DE2350289A1 - NON-ADHESIVE ADHESIVE LAYERS FOR POLYESTER FILMS - Google Patents

Description

AGFA ^L GEVAERTAG

it, K

PATENT DEPARTMENT

LEVERKUSEN

Non-stick adhesive layers for polyester films

The invention relates to "non-adhesive" adhesive layers for Polyester films, particularly polyethylene terephthalate films and on 'films containing these non-adhesive subbing layers.

By the term "non-stick adhesive layers", which is used hereinafter, it is meant layers which are applied to polyester films for the purpose of improving the adhesion of the hydrophilic layers to these films and which are characterized by the fact that they do not adhere to one another if they are pressed together at temperatures up to 130 ⁰ C and pressures up to 100 kg / cm.

When polyethylene terephthalate films are used as supports in the graphic arts industry, it is common to use them To provide a subbing layer to polyester films to improve the adhesion of other layers to them, such as photosensitive ones Silver halide emulsion layers, layers containing diazo compounds, matting layers for drawing purposes , antistatic layers, colored layers and the like.

A large number of polymeric compounds, namely copolymers, have been described as binders for these adhesive layers made of vinyl chloride and / or vinylidene chloride (British Patent 1,234,755), copolymers "made of butadiene (German Offenlegungsschrift 2 105 527) and copolymers of unsaturated chlorine or cyanoacetyl esters (British Patent 1,143,843). .,

AG 1180
GV 646

409817/1013

Most of these copolymers are applied to the polyester film surface attached in the form of latices for economic reasons; the most important reason is the fact that one these latices directly in water by known emulsion polymerization techniques so that the use of expensive organic solvents is avoided »These latices can be applied to the polyester film either before or after the biaxial orientation of the film base.

By a suitable selection of the copolymerization composition, the glass transition temperature of these latices is not selected too high, so that the latices have good film-forming and adhesive properties. The glass transition temperature of the copolymer .erwähnten usually varies between 20 and 50 ⁰ C. Accordingly, the Mischpolymerisatschichten become sticky when heated in drying ovens which use usually dry air of 80 to 12O ⁰ C. The polyester film, which is provided with its adhesive layer, should therefore have cooled down sufficiently when it leaves the drying chamber. If this is not the case, the adhesive layer will stick to the rollers and thereby be damaged or torn off.

The invention is based on the task, the stickiness of Adhesive layers on polyester films to degrade without their others Affect properties.

The invention relates to non-tacky adhesive coatings on polyester films containing ^ as binders copolymers of vinyl chloride, vinylidene chloride, acrylic or methacrylic Vinylestern or butadiene, and which are characterized in that they contain 5 to 100%, preferably _t 15 to 50 wt. -%, based on the weight of the binder, contain a silane compound which corresponds to the following formula:

AG 1180
GV 646

409817/1013

. ■■ ■ ν. ■ ■ ...

R ¹ R " ¹

in which:. · ■ -

R and E ^{1 are} each hydrogen, alkyl, chloroalkyl, aminoalkyl, alkoxy, hydroxyalkoxy, amino alkoxy, epoxy alkoxy, alkoxyalkoxy. Acetyloxy, vinyl or phenyl, the various alky 1- and alkoxy groups. Have 1 to -4 carbon atoms, and R "and R"'each. Cyano alkyl, aminoalkyl, amino alkoxy alkyl, epoxy ^ - alkoxyalkyl, alkoxycarbony! Alkyl, (meth) acryloxloxyalkyl, (meth) acrylamidoalkyl, chloroacetamidoalkyl, N- (aminoalkyl) aminoalkyl, bis (N-hydroxyalkyl) aminoalkyl, alkoxy , Hydroxyalkoxy, aminoalkoxy, epoxyalkoxy, alkoxyalkoxy, phenoxy, acetyloxy, and 3 -] [7-0xabicyclo- <4,1, OO-heptylJ-alkyl, where the various alkyl or alkoxy groups are 1 to 4-

have material atoms. ''

Suitable silane compounds according to the invention are, for example:

Dimethyl diphenoxy silane

Dimethyl bis (2,3-epoxypropoxy) silane

Diphenoxy-diphenyl-silane

Diethoxy-dimethyl-silane

Diethoxy-methyl- (4-aminobutyl) -silane.

Diethoxy-diphenyl-silane

2- (S.thoxycarbonyl) -propyl-diethoxy-silane ^:

Whore thoxy-me thy 1 - [[N- (2- amino ethy 1.) - 3-amino -2-me thy 1-propyl J * silane Whore thoxy-bis |] N- (2-hydroxyethyl) 3-3-aminopropyl-silane

3-chloropropyl-trimethpxy-silane ■

Trimetb.oxy-3- (methacryloyloxy) -propyl-silane

Trimethoxy-p- (2-aminoethyl) -3-aminopropyl-silane ...

