CA1215624A

CA1215624A - Polyvinyl butyral laminates

Info

Publication number: CA1215624A
Application number: CA000450906A
Authority: CA
Inventors: Timothy G. Hiss
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1983-03-14
Filing date: 1984-03-29
Publication date: 1986-12-23
Also published as: EP0157965B1; AU2628084A; AU579313B2; JPS60210953A; EP0157965A1; US4469743A

Abstract

TITLE
POLYVINYL BUTYRAL LAMINATES
ABSTRACT OF THE DISCLOSURE
Polyvinyl butyral laminates with polyethylene terephthalate having an abrasion-resistant silanol coating and their preparation.

Description

TITLE
POLYVINYL BITTERLY LAMINATES
BACKGROUND OF THE INVENTION
Polyvinyl bitterly is widely used in combination with one or more layers of glass or other glazing material to provide a laminate which it resistant to shattering. In recent years, effort has been directed to the preparation of other composites which can be used in combination with glass to provide not only resistance to shattering but protection against abrasion and scratching when used as a component of a glazing material.
The preparation of laminates for use in automotive windshields present unusually stringent requirements. In addition to the basic requirements noted above, an automotive windshield must provide high impact resistance and excellent optical clarity. beyond this, for improved fuel efficiency, these characteristics should desirably be provided at a minimum weight. Previously, attempts to provide this combination of properties have often resulted in a laminate that performed well at ambient conditions, but crazed when exposed to especially high or low temperatures or humidity.
Summer The present invention provides an improved process for the production of polymeric laminates useful in conjunction with glazing material, as well as the resulting products, which are characterized by 30 outstanding abrasion resistance, clarity and adhesion to glazing material.
Specifically the instant invention provides a process for preparing a polymeric laminate comprising:

:~2::L562~

a) coating at least one surface of a biaxially oriented, dimensionally stable, polyethylene terephthalate film having a thickness of about 2-7 miss and a haze level of less than about 1.0~, to provide a dry thickness of about 1-20 microns with an organic sullenly coating composition comprising:
i) about 5-50 weight percent solid, the solid being partially polymerized and complemen~ally comprising about 10-69 tight Percent silica; bout 0.01 4 weight percent ox Acadia functional sullenly; up to 20 weigh percent of epoxy functional ~ilanol; and about 30-89 weight percent of organic ~ilanol of the general formula RSi(OH~3, wherein R is selected from methyl and up to 40~ of a radical selected from vinyl and phenol, and bout 95~50 weight percent vent, the solvent cvmpri~iny about 10-90 weight percent water and about 90-10 weight percent lower aliphatic alcohol and containing about 0.01-1.0~ non-ionic ~urfactant:
the coating composition having a pi of about 6.2-6.5;
and b) bonding the polyethylene terephthalate film at elevated heat and prowar Jo a sheet of plasticized polyvinyl bitterly to provide a laminate:
in which the surface of the polyethylene terephthalate not bonded to the polyvinyl bitterly it coated with the organic ailanol composition.
The instant invention further provide a polymeric laminate comprising, a) a sheet of plasticized polyvinyl bitterly;
b) a biaxially oriented, dimensionally table, polyethylene terephthalate film bonded to the I

polyvinyl bitterly and having a thickness of about 2-7 miss and a haze level of less thin about 1.0~; and c) a coating on the polyethylene terephthalate film having a thickness of about 1-20 irons the coating having been produced from an organic ~ilanol composition comparing (i) about 5-50 weight percent iodize, the slides being partially polymerized and complemental comprising bout 10-69 weight percent silica; abut 0.01-4 weight percent of Acadia functional ~ilanol; up to 20 weight percent of epoxy functional sullenly; and abut 30-89 weight percent of organic sullenly of the general formula RSi(0~)3, wherein it selected from methyl an up to 40% of a radical selected from vinyl and phenol, and (ii) about ~5-50 weight percent Solvent, the solvent comprising Ahab 10-90 weight percent water and about ~0-10 weight percent lower ~liphatic alcohol and containing abut 0.01-1.0~ non-ionic surfactant;
the coating composition having a pi of about 6.2-6.5;
end in which at let the efface of the polyethylene terephthalate film not bonded to the polyvinyl bitterly bear a coaxing (c).
Preferably, the polyethylene terephthalate film it treater on at least one wide to enhance the ability of the film to adhere to other arterial Detailed Description ox the Invention the preserJt invention it bayed on the discovery that in the preparation of a laminate of polyvinyl bitterly and polyethylene terephthalate having an abrasion resistant coating, the selection of specific components and prows verbal will result in a laminate particularly suitable or use I

