CA2014175A1 - Bonding polyvinyl butyral and polyurethane - Google Patents

Abstract

06-12(9859)A

ABSTRACT OF THE INVENTION
BONDING POLYVINYL BUTYRAL AND POLYURETHANE
A process for inseparably bonding layers of plasticized partial polyvinyl butyral and polyurethane which comprises chemically reacting hydroxyl groups of the partial polyvinyl butyral with isocyanate groups associated with formation of the polyurethane.

Description

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ONDING POLYVINYL BUTYRAL AND POLYURETHANE

BACKGROUND OF THE INVENTION
This invention relates to laminated safety glass and more particulaxly to a process for bonding layers of plasticized polyvinyl butyral (PVB) and polyurethane to form a polymeric laminate for use in such structures.
The present most widely used vehicle wind-shield is a three ply laminate comprising an energy absorbing plastic sheet sandwiched between two glass sheets. Such windshields can absorb a blow from an occupant's head without shattering and in doing so dissipate significant impact energy as the windshield undergoes essentially plastic deformation.
With such a three ply structure the occupant can receive facial lacerations from sharp edges of broken glass of the inner glass sheet of the wind-shield. To reduce this the inside glass surface has been coated or covered with a protective plastic layer intended to prevent an occupant's skin from contacting the glass and further increase the penetration resis-tance of the conventional three ply laminate. Such protective layer usually comprises two or more plies and is known as an anti-lacerative shield (ALS).
~5 Alternatively, to address this occupant laceration problem and improve vehicle fuel efficiency by reduc-ing weight, it has been proposed to reduce ~he conven-tional three ply structure to a single glass l~yer having a layer of energy absorbing material and a protective covering on its inboard side. Such a composite structure is known as a bilayer windshield and is especially suitable for ease of fabrication into relatively complex shapes.
As typically represented by U.S. 4,584,229, for bilayer and ALS structures the prior art proposes ~' ~" , .

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,, spraying special adhesive polyurethanes (PU) onto the glass layer over which is then deposited a different, wear-resistant inboard polyurethane layer. However, sprayed liquid adhesive coatings are not usually encountered in commercial glass laminating systems which have long been based on polyvinyl butyral (PVB) with which laminators are quite familiar in handling and use. Such polyvinyl butyral is more par~icularly described as partial polyvinyl butyral insofar as containing about 17 to 25 weight % residual hydroxyl groups which promot~ adhesion to the glass. Moreover, plasticized polyvinyl butyral or partial polyvinyl butyral ~interchangeably referred to as "PVB") as an energy absorbing layer (sometimes referred to as l'PVB
layer") has performance advantages over polyurethane.
For example, the impact tear resistance of a PVB layer is greater than polyurethane over most of the opera ting temperature range encountered in vehicle window use. At thicknesses providing the expected degree of safety in use, the component cost of an all-polyure-thane system is about twice that of one containing a PVB layer. Optical clarity can and has been designed into plasticized PVB sheet supplied by sheet manufac-turers to glass laminators which may be more difficult to achieve when being developed by depositing liquid polyurethane susceptible to uneven gravity flow on a contoured automotive window panel.
In copending application Serial No. 279,742, Filed December 5, 1988 and assigned to the assignee of this application, a polymeric laminate contalning a PVB layer for laminating to a glass sheet in bilayer and ALS applications is disclosed. As known, such a soft, vulnerable PVB layer must be covered with an additional inboard layer for various per~ormance rea-sons which include: i) preventing plasticizer losssince if this occurs impact absorption is dissipated;