Trimethoxy - [] 3- (2,3-epoxypropoxy) -propylJ-silane -,

Bi s (2-amino ethoxy) -me thy l-j [3- (2-amino ethoxy.) -Propy l3 ~ silane

Trimethoxy-24 3-r7-oxabicyclo- (4,1, ΰ-heptyl) J-ethyl-silane Triethoxy-silane

Mothyl-triethoxy-silane

GV.646 409817 / 1DV3. ^;

Triethoxy-vinyl-silane

Phenyl-triatho: xy-silane

2-Gyanät33yl-triethoxy-silane

3-aminopropyl-triethoxy-silane

^ -Ethoxyeaxbonyl-ethyl ^ triethoxy-silane (3-chloroacetamido-propyl) -triethQ: xy-sil · an (3-Acrylamidopropyl) -triethoxy-silane

Tripropoxysilane ■ *,

Tributoxysilane

Tris (2-methoxyetho: xy) -vinyl-silane -

Tris (2,3-epoxypropoxy) ethyl silane

Tetraethoxysilane

Tetrapropoacysilane

Tetrabutoxysilane ■ .....

Tetrabis (2,3 ~ dibydroxypropoxy) silane

Vinyl triacetoxy silane

These Sllanverbindungen become the casting composition of the adhesive layer in amounts of 5 to 100% by weight, preferably 15 "to 50% by weight in terms of the binder weight of the adhesive layer added.

Adhesive layers according to the invention for Po lye st or films that through Improved addition of silane compounds to their casting composition contain copolymers as binders, the main monomeric constituents of which are vinyl chloride, Contain vinylidene chloride, acrylic or methacrylic acid esters, vinyl esters or butadiene. Suitable copolymers are e.g. (Vinyl chloride / vinylidene chloride / n-butyl acrylate / itaconic acid) -

Copolymer (63: 30: 5: 2% by weight) | " (Vinyl chloride / vinylidene chloride / n-butyl acrylate / itaconic acid) -

Copolymer (58: 30: 10: 2% by weight) (vinylidene chloride / methyl acrylate / itaconic acid) copolymer (88i10: 2% by weight )

409817/1013

(Vinyl acetate / crotonic acid) copolymer (95-5% by weight) (Ethyl acrylate / methacrylic acid ^ mixed polymer (80:20 wt. ~%) (Butadiene / methyl methacrylate / itaconic acid) copolymer (47.5: 47.5: 5 weight percent).

These copolymers are preferred on the polyester film from aqueous dispersions attached, which one directly obtained from the interpolymerization of the various monomers by emulsion polymerization. The casting composition for the adhesive layer can be mixed with known casting additives, such as dispersants, spreading agents and thickeners, which are generally highly viscous water-soluble polymers, the sole purpose of which is to reduce the viscosity of the casting composition to bring it to the desired size. An overview of the thickening of the latices and the thickeners that can be used is in Houben-Weyl "Methods of Organic Chemistry, Macromolecular" Fabrics ", Volume 14/1, Pages 519 and 536, Georg Thieme-Verlag, Stuttgart (1961) to find.

The casting composition for the adhesive layer is applied to the polyester film applied in a ratio that, after drying, a layer is formed on the stretched polyester film, which has a thickness between 0.10 and 2 µm.

The tackiness of the adhesive layer and the reduction of this tackiness by adding the silane compounds according to the invention can be measured in a very simple way. Two strips of film of the material are placed in a heated press for 150 seconds. .wherein the two adhesive layers are facing each other. The press is then heated to 125 ° C. During the pressing process this temperature and a pressure of 70 kg / cm is maintained. A Carver Laboratory press from Fred S-. Carver, New York. Sticky layers that do not contain any silane compounds according to the invention Welded in such a way that the two strips of film cannot be separated from one another without damaging them.

AG 1180
GV 646

409817/1013

By adding the silane compounds according to the invention in amounts of 5 "to 100 wt. %, Preferably 15 to 50 wt Coverage of the adhesive layer, the adjacent layer, the gloss or the appearance of the layer, the adhesion of the adhesive layer to the polyester film support or the adhesion of the subsequent layers to the adhesive layer.

Polyester film base with adhesive layers containing silane compounds Can be used as a support in the manufacture of photographic materials, the light-sensitive silver halide included. They can also be used as a carrier in the production of drawing film, color film materials, antistatic Film materials and for all uses known in the graphic arts.