with glazing materials which exhibits outstanding optical properties, integrity, resistance to crazing at extreme temperatures and humidity, abrasion resistance and adhesion to glazing materials. In addition, the laminates provide glazing materials with markedly improved penetration resistance.
The polyethylene terephthalate sheeting used in the present invention is biaxially oriented by stretching at least about 2.5 times in each of the longitudinal and transverse directions in the plane of the film. An important feature of the polyethylene terephthalate films used in the present invention is that they exhibit a haze level of less than about 1.0%, as measured according to ANSI/ASTM D
1003-61, using the haze meter specified in that test.
This haze level is attained by the absence of filler and uniform surface characteristics resulting from the processing conditions described in Altos, US.
Patent 2,779,684. In addition, the film is dimensionally stabilized, for example, by heating under tension as described in the Altos patent. This dimensional stabilization should be carried out at a temperature at least equal to the temperature of intended use.
One or both surfaces of the polyethylene terephthalate film may be conditioned to enhance their ability to adhere to other materials. However it has been found that the coating compositions used in the present invention provide excellent adhesion to the polyethylene terephthalate film without the need for flame treatment. However, it is often desirable to treat the surface of the polyethylene terephthalate film on the side which is to be bonded to the polyvinyl bitterly for improved adhesion. For example, the surface of the film to be bonded with .

the polyvinyl bitterly can be coated with an adhesion-promoting material, such as the water-permeable killed substratum described in the Altos patent to which reference is made above. In the alternatative, one or both surfaces can be conditioned by direct contact with a gas flame for a period of time sufficient to alter the surface characteristics of the treated material, but not for so long a period as to change the bulk properties of the film. Flame treating techniques previously known which can be used in the present invention include those described in Crudely US. Patent 2,632,921, ~ritchever US. Patent 2,648,097, Kritchever US.
Patent 2,S83,894 and Crudely US. Patent 2,704,382.
Preferably a reducing flame having a high fuel to oxygen ratio is used.
Other electrical and chemical surface conditioning treatments known to improve adhesion of polymeric films can also be used in the instant invention-The polyethylene terephthalate film is coated on at least one side with an abrasion resistant coating of the composition indicated above.
The coating is generally present in a final coating thickness of about 1-20 microns. The silica and organic sullenly components and the general preparation of these coating compositions are described in detail in Ubersax US. Patent 4,177,315.
However, in addition to the silica and organic sullenly described in that patent, the present coating composition further comprises, as about 0.01-4 percent of the solids in the coating composition, at least one azido-functional sullenly. The silanols are obtained from the Solon compounds of the general formula:

by c -So [R-(Z)c]d wherein R is an organic radical, X is selected from halo, hydroxy, alkoxy, airlocks, organ oxycarbonyl, Acadia, amine, and aside radicals; T is selected from alkyd, cycloalkyl, aureole, alkaryl, and aralkyl radicals; a is an integer from 1 to 3; b is an integer from 0 to 2; c is an integer from 1 to 10; d is an integer from 1 to 3; and abode equals 4; and Z
is selected from O R' O
.. . ..
o - C - CN2, -O CN3, and -SWEENEY
where R' is selected from hydrogen, alkyd, cycloalkyl, aureole and -COO" radicals; where R" is selected from alkyd, cycloalkyl, and aureole radicals.
These sullenness can be prepared as described in Thompson U S. Patent 3,706,592. The silanols are obtained by the addition of the sullenness to the aqueous components of the coating composition.
Preferably, the sullenness used to obtain the silanols in the coating composition are dip or trialkoxy sullenness, that is, compounds ox the above formula in which X is alkoxy of 1-3 carbon atoms and a is 1 or 3.
Also preferred are those sullenness in which Z
is sulfonyl aside, that is, -SWEENEY.
The R groups in the Solon compounds can vary widely, but will generally contain from 6-28 carbon atoms. In addition, the R group will generally be aromatic, and those Solon compounds in which R is an alkaline Arlene have been found to be particularly satisfactory.