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and ii) protection from abrasion, staining, cleaning solvents and various forms of d~maging environmental exposure, one or more of which are likely to be encountered in use. Obviously, the bond between the S PVB and covering layer is important and desirably strong to preserve the integrity of the laminated system in use. Before laminating to a PVB layer some plastic covering layers require initial surface treatment or the presence of a separate tie layer to promote adhesion. Nevertheless, over time a reduction in bond strength has been noted with prior art systems of this latter type. It would be desirable in a polymeric laminate for bilayer and ALS applications containing a PVB layer to provide a strong bond with a protective covering layer with which it is in face-to-face contact.
SUMMARY OF THE INVENTION
v Now bond improvements have been made which facilitate using plasticized PVB sheet in bilayer and ALS safety glass applications.
Accordingly, a principal object of this invention is to provide a process for forming a tena-cious interfacial bond between layers of plasticized PVB and PU.
Another object is to provide such a bond without use of an adhesive.
A further object is to provide such a process while simultaneously developing a functional PU covering over the PVB layer which is specifically tailored for ALS and bilayer applications.
These and other objects are accomplished by providing a process for inseparably bonding layers of plasticized partial polyvinyl butyral and polyurethane which comprises chemically reacting hydroxyl groups of the partial polyvinyl butyral with isocyanate groups associated with formation of the polyurethane.

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Urethane groups having the formula O
Il --O~C--NH--bond the layers. Such reaction preferably occurs in coating the PVB layer with a liquid polyurethane composition having free terminal isocyanate groups on the polyurethane chains which react with hydroxyl groups of the partial polyvinyl butyral. The process preferably includes curing to cross-link the polyure-thane preferably using a photoinitiator and exposureto ultraviolet ( W ) light.
DETAILED DESCRIPTION OF THE INVENTION
Partial PVB as plasticized sheet for use with glass in laminated glazings must contain vinyl alcohol groups in the polymer primarily for reaction with SiO~ groups on the glass surface to develop the desired adhesion for impact absorption. In broadest aspects this invention recognizes that in providing a polymeric laminate for bilayer or ALS applications, isocyanate groups associated with application of a polyurethane layer on such PVB sheet can react with hydrogen atoms of hydroxyl groups on the surface of such partial PVB sheet to develop a strong, insepar-able chemical bond functionally linking the partial PVB and polyurethane layers together. It is critical in the invention that residual free isocyanate (NCO) groups be available for reaction with hydroxyls of the partial PVB at the time the PU Iayer or the mixture to form such layer is brought into contact with the plasticized partial PVB sheet. More specifically, the isocyanate groups for developing the inventive bond are actually terminal isocyanate groups on polyure~
thane chains which chemically link the two layers together. Toward this end, when developing ~he bond in conjuction with formation of the PU, the NCO/O~
equivalent ratio (reactive ~CO groups/reactive OH
groups) in the reaction mi~tuFe is prefer~bly greater `
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than 1/1, e.g. about 1.01/1 to 1.5/l and most prefer-ably l.01/1 to 1.3/1. A section of partial PVB and polyurethane chemically linked by a urethane group has the following representative formula:

Il I
HN-R-N-C-O-Rl-O-I H
o=C

o o 0 CH
(CH2)2 where R and Rl ~to be further described) respectively originate from diisocyanate and polyol used to form the polyurethane. In orming the linkage shown an ~5 active hydrogen atom from a hydroxyl group of a vinyl alcohol segment of the partial PVB moves to a nitrogen atom of an 0=C=N- isocyanate group to break the C=N
double bond and provide the urethane --O--C--N~--linkage between the partial PVB and polyurethane backbones.
Though it is preferred, as more fully hereafter described, to develop the bond linking the layers together as a result of applying the polyure-thane formulation to the surface of the PVB layer, it is possible to initially block the reactive terminal isocyanate group and, by mild exposure to heat after contact with the PVB layer, to u~block and convert the isocyanate groups to reactive sites available to react with hydroxyls of the partial PVB.

