of the triphenylmethane dye ITr.

' solved.

1098 51/1851

Both solutions are used as one in the ratio of 60 m2 per liter Antihalation Composition on one side of a "biaxial oriented polyethylene terephthalate film applied, whereupon de solvents are evaporated.

Me dried antihalation layer containing the quiriphenylmethane dye adheres very strongly to the polyester carrier and loosened and completely discolored in a photographicchen Developer bath. . "· '-.

But the layer that did not contain any iriphenylmethane dye did not adhere to the polyester backing and could easily be peeled off will, -

* Example 3 - -

0-5 are added to 5 solutions of 30 g of Oo (styxol / maleic acid) (50:50 Eo 1%) in 1 liter of ethanol, to which 2 ml of 35% by weight aqueous solution of hydrochloric acid have been added 7.5 - Ί0 or 15 g of the triphenyl methane dye Ur.5 are added The solutions are applied in a ratio of 40 E.2 / liter to a polyethylene terephthalate film support.

After the solvent has evaporated, the layers, which do not contain 0 g or 5 S triphenylmethane dye on the polyester support. The adhesion of the layer, which 7? 5 g Contains dye is insufficient, but the layers which contain P "10 g or 15 S triphenylmethane dye are very adherent strong am. Polyethylene terephthalate film.

Example 4- * -

20 g CoCStyrQl / monoisobutyl maleate / maleic acid) (41: 57: 2% by weight) and 10g of the azomethine dye of the formula:

^H 3 ^C v

Ν ^ ~ ^ ναΗΝ £ ^> HCl

- "COOH

are dissolved in 1 liter of ethanol, to which 1 ml of 35 5o aqueous

p-y Cot

TOtSSI / 18pcs

Hydrochloric acid solution is added

The solution is in the ratio of 55 m2 per liter on one Polyäthylentereplithalatfilm applied. The dried one Layer did not adhere to the polyester surface. If 15 g of the triphenylmethanine substance Hr. 7 also for the casting composition are added, a layer is obtained whose Adhesion to the Folycster film is excellent.

Example 5

Four parts of 20 g each of cocstyrene / acrylic acid) (70:30 wt.? '), which each 15 g of one of the triphenylmethane dyes Kr. 2, 6, 8 or 9 contain, are dissolved in 1 liter of ethanol, whereupon each Solution in the ratio of 4-5 egg2 / liter on a biaxially stretched one Polyethylene terephthalate film applied v / ground.

The colored layers adhere very well to the polyester film carrier.

When the same amount of the copolymer is dissolved in ethanol is without the addition of a dye, it can be applied to a polyethylene terephthalate film formed layer can be easily peeled off therefrom.

Example 6

Four parts of 10 g each of CoiCtyrene / acrylic acid) (70:30% by weight), each containing 10 g of one of the oxynol dyes No. 10 ₄ 11, 12 or 13, are dissolved in 1 liter of ethanol of 55 m2 per liter applied to a biaxially oriented polyethylene terephthalate film.

The colored layers adhere very well to the polyester films. However, when no dye was added to the above coating compositions, a colorless layer was obtained. that did not adhere to the polyester film

Example 7

One side of a biaxially stretched polyethylene terephthalate film is coated in a ratio of 1 liter per 55 e2 with the following composition r ^{c; ;} - r; - ".

1098 5.1 ^ 185 1

BATH ORIGINAL

CoC styrene / acrylic acid) (70:30 wt.%) 3Ce-

Ethanol .1 litei

35 c ^: e ^w '% aqueous solution of hydrochloric acid 1 nl

Triphenylmethane dye No. 5 '15 ζ

Triphenylmethane Dye No. 7-10 r-j. '

The other side of the carrier is provided with a known adhesive layer and then with a lichteiapf ir_dlicr_er_ "Gelatin silver halide emulsion layer coated.

The colored layer adheres very well to the polyester film carrier and was completely decolorized in a photographic er_tv: ic> - * lungsbad ..

Example 8 .

An antihalation layer is in the ratio of 50 liters per m2 from the following casting composition on a biaxially stretched one Polyethylene terephthalate film base applied:

CoC styrene / acrylic acid) (65; 35% by weight) ethanol

35% strength by weight aqueous solution of hydrochloric acid

Triphenylmethane Dye No. 5 Triphenylmethane Dye No. 4-Azomethine Dye the formula

: · :: ^; / GOOH

³ N-. ''.-GH = N-.''. .HCl- 7 E

The other side of the girder is one behind the other with a locomotive Adhesive layer and a photosensitive gelatinous halide emulsion layer overdrawn·

The atrium protection layer adheres very strongly to the polyester film carrier. It became discolored; ^^^ and was completely dissolved away after treatment in a photographic developer solution.

GV.525 '·, ... "" - ■■. : ^; ν XX; ' } X- ■ ■ '■■ -. '.' ■

; BATH ORIGINAL

109661 / 1ÖB1

30th liter 1 nl 2 CT 13th 9

Example 9

In the LichthofschuttNGiessrusanmensetinmg of Example 8, the dyes are replaced by the following j

Triphenylmethai Dye Kr x 5 15 g Tripbenylmethane F arbatoff Hr * 1 8 g HeroBtyryl compound Hr · 15 10 g

The properties of the antihalation layer are the same as those of the layer described in Example 8.

Example 10

A light filter composition is prepared as follows: In a mixture of 400 ml of butanes AOO al ethanol and 200 ml of ethylene chlorohydrin, 20 g of polymethyl methylate with a limiting viscosity of 0.214 dl / g _f, measured in acetone at 25%, and 15 g of iriphenyl metal sr.7 solved. The solution obtained is applied in a ratio of 52 μ2 / IAter to a biaxially oriented rolyfitbylene terephthalate film.