So The coating solution, in accordance with the present invention, also contains about 0.01-1.0%, by weight of the solvent, of a non-ionic surfactant. A
wide variety of such surfactants is commercially available, including, for example, fluoro-surfactants available from ELI. duo Pont de Numerous and Company as Zanily* non-ionic fluoro-surfactants, and from EM as Flurried non-ionic fluoro-surfactants. Particularly preferred because of compatibility with the other components of the coating solution are silicone surfactants. Such silicone surfactants include, for example, polyalkylene oxide methylpolysiloxanes, such as those commercially available from Union Carbide as Solute* surface active copolymers and those commercially available from Dow Corning Corporation as silicone glycol copolymer fluids. One such silicone surfactant found to be particularly useful is the polyethylene oxide methyl selection commercially available from Union Carbide Corporation as Solute*
L-720.
The coated polyethylene terephthalate film is next laminated, under typical conditions of elevate Ed temperature and pressure, to a plasticized polyp vinyl bitterly sheet. The lamination is carried out to provide a polyethylene terephthalate film surface coated with the abrasion resistant coating opposite to the surface of the film bonded to the polyvinyl bitterly. The preparation of such polyvinyl bitterly sheeting is described, for example, in Vainness US.
Patent 2,720,501, Stamatoff US. Patent 2,400,957, and Woolworth US. Patent 2,739,080. The polyvinyl bitterly can contain a wide variety of plasticizers, as known in the art, including, for example, triethylene glycol di-2-ethylbutyrate, dihexyl * denotes trade mark ~lS6Z~L

a irate, if i e thy Len g luckily if inn twenty I, tetraethylene glycol d~-n-hept~lnoat~, praline ox ol~gon~rs and mixture ox these an oil or pl~3'cic'~ hers- Particularly ~atit3~tory polyvinyl S bitterly sheeting that ~ommerl~ally available ELM
Buta~ite*pla~tici~ed polyvinyl bitterly resin lotting ire I I. duo Pont de Namer an Company.
The polyvinyl bitterly used in lath present invention should exhibit a satisfactorily h level 10 of adhesion to glazing arterial This level of Edition it attained by Dinimi~ing thy adhesion control additives, for escalaple, used in tile polyvinyl bitterly sheeting. A alum ox about ~00 parts per million of potas~ilan based adhesion control additives 15 can be used in polyvinyl bitterly plastic Ted White tetraethylene glycol di-n-heptanoate. The level so adhe~on control additive should be such a Jo provide a peel force between the polyvinyl bitterly sheeting and the polyester film or glass of at least 20 bullet 5 pounds per inch.
The polyvinyl bitterly surface of the present laminate Ann be bonded to glass using elevated heat and pressure in conventional laminating techniques The present laminate can be owned to either a 25 Jingle layer ox glue or a glass lunate, such a a conventional thriller glass sandwich ~o~npri~ing two layers of lass and an ~nterDediate layer of polyvinyl utterly sheeting. In either case, the componentfi are typically assembled in the desired 30 order, heated to a temperature of Luke, and then either rolled or otherwise pressurized or played in a vacuum chamber to remove air trapped between the layer. The edges of the laminate are then typically elude tic prevent the reentry of air eighteen the I layers end the assembly then placed in an autoclave *denotes trade mark to effect the final bonding of the layers.
Typically, the autoclave is operated at a temperature of about 100-160C with an applied pressure of about 150-300 psi. The lamination is generally complete at about 5-120 minutes.
In the preparation of the laminates of the present invention in which a polymeric laminate of polyvinyl bitterly, polyethylene tPrephthalate and coating is laminated to glass, an additional glass sheet is conveniently placed on top of the coating during the laminating operation. To permit the easy removal of this glass sheet after the lamination operation a release agent or nQn-sticX film can be provided between the coating surface and the glass I sheet. In the alternative, a slip agent can be applied to the coated polyethylene terephthalate, so long as the release agent does not contain particles of sufficient size to adversely affect the optical characteristics of the finished product.
The resulting glass structure exhibits excellent optical characteristics, abrasion resistance, and penetration resistance. In addition, the polymeric laminates, alone or in combination with glass, show exceptional resistance to crazing at extremely high and low temperature and high humidity. As noted previously, the coating compositions used in the prevent invention provide excellent adhesion without the need of flame treatment or other surface modification.
The invention is further illustrated in the following samples, in which parts and percentages are by weight unless otherwise indicated.
Example 1-7 and Comparative Examples A-C
In Examples 1-3, 468 parts ox a 30 percent aqueous solution of colloidal silica were added to a :~2~56~