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With the foregoing in mind, the partial PVB
resin in the inventive polymeric laminate comprises, on a weight basis, from about 17 to 25 wt. % hydroxyl groups, calculated as polyvinyl alcohol, O to 4 wt. %
acetate groups, calculated as polyvinyl acetate with the balance being butyraldehyde acetal. Before shaping into sheet, the partial PVB resin must be plasticized with from about 20 to 80 parts, preferably 25 to 45 parts plasticizer per 100 parts resin.
Plasticizers commonly employed are esters of a poly-basic acid and a polyhydric alcohol. Particularly suitable plasticizers are triethylene glycol di-(2-ethylbutyrate), dihexyl adipate, dioctyl adipate, mixtures of heptyl and nonyl adipates, dibutyl seba-cate, polymeric plasticizers such as the oil-modified sebacic alkyds, and mixtures of phosphates and adi-pates such as disclosed in U.S. No. 3,841,890 and adipates and alkyl benzyl phthalates such as disclosed in U.S. No. 4,144,217. Other suitable plasticizers are well known or will be o~vious to those skilled in the art.
The process for preparing PVB sheet involves mixing the partial PVB resin with plasticizer and melt shaping the plasticized resin according to known prior art techniques to form the sheet. Systems for forming such sheet typically involve extrusion by forcing polymer melt through a sheeting die having temperature-controlled die lips, or by using a die roll system where molten polymer issuing from the die is cagt onto a specially prepared surface of a roll closely adjacent the die exit to impart the desired~surface characteris- -tics to one side of~the molten polymer. Thus, a roll having a surface with minute peaks and valleys forms a sheet from polymer cast thereon with a rough surface generally conforming to the~peaks and valleys of the roll surface. Further details of construction of a :: ~ : : :

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die roll system are disclosPd in U.S. No. 4,035,549, col. 3, line 46 through col. 4 line 4, the content of which is incorporated herein by reference.
Alternative techniques known in the art may be employed in association with extrusion to produce a rough surface on either or both sides of the extruding sheet. These involve the specification and control of one or more of the following: polymer molecular weight distribution, water content of the melt, melt and die exit temperature, die exit geometry etc.
Systems describing such techniques are disclosed in U.S. Nos. 2,904,844; 2,909,810; 3,994,654; 4,575,540 and published European Application No. 0185,863.
In addition to plasticizers, the PVB sheet may contain other additives such as dyes, ultra violet light stabilizers, adhesion control salts, anti-oxidants and the like. The sheet may also be provided with an integral, gradient color band during extrusion by known systems as typically disclosed in U.S.
4,316,868.
Any PU formed by reacting one or more polyisocyanates, such as diisocyanates~ with one or more polyols may be used provided isocyanate groups are present which are capable of chemically reacting with hydroxyl groups of partial PVB of the sheet on which the polyurethane is deposited. Though systems with less than the stoichiometric amount of isocyanate required to react with polyol are usable, for optimum polyurethane performance properties excess diisocyan-ate in the polyol reaction is preferred so that an NCO
group of a polyisocyanate reacts with residual hydroxyl while another NCO group becomes incorporated into a PU
chain. This excess is defined by the isocyanate/
hydroxyl (NCO/OH) equivalent ratio (i.e. the ratio of reactive isocyanate to hydroxyl groups) in the formulation used to form the PU, taking into account the molecular weight of the diisocyanate(s~ and - -; . ' ' ' ' .