The following examples are particularly directed to the use of polyethylene terephthalate film as a support for the Adhesive layer and the other hydrophilic layers applied thereon aligned. However, the adhesive layer can also be on other polyester films, such as films from polyesters obtained from the polycondensation of glycol or mixtures of glycols with terephthalic acid or mixtures of terephthalic acid with small amounts of other dicarboxylic acids, such as Isophthalic acid, diphenic acid and sebacic acid. ·

The invention is illustrated by the following examples,

example 1

On an elongated polyethylene terephthalate film with a Thickness of 0.35 mm, the following casting composition is applied in a ratio of 75 m / liter:

AG 1180
GV 646

409817/1013

Mixed polymer A 350 ml

Copolymer B 1 _} 8 pi

Water 639 ml

Ammonium hydroxide until a pH of 8.15 is reached.

The copolymer A is a 20% by weight latex made of vinyl

Chloride, vinylidene chloride, n-butyl acrylate and itaconic acid (63: 30: 5: 2

The copolymer B is a 20% strength by weight latex made from ethyl acrylate and methacrylic acid (80:20

After drying, the polyester film becomes' up to 3.5 times stretched transversely together with the layer. Two strips of film of the resulting material are coated with opposing adhesive layers in a heated press as defined above pressed together.

After 150 seconds of heating at 125 ° C. and a pressure of 70 kg / cm ² , the two films are sealed and cannot be separated from one another without the adhesive layers being considerably damaged.

If the above-mentioned coating composition for the adhesive layer with 25 ml of trimethoxy- / 3- (2,3-epoxypropoxy) -propyl7-siian pro Liter is mixed and the coated films are heated and pressed in the same way in the press, separate the film strips immediately after cooling.

Both footage, one of which has an adhesive layer without Silane compound, the other an adhesive layer with a silane compound on the side of the adhesive layer with a second adhesive layer in a ratio of 35 m / liter coated from the following casting combination:

10% aqueous gelatin solution 100 ml

30% aqueous colloidal dispersion of

Silica x 50 ml

A-G 1180 ■

GV 646 409817/1013; . '

10% aqueous solution of 3-hydroxy

methyl-2,4-pentanediol '· "25 ml

10% aqueous solution of caprolactam 50 ml

10% aqueous solution of ULTRAVON W 5 ml

10% solution of HEXAPON D in methanol 2.5 ml

Methanol, 400 ml

Water 362.5 ml

10% aqueous solution of glyoxal 5 ml

ULTRAVON W is the trade name of Ciba AG, Switzerland, for a dispersant that consists of the disodium salt of heptadecylbenzimidazole disulfonic acid consists.

HEXAPON D is the trading name of the Societe. Chimique Elbeuvienne for a dispersant of the following formula: '

When the IT film materials so subbed with a gelatin silver halide emulsion layer as it is used for lithographic purposes, there can be no difference be noted for their photographic properties.

There is also no difference in the adhesion of the two photosensitive ones To find layers on the polyester carrier.

Example 2

An adhesive layer is applied to a longitudinally stretched polyethylene terephthalate film with a thickness of -0.63 mm in a ratio of 75 m ^ / liter from the following coating composition:

(Vinylidene chloride / methyl acrylate /,

Itaconic acid) copolymer

(88: 10: 2% by weight) as 20% latex 350 ml

Water 650 ml

After drying, the polyester film is stretched transversely up to 3.5 times. Two IT film strips of the received

AG 1180
GV 646

4098 17/1013.

Materials are pressed onto one another with opposing adhesive layers in a heated press as defined above. The press is heated to 125 ⁰ C and it is finally presented 150 sec. Pressed. The two film strips are then sealed and can no longer be separated without being ejected. "

Other patterns of the above elongated polyethylene handlebar Ephthalate films are made with the same casting composition covered, to which, however, 30 ml of trimethoxy-3- (methacryloyloxy) -propylsilane have been added per liter of casting composition. When two strips of film of this material are heated - and pressed together the film strips separate immediately after cooling. ·

The same good results are obtained if the above Silane compound by 25 ml of dimethoxymethyl / N- (2-aminoethyl) -3-amino-2-methylpropylJeilan is replaced *. ~~

Both film materials, the adhesive layers with silane compounds are covered with a second layer of adhesive, as in Example 1 given; this is followed by a gelatin silver halide emulsion layer of the type used for lithographic purposes will. The photographic properties of both materials are enhanced by the presence of silane compounds in the subbing layers not concerned. The adhesion of the emulsion layers to the support is also excellent.!