reaction vessel. the pi of thy solution was adjusted to 5.0 by the addition of glacial acetic acid. 342 parts of ~ethyltrimethoxysilane and 23 part of a 41 percent ethylene chloride solution of Hercules Coupling Agent S3076*trimethoxy Solon alkyl-aryl sulfonyl aside were added, and the solution was mixed for 6 hour at room temperature. 1062 part of a 2/1 isopropanol/water mixture was then added along with 0.4 part of a silicone urfactant. The pi of the resulting solution was adjusted to 6.2 by the addition of glacial acetic acid.
A Molly biaxially oriented polyethylene terephthalate film was then moated on both tides with the ~ilanol solution. Excess solution was allowed to drain from the polyethylene terephthalate film, which was then placed in an oven with a circulating air flow maintained at about 150~C for 30 minute in Example 1, at about 150C for 6 hours in Example 2, and at about 120C for 36 hours in Example 3. the times used in Examples 2 and 3 corresponded to reaction times for the Audi 6ilane as published by the manufacturer, The dried thickness of the coating was about 4 microns in Mach case.
In Example 4, the procedure of Example 1 WAS
25 repeated, except that 5 part ox S3076 inane sulfonyl wide solution was used instead ox 23 parts.
In Example 5, the procedure of Eagle 2 was repeated, except that 1 part of S3076 Solon ~ulfonyl Swede solution was used instead of 23 parts.
In Example 6, the procedure of Example 1 was repeated, except that the Molly biaxially oriented polyethylene terepthalate film was flame treated by contact with a reducing flame to improve adhesion characteristics prior to being coated with the sullenly solution.
*denotes trade mark SLUICE

In Example 7, the procedure of Example 1 was repeated, except that the 23 parts of S3076 inane sulfonyl aside was replaced with 12 part of S3076 Solon sulfonyl aside solution and 19 parts of gamma glycidoxypropyl trimethoxy Solon (Aye* from Union Carbide Corporation In Comparative Examples A and B, the procedure of Example. 1 and was repeated, except what the 23 part of S3076 Qilane Rulfonyl aside solution was replaced with 37 parts of gamma glycidoxypropyl trimethoxy Solon AYE prom Union Carbide Corporation). In addition, the Molly biaxially oriented polyethylene terephthalate film was flame treated by contact with a reducing flame to improve adhesion ~haracteriatics prior to being coated with the ~ilanol solution.
In Comparative Example C, the procedure of Comparative Example B was repeated except that the Molly biaxially oriented polyethylene tereph~halate film was not flame treated.
The coated films of Examples 1-7 and Comparative Examples A-C were tested for adhesion of the coating to the polyethylene terephthalate film as-produeed and after pushed of about 7 day and about 14 days in a chamber maintainer a about 53C
and at about 100 percent relative tumidity. The coating adhesion was determined by the tape adhesion parallel cut method (ASTM D 3002-71). A
pre~sure-~ensitive tape was applied to 3 3 pattern of 9 Corey of about inn Bides scribed through the coating on the polyethylene terephthalate film.
The tape was then quickly removed end the fraction of film surface within the quarts till covered by the coating was estimated. The coating applied according to the present invention was clearly superior to the *denotes trade mark ~Z~5~

Comparative Example in adhesion and adhesion retention. The results are summarized in Table I.
TABLE I
Adhesion OF COATING TO POLYETHYLENE TEREPHTHALATE FILM
TAPE PEEL TEST
Coating Remaining on Substrate (%) Aster 7 days After 14 day Example Descri~tionAs-Produced53C/100% RH53CLlOO~RH