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polyol(s) employed. This NCO/OH equivalent ratio should not be too high to avoid bubbles from moisture absorptlon nor too low to avoid tackiness and smudging of the PU and less than optimum adherence to the PVB
substrate. With this in mind, the NCO/OH equivalent ratio should be greater than l/1, preferably about 1.01/l to about 1.5/1, and most preferably 1.01/1 to 1.3/l.
Usable diisocyanates and diisocyanate mixtures include aliphatic and cycloaliphatic diisocy-anates such as he~amethylene diisocyanate; 2,4,4-tri-methyl 1,6 hexamethylene diisocyanate; 1,4-bis ~3-isocyanotopropyl) cyclohexane; 1,3 or 1,4-methyl cyclohexyl diisocyanate; isophorone diisocyanate;
3-isocyanotomethyl 3,5,5-trimethylocyclohexylisocy-anate (IPDI); methylene bis (4-cyclohexylisocyanate);
methylene bis (cyclohexyl 3-methyl 4 isocyanate) 2,2-bis (4-isocyanotocyclohexyl) propane; meta and para tetramethyl xylene diisocyanate (TMXDI) and the like. Usable aromatic diisocyanates include ortho, meta or para toluene diisocyanate; diphenyl methane diisocyanate; meta and para phenylene diisocyanate;
ortho and para alkyl phenyl diisocyanates; 2,2-bis(4-isocyanatophenyl) propane and the like. Diiso-cyanates of molecular weight about 168 to about 310 having NCO groups bound to primary aliphatic carbons and/or NCO groups bound to secondary or tertiary aliphatic or cycloaliphatic carbons are preferred, with methylene bis (4-cyclohexylisocyanate~ most preferred, particulary because of its ultraviolet light stability.
Any polyol which represents the soft segment o the polyurethane chain is usable such as polyether or polyester polyols including mixtures thereof.
Representative polyols include diols such as 1,4-butanediol; 1,4-butenediol; 1,5-pentanediol; 1,6-2 ~

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hexanediol, neopentyl glycol; polyether glycols con-taining primary hydroxyl groups such as polytetra-methylene ether glycol; polyether diols containing secondary hydroxyl groups such as adducts of propylene oxide; polyether diols containing prlmary hydroxyl groups capped with ethylene oxide; polyether triols with secondary hydroxyl groups such as glycerine-propylene oxide adduct; polyether triols containing primary hydroxyl groups such as glycerine-propylene iO oxide adduct capped with ethylene oxide; and polyester glycols such as poly (diethylene glycol adipate); poly (neopentyl glycol) adipate; poly (1,6-hexanedioladi-pate); and the like.
To obtain the desired balance of polyure-thane performance properties, more than one polyol containing two or more hydroxyl groups per molecule may be required, the higher the polyol molecular weight the more flexible and rubbery will be the polyurethane, while lower polyol molecular weight promotes hardness. Also, as polyol molecular weight increases the hydrolytic stability of ~he polyurethane (i.e. its propensity to absorb atmospheric moisture and develop haze) is reduced and vice versa.
Generally polyol molecular weight should be between about 250 to about 8,000 and it should have hydroxyl functionality (i.e. the number of hydroxyl groups per molecule) of two or three, e.g. be a polyhydric, preferably aliphatic, alcohol.
The reaction forming polyurethane is prefer- :
ably catalyzed with known, conventional catalysts used for this purpose. Typical catalysts include dibutyl tin dilaurate; dibutyl tin maleate; dibutyl tin dilauryl mercaptide; dimethyl tin dichloride; dibutyl tin diacetate; stannous octoate; cadmium octoate;
bismuth stearate; zinc octoate; stannous napthenate;
stannous oxalate; stannous stearate; bismuth nitrate;

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zirconium octoate; triphenyl antimony dichloride and the like.
Though uncrosslinked polyurethane may be inseparably bonded to PVB sheet according to the invention in the manner described, for optimum performance in a polymeric laminate for bilayer and ALS applications the polyurethane is preferably cross-linked and therefore thermoset by including a cross-linking agent in the formulation and curing the polyurethane after deposition of the formulation on the PVB sheet by exposure to heat alone or successive exposure to heat and radiation, such as ultraviolet (W ) light or electron beam. Cross-linking agents usable in thermally curable systems include trimethy-lol propane, glycerol, low molecular weight polyether triols, polyether triols with a functionality greater than two, including mixtures of the foregoing. When W curing is employed the cross-linking system can include trimethylol propane triacrylate, trimethylol propane trimethacrylate, ethoxylated trimethylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentacrylate, pentaerythritol triacrylate and the like including mixtures thereof.
When W curing is employed, it is desirable to include a photoinitiator in the formulation.
Representative photoinitiators include:
l-hydroxycyclohexylphenylketone mixed with ben2ophe-none available from Ciba Geigy as Irgacure 500;
l-hydroxycyclohexylphenylketone available from Ciba Geigy as Irgacure 184; 2,2-diethyoxyacetophenone available as DEAP from Upjohn; 2,2 di-sec-butoxy acetophenone available as Uvatone 8301 from Upjohn;
diethoxyphenolacetophenone available as Uvatone 8302 from Upjohn and 2-hydroxy-2-methyl-1-phenyl propan-l-one available as Darocur 173 from EM Industries.