Example 3 "' ^:

Following the procedure of Example 1 it becomes more blue Polyethylene terephthalate film such as that used for X-ray purposes is used, covered with an adhesive layer that. as a binder the same (vinyl chloride / vinylidene chloride / n-butyl acrylate / itaconic acid) copolymer (63: 30: 5: 2% by weight), as in Example 1. If per liter of casting composition for the adhesive layer 10 ml trimethoxy-2 ^ 3- [7-oxabicyclo- (4,1, Q) -

AG 1180
GV 646

409817/1013

30th ml 1 ml 7, 5 ml 100. ml 665, 5.ml

^Λ0

heptyl-äthylt -silan are added, no seal is found in the hot-pressing test. ' / 35 ^ W5

The dried adhesive layers are applied in a ratio of 35 m / Liters covered with an adhesive layer of the following composition :

10% aqueous gelatin solution 80 ml

20% aqueous latex made from (Bujadiene / methyl methacrylate) copolymer (50:50 wt. (%) 50 ml

30% aqueous dispersion of colloidal Silicon dioxide. · "*." * 66 ml

.-10% aqueous solution of sodium sulf ο salicylate - · "

1,3-glycidyl-2-hydroxypropane

10% aqueous solution of ULTEAVON V (hands 1 sname)

Methanol
water

The subbed materials are covered with a photographic silver halide emulsion layer of the type used in X-ray photography. Regarding the photographic properties of the photosensitive materials, no difference can be noticed between the material without a silane compound in the adhesive layer and the material with a silane compound in the adhesive layer. Also, the adhesion of the emulsion layers to the support is excellent in both materials.

Example 4-

In accordance with the procedure of. Example 1 becomes a Made of polyethylene terephthalate film with an adhesive layer, the (vinyl chloride / vinylidene chloride / n-butyl acrylate / itaconic acid) copolymer (58: 30: 10: 2% by weight) as a binder.

In the first sample, the adhesive layer includes casting composition no silane compound, while in a second sample 4-0 ml trimethoxy - {] bis-N- (2-hydroxyethyl) -3-aminopropyl2J-silane pro Liters of casting composition are added.

AG 1180 GV 646 .

40 9817 / 10-1 3

73ζΟ2β9

The presence of the silane compound makes the second adhesive layer non-adhesive, "as is proven in the heated press»

The adhesive layer of both samples is covered with a matting layer 12 µm thick made from the following coating composition:

crystalline silicon dioxide (maximum particle size 10 µm)

Melamine formaldehyde resin
Phenyltrichlorosilane
Hydroxypropyl cellulose
Polyethylene oxide (mol. Wt. 20,000) ammonium salt of perf luorcapryläure. · -. _,. "'Water ■. ^

Ethylene glycol monome thy lather, _ ^; Acetone. "! '

Excellent drawing films for pencil and ink are obtained. The presence of the silane compound in the second material has no effect on the properties of the matting layer.

BoisOiel 5 ''

200 S. 100 S. 5 ml 20th ε 25th S. 40 ml 180 ml 430 ml

The copolymer, which forms the binder of the adhesive layer in Example 2, is replaced by the same amount of (butadiene / Methyl methacrylate / itaconic acid) copolymer (47.5: 47.5: 5 Gcw .-%) replaced. The coating composition is applied to the polyethylene terephthalate film support prior to stretching.

The adhesive layer does not stick if 25 ml of trimethoxy - [] 3- (2,3-cpoxyproppxy) -propyl] -silane can be added per liter of casting composition.

Example 6

A biaxially oriented polyethylene terephthalate film is made with an adhesive layer in a ratio of 75 m / liter from the the following composition is appropriate:

A-G 1180 '. '

GV 646. . '

409817/1013

(Viaylacetat / crotonic acid) copolymer (95: 5% by weight) "25 S

Methanol '500 ml.

Water 500 ml

Ammonium hydroxide until a pH of 8.5 is reached.

The dried layer appears sticky when it is pressed in the heated press described.

The addition of 5 g of trimethoxy- £ 3- (2,3-epoxypropoxy) propyl [] - silane per liter of casting composition ^ makes oils under the layer completely non-adhesive under the same circumstances.

Example 7 - '. . ·

A substantially amorphous polyethylene terephthalate film having thickness of approximately 2.2 mm a, is formed by extrusion of molten polyethylene terephthalate at about 280 ⁰ C on a Absehreckzylinder, cooled to about 75 ° C and then in a 'rolling-stretching device with variable speed elongated to "" 3.5 times its original dimension at 84 ^{° C.}

On the film stretched in this way, a ratio of 70 m / Liter a layer of the following casting composition applied :

Latex '335 ml

1,1,1-tri (hydroxymethyl) propane 12 g

Thickener 14.25 ml

Sodium salt of sulfosalicylic acid _ ■ '10 g.