1 Untreated PUT 100 89 1.9% azido-silane added; 30-minute cure at 150

2 Untreated PUT 100 100 1.9% azido-silan~
added; 6-hour cure at 150C

3 Untreated PUT 100 97 1.9% azido-silane added; 36-hour cure at 120C

4 Untreated PUT 100 98 0.4% azido-silane added 30-minute cure at 150C
Untreated PUT 100 61 0.08~ azido-silane added; 6-hour cure at 150C
3 6 Flame-treated PET; 100 100 67 1.9% azido-silane added;
30-minute cure at 150C
7 Untreated PUT 56 25 0.9% azido-silane and 3.7~ epoxy-inane added;
30-minute cure at 150C

~2~56~

A Flame-treated PET; 100 50 56 7% epoxy-silane added; 30-minute cure at 150~C
B Flame-treated PET; 100 100 67 7% epoxy-silane added; 6-hour cure at 150C
C Untreated PET; 80 0 0 7% epoxy-silane added; 6-hour cure at 150C

Abrasion Resistance In example 8, the procedure of Example 7 was repeated, except that the polyethylene terephthalate film was flame treated on the surface to be coated as in example 6.
In Comparative Example D, the procedure of example 6 was repeated except that the biaxially oriented, flame-treated, heat-relaxed polyethylene terephthalate f ill was not coated with any solution.
The coated films of Examples 1-8 and Comparative Examples A-D were compared for abrasion I resistance on the coated surface. The abrasion resistance was determined by the method described in ANSI Z 26.1-1977 Section 5.17. An integrating sphere, photoelectric photometer (ASTM D 1003-61-1977~ was used to measure the light 3 scattered by the samples be ore and after being exposed to 100 revolutions of an abrasive wheel carrying a load of 500 grams (Tuber Abrader, ASTM D
1044-76). The Examples of this invention were at least as abrasion resistant as those ox the Comparative Examples. The results are summarized in the following Table II.

Sty I
TABLE II
ABRASION RESISTANCE
TUBER ABRADER TEST
Change in Percent Haze Example Description 1 Untreated PET; 4.0 1.9% azido-silane added; 30-minute cur at 150C
2 Untreated PET; 2.0 1.9~ azido-silane added; 6-hour cure at 150C
3 Untreated PET; 3.1 1.9% azido-silane added; 36-hour cure at 12Q~C
4 Untreated PET; 1.2 0.4% azido-silane added; 30-minute cure at 150C
Untreated PET; 1.2 0.0R% azido-silane added; 6-hour 2 5 cure at 150 C
6 Flame-treated PET, 2.9 lo a~ido-silane added; 30-minute cure at lS0C

so TABLE II (keynoted.) ABRASION RESISTANCE
TUBER ABRAS~R TEST
Change in Percent Haze