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Cross-linkable polyurethanes within the scope of the invention may be initially in the form of a prepolymer composition where isocyanate and polyol components are partially reacted at elevated tempera~
tures to form a viscous liquid mixture which is then diluted to a manageable viscosity with cross-linking agent and photoinitiator and, after deposition on the PVB sheet, then cured. The average molecular weight of the prepolymer should be about 800 to about 13,500 and it should have an NC0 content of 3.6 to 11 wt %.
The prepolymer should be used relatively promptly after preparation since viscosity increases noticably with shelf life and if too high it cannot be conveni-ently applied using continuous, commercial coating equipment. Time at curing temperatures should not be too long to avoid adversely affecting the PVB sub-strate, for example evaporating plasticizer.
The foregoing curing concerns are avoided with an alternative, preferred dual cured (radiation, e.g. W or electxon beam followed by heat) formulation using monomeric constituents combined at room tempera-ture (20-25C) to form a low viscosity liquid mixture which can be readily continuously deposited on endless PVB sheeting by commercial coating equipment. After deposition, radiation (e.g. W ) exposure partially cures the composition to a tack~free state followed by heat curing to a fully cross-linked condition by exposure to elevated temperature on the order of about 70-100C for up to about 60 min. This alternative is particularly desirable since curing can be relatively rapid to facilitate the manufacturing process and time-temperature exposure of the laminate can be minimal. More specifically, separate solutions of:
i) monomeric diisosyanate and photoinitiator and ii) monomeric polyol(s), catalyst and hydroxylated acryla-ted monomers are prepared and then mixed together at - .

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-room temperature (20-25C.) to form the low viscosity mixture (i.e about 200 to lOOo cps or o.2 to 1.O Pa.s, preferably 200 to 600 cps - 0.2 to 0.6 Pa.s) which is then evenly deposited on the PVB sheet by a coating apparatus. The uncured coating is then sequentially exposed to W light and elevated temperature. The preferred dual cure formulation requires both W and thermal curing with either of such cure steps alone being inadequate to develop the desired balance of polyurethane properties. This preferred dual cure formulation comprises: i) cycloaliphatic diisocyanate having NCO groups chemically attached to secondary cycloaliphatic carbons, e.g. methylene bis(4-cyclohex-ylisocyanate) and ii) polyether diol containing primary or secondary hydroxyl groups having a molecu-lar weiqht between about 250 to about 8,000 selected from: polytetramethylene ether glycol (molecular weight about 250-l,000); adducts of glycerine and propylene oxide (molecular weight about 1000); adducts of glycerine and propylene oxide capped with ethylene oxide (molecular weight about 6200) and mixtures thereof.
The polyurethane layer of the polymeric laminate of the invention can vary in thickness and be a preformed sheet or film of thickness about 10 to 50 mils (0.254-1.27 mm) or preferably is an initially li~uid coating of thickness after drying on the order of l to 10, preferably 4 to 8 mils (O.0254-0.254 mm -0.1-0.2 mm).
Known additives can optionally be included in the formulation forming the PU layer such as, for example, wetting agent(s), exposure stability agents, slip agents to improve coefficient of friction and the like. Selective use of surfactants can provide antistatic properties. The PU layer itself may be coated with functional layer(s), for example, to .: :
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further enhance abrasion resistance, to lower coeffi-cient of friction etc.
The invention is further described in the following examples which are for illustration only and not to limit or restrict the invention. Unless otherwise indicated all quantities are expressed in weight.
The following tests provided the values and results tabulated in the examples.
Nitrogen - by elemental analysis using a Carlo Erba 1106 Analyzer which is accurate to about O.1%.
Isocyanate Groups - according to the proce-dure in "Handbook of Analysis of Synthetic Polymers and Plasticsl', Urbanski, J., et al, p. 328, John Wiley and Sons Inc.,-N.Y., 1977.
Boil Test - the polymeric laminate was press laminated to glass at 350F. (177C), 180 psi ~1240 kPa) to simulate a bilayer product and then placed in boiling water for six hrs. The polymeric laminate was then manually pèeled from the glass and the quality of adhesion of the layers was checked by manualIy stretch-ing the laminate to determine if the PU layer delamina-ted from the PVB layer.
Tape Test - ASTM D3359-78 - on the pol~meric laminate~