Trimethoxy-j [3- (2,3-epoxypropoxy) propyl "j-

silane ~ 50 ml

Gelatin 5 g

10 & Lge aqueous solution of ULTEAVON W

(Trade name) '5 ml

Water 600 ml

The pH of the casting composition is increased with ammonia 8.2 set.

AG 1180
GV 646

409817/101 3

The latex used is 20% by weight and is made up of emulsions. copolymerization of vinyl chloride, vinylidene chloride, n-butyl acrylate and Itaconic acid (63: 30: 5: 2% by weight) prepared as described in British Patent 1,234-755.

The thickener is the copolymer of ethyl acrylate and methacrylic acid (80:20% by weight). It comes in the form of a aqueous 20% strength by weight dispersion added.

After the layer has dried, the film is placed in a tenter frame transversely stretched 3.5 times at about 87 ° C. the final thickness of the film is about 0.180mm. **

In an extension of the tenter frame, the film at 200 ⁰ C is heat-cured for about 1 min., While being maintained under tension. Then the film is cooled down. The thermoset and cooled film is passed through a relaxation zone, where it is heated for about 2 minutes at 125 ° C. under reduced tension so that it can shrink.

Both strips of thermoset and relaxed film material are put together in a heated press as described above, pressed together, the adhesive layers facing each other are. After 150 seconds of heating at 125 ° C and pressing together at

2
70 kg / cm the strips separate spontaneously after cooling.

If the trimethoxy - (] 3- (2,3-epoxypropoxy) -propylJ-silane in the above-described casting composition is omitted, the two strips of film are compressed as defined above is sealed and can no longer without tearing the Film strips are separated. *

The heated film continues to be treated with a corona discharge and provided with a gelatin silver halide emulsion layer as used in X-ray photographic film material will. The layers of the thus obtained photographic Materials show very good adhesion to the polyester film carrier in both wet and dry condition. A-G 1180

GV 646 40 9817/1013

Claims (2)

Claims 1. Non-adhesive adhesive layer on polyester film, which as Binder Copolymers of vinyl chloride, vinylidene chloride, Acrylic or kethacrylic acid esters, vinyl esters or butadiene contains., Characterized in that the casting composition of the adhesive layer in terms of the binder weight, 5-100 crew% of a silane compound of the following general Formula contains: . _EE " in which: R and R 'each hydrogen, alkyl, chloroalkyl, aminoalkyl, alkoxy, Hydroxoxyalkoxy, amino alkoxy, epoxyalkoxy, alkoxyalkoxy, Acetyloxy, vinyl or phenyl, where the various alkyl and alkoxy groups have 1 to 4 carbon atoms, and R "and R" 'each cyanoalkyl, aminoalkyl, aminoalkoxyalkyl, Epoxyalkoxyalkyl, alkoxycarbonylalkyl, (meth) acryloyloxyalkyl, (Meth) acrylamidoalkyl, chloroacetamidoalkyl, H- ( amino alkyl) -amino alkyl, bis (hydroxyalkyl) -aminoalkyl, Alkoxy, hydroxyalkoxy, aminoalkoxy, epoxyalkoxy, alkoxyalkoxy, Phenoxy, acetyloxy, and 3- £ 7-oxabicyclo- (4-, 1,0) -heptylJ-alkyl, above the various alky 1 ^ or alkoxy groups Have 1 to 4 carbon atoms. 2. Non-adhesive adhesive layers according to claim 1, characterized in that characterized in that, with regard to the weight of the binder, it contains between 15 and 50% by weight of the silane compound are. 3- Non-adhesive adhesive layers according to claim 1 or 2, characterized in that the polyester film is made up of a film Is polyethylene terephthalate. AG 1180
GV.646 409817/1013 Correctly sticky adhesive layers according to one of the preceding
Claims, dadu-rch characterized that the silane compound "Trime" bhoxy- £ 3- (2,3-epdxypropoxy) -propyl]] - silane, trimethoxy- £ 3- (aethacryloyloxy) -propyl] -silane, dirnethoxymethyl- [ ] N- (2- aminomethyl) -5-amino-2-iaethyl-pi ^> opyl ^ j-silane, G? Rimethoxy-2-f3-f? -Oxabicyclo (4-, i, (^ - heptyl.]] -äthyll-silan or trimethoxy-J ^ bis-li (2-hydroxyethyl) -3 - aminopropyl ^] - sila ^ is. AG 1180
CV. 646 409817/1013