5 Example Roy After 100 Cycles 7 Untreated PET; 5.4 0.9~ azido-silane and 3.7%
epoxy-silane added;
30-minute cure at 150C
8 Flame treated PET; Ox azido-silane and 1.4 3.7% epoxy-silane added;
30- minute cure at 150C
Flame-treated PET;
7% epoxy-silane added; Monet cure 1.6 a 150C
B Flame treated PET;
I epoxy-silane - added; 6-hour cure 1.4 a 150 C Untreated PET;
I epoxy-~ilane added; 6-hour cure 2.2 at 150C
D Flame-treated PET; 34 No coating Examples 9 and 10 Comparative Examples and F
CRAZE RESISTANCE OF THE COSTED LAYER ON THE
POLYETHYLENE TEREPHTHALATE FILM
In Example 9, the procedure of Example 3 was repeated, except that the polyethylene terephthalate film was heated to a temperature of about 120C while ~LZ~5~4 under tension. the coated film was laminated to polyvinyl bitterly sheeting having a hydroxyl content of about 23%, a potassium-based adhesion control additive content of about 250 Pam, a thickness of about 30 miss, and plasticized with about 28~ of tetraethyleneglycol di-n-heptanoate and further laminated to a sheet of 3/32-inch nominal thickness glass. The components were laminated at a pressure of 225 pounds per square inch and a temperature of about 120C for a period of 9 minutes to provide a unitary structure with excellent clarity.
In Example 10, the procedure of Example 6 was repeated, except that the polyethylene terephthalate film was heated to a temperature of about 150C while under tension. The coated film was laminated to polyvinylbutyral sheeting having a hydroxyl content of about 23%, a pota~sium-based adhesion control additive content of about 250 Pam, a thickness of about 30 miss, and plasticized with about 28~ of tetraethyleneglycol di-n-heptanoate and further laminated to a sheet of 3/32-inch nominal thickness glass The components were laminated at a pressure of 225 pounds per square inch and a temperature of about 135C for a period of 9 minutes to provide a unitary structure with excellent clarity.
In Comparative Example E, the procedure of Comparative example C was repeated, except what the polyethylene terephthalate film was heated to a temperature of about 120C while under tension. The coated film was laminated to polyvinyl bitterly sheeting having a hydroxyl content of about 23%, a potassium-based adhesion control additive content of about 250 Pam, a thickness of about 30 mill, and plasticized with about 28% of tetraet~yleneglycol I di-n-heptanoate and further laminated to a sheet of lo 4 3/32-inch nominal thicken glass. The components were laminated at a pressure of 225 pounds per square inch and a temperature of about 135C for a period of 9 minutes to provide a unitary structure with excellent clarity.
In Comparative Example F, the procedure of Comparative Example E was repeated, except that 298 parts of methyl trimethoxy Solon was used instead of 342 parts, and the flame treated polyethylene terephthalate film was replaced with a polyethylene terephthalate film having a water-permeable killed coating which it available from E. I. duo Pont de Numerous and Company as Crooner P-42. Also, the temperature of laminating was increased to about 149C and he time way increased to 90 minutes.
The laminates of Example 9 and 10 and Comparative Examples E and were compared or integrity or lack of crazing or cracking after expo use to environmental extremes. The laminates were compared as-made, after exposure to 53C and 100% relative humidity for 1 week and after exposure to -54C or 12 hours. The results are summarized in the following Table III.

I

TABLE III
CRAZE RESISTANCE OF THE
COATED LAYER ON THE POLYETHYLENE TEREPHTHALAT
CONDITION AFTER EXPOSURE TO:
Room 53C
Example Description Temp. -54C100% RHO
9 Azido,silane Clear Clear Clear added;
PET heat relaxed at 120~C; Curing and laminating at 120C
Azido-silane Clear Clear Clear added;
PET heat relaxed at 150~C; Curing and laminating at 150C
E ~poxy-silane Clear Crazed Clear added;
relaxed at 120C: Curing and laminating at 1~0 C
F Epoxy-~ilane in Clear -- Crazed coating; killed pre-coated PET

I

so Example 11 and Comparative examples and H
In Example 11, the procedure of Comparative Example A was repeated, except that the film was coated on one side with the sullenly solution and placed in an air circulating oven at about 1~0C for about 3 minutes. The uncoated side of the film was then laminated to polyvinyl bitterly sheeting having a hydroxyl content of 23%, a potassium-ba Ed adhesion control additive content of about 250 Pam, a thickness of about 30 miss, and plasticized with about I of tetraethyleneglycol di-n-heptanoate and further laminated to a sheet of inn nominal thickness glass. The films and glass were laminated at a pressure of 225 pounds per square inch and a temperature of about 135C for a period of 9 minutes to provide a unitary structure with excellent clarity.
In Comparative Examples and H, the procedure of Example 11 was repeated, except that the coated film was omitted in Comparative Example G and was replaced by 3/32-inch nominal thickness glass in Comparative Example H.
The laminates of Example 11 and Comparative Examples G and H were compared for penetration nest lance. The penetration resistance was determined by a changing height staircase method of dropping a 5-pound steel ball onto the 12-inch square laminates. The laminates ox Example 11 were clamped in the support frame to insure failure by penetration and the laminates of Example 11 and Comparative Example G were contacted by the ball on the polymeric side of the glass. The results obtained are summarized in the following Table IVY.