The liability of the dried colored layer on Polyestertriger was excellent, "even after a olgenden" nfeinander * treatment of the material in a photographiechen Entwickltmgsbad _v a photographiechen Pixisrbad "and after rinsing nit Uasaer. There is no etching of the layer. An identical layer, which does not contain any dye, can easily be separated from the polyester filiQ.

• BeisDiel 11

Example 10 is repeated with the difference, however, that the polymeric binder is replaced by an equal amount of Co (n-butyl methacrylate / ethyl methacrylate) (6 to 33% by weight).

The characteristics of the light filter assembly were that same as given in example 10

Example 12

In a mixture τοη 400 ml of butanone, 400 ml of ethanol and 2CO ml Ethylene chlorohydrin are 25 g of polymethyl ethacitrate and 20 g

109851/1851

BATHROOM 0RK31NAL

of the yellow azo dye Mr. 14 dissolved · The solution is in Ratio of 45 m2 / liter on a biaxially stretched polyethylene terephthalate film applied · The colored layer of the filter material thus obtained adheres very strongly to the polyester film. Without dye in the casting composition, the applied Layer no adhesion can be achieved.

Example 15

15 g of polystyrene with a molecular weight of 180,000 and 7 g of xriphenyl methane dye no. 7 are dissolved in a mixture of? 00 al butanone, 200 ml of ethanol and 100 ml of dioxane. The solution obtained is im. Ratio of 70 ia2 / liter applied to a biaxially stretched polyethylene terephthalate film. The colored layer adheres very well to the polyester film. Without a dye in the coating composition, no adhesion can be obtained.

Example 14-

The following casting composition will be one-sided in proportion of 45 n2 / liter on a biaxially stretched polyethylene terephthalate film applied from 65] i thickness:

Chloral hydrate 100 g

Resorcinol 30 g

30 yoige aqueous dispersion of colloidal er

Silica with a particle size of

15na (pH-Vert 9.5) 33 ml

Water 562 ml

Methanol 400 ml

10% aqueous solution of the disodium salt

the Heptadecylbenimidasoldieulfosic acid 5 ml «

On top of the dried layer, apply a second layer in the same way. Altitude of 55 m? /ld.ter from the following pouring composition applied: ·

Water 10 ml

Gelatin 10 g

Ethylene chloride 13 ml

25 / 'ethanolic balicylic acid solution 15 ml Methanol 762 ml

GV.525. - - ''

BATHROOM OFTIGlNAL 109851/185 1

Butanol 150 ml

StliyleiiglycolnonoiaethylBther- 50 ml Nitrocellulose 7 g

After drying, this layer becomes light-sensitive Gelatin silver halide emulsion applied, which emulsion is prepared as follows

A solution of 100 g of silver exnitxate in 1 liter of water is used 4-7 ° added within 30 seconds to a solution of 70 g of potassium bromide, 1 g of potassium iodide and 25 g of gelatin in 500 ml of water.

10 Hinutons later, 70 g of gelatin are added and another 30 ' Minutes later the emulsion is allowed to solidify · Bann If this emulsion is noodled, rinsed 5 times, with 40 g of beifung Gelatine was added and kept at 50 * for 4 minutes a Henge silver halide equivalent to 4 g silver is present

The back of the polyethylene terephthalate film support is with provided an antihalation layer by means of the following Casting composition in the ratio of 60 m2 / liter:

Cocstyrene / acrylic acid) (7Οι3θ Μο15έ) 4C g

Tr5 phenylaethene dye Mr. 5 20 g

Triphenylmethane dye Mr. 7 13 6

Methanol 200 ml

ethanol 200 ml

Acetone 6CC ml

A protective layer of the following composition is applied to this antihalation layer in a ratio of 50 m2 / liter :,

CoCEtyrene / sodium maleate) (50:50 mol ^) 7.5 g

10% aqueous polyhydric dieperession 7.6 ml

30 % i & e aqueous dispersion of colloidal silica

with a particle size νοηΈ nm (pH value: ^c ;, 5) 1 ntl

Potato starch. 5 E.

\. ^T aeser 8 ^ 8 ,? ml

Isopropanol 150 ml

109851/1851

12.5% aqueous solution of polyethylated
Nonylphenol 3.2 ml.

Before, during and also after the treatment in the photographic baths, good adhesion is achieved between the polyethylene terephthalate film and the silver halide emulsion layer
Antihalation layer spontaneously with complete discoloration

109851/1851 BAD

Claims (1)

Vf - Pat ent claims 1 .. Method of improving adhesion to an untreated Polyester film support of layers which contain polymeric binders, characterized in that the polymeric Binder intimately mixed with at least 15% by weight, "based on on the polymeric binder, of at least one dye, -der in its molecule, in addition to a carboxyl group, at least one hydroxyl group, one amino group, one halogen atom or contains a second carboxyl group, or at least one Dye containing two or more hydroxyl groups. 2. The method according to claim 1, characterized in that the . Polyester film is a polyethylene terephthalate film. 5. The method according to any one of claims 1 and 2, characterized thereby that the polymeric binder is Co (styrene / acrylic acid) (70:30 wt.%). ' 4. The method according to any one of claims 1 to 3, characterized in that that as a dye a> mixture of the following two Triphenylmethane dyes are used: COOH Cl .-C COOH COOH COOH 109851/1851 5. A polyeater film, characterized in that ^m T carries a colored layer, produced according to the method of one of claims 1 "to 4 · 109851/1851