12~6~

TABLE IV
PENETRATION RESISTANCE OF LAMINATES
En Description Mean Surety Height (Feet) 11 PET/PVB/GLASS Laminate 31.7 G PVB/GLASS Laminate 11.3 H GLASS/PVB/GLASS Laminate 21.0 Example 12 and Comparative Examples I and J
The procedure of Example 11 was repeated, except that the biaxially-stretched, flame treated, heat-relaxed polyethylene terephthalate film was replaced with an adhesion-promoting colloid-coated biaxially stretched film available from E. I. duo Pont de Numerous and Company as Crooner P-42 in Example 12;
with an untreated, biaxially-stretched polyethylene terephthalate film in Comparative Example I; and with a biaxially-stretched polyethylene terephthalate film containing an inorganic slip additive, available from E. I. duo Pont de Numerous and Company as Mylar AYE, in Comparative Example J.
The laminate of Examples 11 and 12 and Comparative Examples I and J were compared or adhesion of the polyethylene terephthalate film to the polyvinyl bitterly. The film adhesion was determined by a 180~ peel adhesion test with the samples conditioned at 50~ relative humidity and the example grips moving a 20 inches per minute for a separation rote of 10 inches per minute (ASTM D
903-49 except for spud The results obtained are summarized in the following Table V.

12~56~4 TABLE V
ADHESION OF POLYETHYLENE TEREPHTHhLATE FILMS
TO POLYVINYL BOTTLE
.
Peel Adhesion 5 Example Description Pounds Per Inch 11 Flams-treated PET 9.1 12 Colloid-coated PET 7.7 Uncoated PET 3 . 8 J PET containing slip additive 0.04

Claims

I Claim:
1. A process for preparing a polymeric laminate comprising:
a) coating at least one surface of a biaxially oriented, dimensionally stable, polyethylene terephthalate film having a thickness of about 2-7 mils and a haze level of less than about 1.0%, to provide a dry thickness of about 1-20 microns with an organic silanol coating composition comprising:
(i) about 5-50 weight percent solids, the solids being partially polymerized and complementally comprising about 10-69 weight percent silica; about 0.01-4 weight percent of azido functional silanol; up to 20 weight percent of epoxy functional silanol; and about 30-89 weight percent of organic silanol of the general formula RSi(OH)3, wherein R is selected from methyl and up to about 40%
of a radical selected from vinyl and phenyl; and ii) about 95-50 weight percent solvent, the solvent comprising about 10-90 weight percent water and about 90-10 weight percent lower aliphatic alcohol and containing about 0.01-1.0% non-ionic surfactant;
the coating composition having a pH of about 6.2-6.5;
b) bonding the coated polyethylene terephthalate film at elevated heat and pressure to a sheet of plasticized polyvinyl butyral to provide a laminate in which the surface of the polyethylene terephthalate not bonded to the polyvinyl butyral is coated with the organic silanol composition.
2. A process of Claim 1 wherein the azido functional silanol in the coating solution is obtained by adding to the aqueous components of the coating composition an azido functional silane of the general formula:

wherein R is an organic radical, X is selected from halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl, azido, amine, and amide radicals; T is selected from alkyl, cycloalkyl, aryl, alkaryl, and aralkyl radicals; a is an integer from 1 to 3; b is an integer from 0 to 2, c is an integer from 1 to 10; d is an integer from 1 to 3; and a+b+d equals 4; and Z
is selected from , , and -SO2N3 where R' is selected from hydrogen, alkyl, cycloalkyl, aryl and -COOR" radicals; where R" is selected from alkyl, cycloalkyl, and aryl radicals.
3. A process of Claim 2 wherein R is an aryl radical of from 6-28 carbon atoms.
4. A process of Claim 2 wherein X is alkoxy of 1 to 3 carbon atoms, and a is 1 to 3.
5. A process of Claim 2 wherein Z is a sulfonyl azide of the formula -SO2N3.
6. A process of Claim 2 wherein Z is an azido formate of the formula -OCON3.
7. A process of Claim 3 wherein the aryl radical is an alkylene diarylene radical.
8. A process of Claim 1 wherein the non-ionic surfactant is a silicone surfactant.
9. A process of Claim 1 wherein the polyvinyl butyral contains less than about 400 parts per million of potassium based adhesion control agent.
10. A process of Claim 9 wherein the polyethylene terephthalate film is treated on at least one side to enhance the ability of the film to adhere to other materials.

11. A process of Claim 10 wherein the polyethylene terephthalate film is treated with a reducing gas flame to enhance the ability of the film to adhere to other materials.
12. A process of Claim 1 wherein one side of the polyethylene terephthalate film is coated with the coating composition and the polyvinyl butyral sheeting is bonded to the uncoated side of the polyethylene terephthalate film.
13. A process of Claim 1 further comprising bonding at least one sheet of glass to the surface of the plasticized polyvinyl butyral.
14. A polymeric laminate comprising, a) a sheet of plasticized polyvinyl butyral;
b) a biaxially oriented, dimensionally stable, polyethylene terephthalate film bonded to the polyvinyl butyral and having a thickness of about 2-7 mils and a haze level of less than about 1.0%, and, (c) a coating on the polyethylene terephthalate film having a thickness of about 1-20 microns, the coating having been produced from an organic silanol composition comprising (i) about 5-50 weight percent solids, the solids being partially polymerized and complementally comprising about 10-69 weight percent silica; about 0.01-4 weight percent of azido functional silanol;
up to 20 weight percent of epoxy funtional silanol;
and about 30-89 weight percent of organic silanol of the general formula RSi(OH)3, wherein R is selected from methyl and up to about 40% of a radical selected from vinyl and phenyl; and (ii) about 95-50 weight percent solvent, the solvent comprising about 10-90 weight percent water and about 90-10 weight percent lower aliphatic alcohol and containing about 0.01-1.0% non-ionic surfactant;
the coating composition having a pH of about 6.2-6.5;
and in which at least the surface of the polyethylene terephthalate not bonded to the polyvinyl butyral bears a coating (c).
15. A laminate of Claim 14 wherein the azido functional silanol in the coating solution is obtained by adding to the aqueous components of the coating composition an azido functional silane of the general formula:

wherein R is an organic radical, X is selected from halo, hydroxy, alkoxy, aryloxy, organo oxycarbonyl, azido, amine, and amide radicals; T is selected from alkyl, c?cloalkyl, aryl, alkaryl, and aralkyl radicals; a is an integer from 1 to 3; b is an integer from 0 to 2; c is an integer from 1 to 10; d is an integer from 1 to 3; and a+b+d equals 4; and Z
is selected from , , and -SO2N3 where R' is selected from hydrogen, alkyl, cycloalkyl, aryl and -COOR" raaicals: where R" is selected from alkyl, cycloalkyl, and aryl radicals.
16. A laminate of Claim 14 wherein R is an aryl radical of from 6-28 carbon atoms.
17. A laminate of Claim 14 wherein X is alkoxy of 1 to 3 carbon atoms, and a is 1 to 3, 18. A laminate of Claim 14 wherein Z is a sulfonyl azide of the formula -SO2N3.

19. A laminate of Claim 14 wherein Z is an azido formate of the formula -OCON3.
20. A laminate of Claim 14 wherein the aryl radical is an alkylene diarylene radical.
21. A laminate of Claim 14 wherein the non-ionic surfactant is a silicone surfactant.
220 A laminate of Claim 14 wherein the polyvinyl butyral contains less than about 400 parts per million of potassium based adhesion control agent.
23. A laminate of Claim 14 wherein the polyethylene terephthalate film has been treated on at least one side to enhance the ability of the film to adhere to other materials.
24. A laminate of Claim 23 wherein the polyethylene terephthalate film has been treated on both sides with a reducing gas flame to enhance the ability of the film to adhere to other materials.
25. A laminate of Claim 23 wherein the surface of the polyethylene terephthalate film bonded to the polyvinyl butyral has been treated with a water permeable colloid.
26. A laminate of Claim 14 wherein one side of the polyethylene terephthalate film is coated with the coating composition and the polyvinyl butyral sheeting is bonded to the uncoated side of the polyethylene terephthalate film.
27. A laminate of Claim 14 further comprising at least one sheet of glass bonded to the surface of the plasticized polyvinyl butyral.