These show the chemical reaction between hydroxyl groups of plasticized partial PVB resin in sheet form and diisocyanate of a urethane formulation. ?
The sheet (called TQ-178 sheet) was 30 mils (0.76 mm) thick and made of PVB resin having a residual hydroxyl content of 20.5 wt. % which had been plasticized with 35 par~s of dihexyl adipate per 100 parts resin.

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EXAMPLE 1 (control) Cured PU film from K. J. Quinn Co. of Seabrook, N.H. chemically identified as alicyclic polyurethane (L-413-03) was press laminated at 300F
(148.9C) for 5 min to TQ-178 sheet. After cooling the PU film could be delaminated with minimal effort -i.e. less than O.l lbs per in width (0.0175 kN/m) on an Instron tester. It was concluded that no reaction between hydroxyls of the PVB and the PU had occurred.
The use of various adhesion promoting agents or surface modification techniques were to no avail in improving adhesion between the layers.

A few drops of methylene bis(4-cyclohexyliso-cyanate) (availablP from Mobay Chemical Corp., Pittsburgh, PA as Desmodur W) were deposited on a small section of TQ-178 sheet. The coated sample was covered with a beaker and aged overnight at room temperature. The coated surface was washed with hexane to remove residual free diisocyanate and then analyzed for nitro~en with the result shown in Table I.

The procedur~ of Example 2 was repeated except the diisocyanate was ~irst mixed at room temperature with liguid dibutyl tin dilaurate, a catalyst for urethane reactions, and aged for four hours.

The procedure of Example 2 was repeated except the coated sample was held at 50 C for four hours.

The procedure of Example 3 was repeated except the sample coated with catalyzed diisocyanate was held at`50C for four hours.

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TABLE I
~xample ~ N
Untreated TQ-178 Sheet (control) <0.10 2 <0.10 3 0.21 4 0.27 0.33 The above results support ~he occurrence of a chemical reaction between hydroxyls in the PVB sheet and diisocyanate when catalyzed thermally (E~. 4) or chemically (Ex. 3~ or both thermally and chemically (Ex. 5), the increase in nitrogen content evidencing the presence of -OC0-N~- linkages at the hydroxyl sites.
EXAMoeLE 6 This shows a chemical linkage tvia the reaction of Examples 3-5 above~ between vinyl alcohol groups in plasticized PVB sheet and a Pu coating lay~r formed in conjunction with development of such linkages by reaction of diisocyanate and glycol. The formula-tion was:
Component Charge~q) Methyle~e bis(4-cyclohexylisocyanate) (Desmodur W) 58.10 1Polyether triol 48.05 2Polyether capped triol 51.95 Trimethylol Propane (crosslinker) ~T~P) 10.97 Dimethyl tin dichloride (catalyst)200 ppm Additives: :
FC-430 (3~) (slip agent) 0.51 Dow Corning 193 (surfactant) 0.17 Dow Corning 57 (leVeliAg ageAt) 300 ppm .

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Niax LG-168, mol. wt. = 1000, from Union Carbide Corp., Danbury, CT, syntheslzed by condensing glycerine and propylene oxide.
2Niax 11-27, mol. wt. = 6200 from Union Carbide Corp., synthesized by capping the glycerine-propylene oxide adduct with ethylene oxide.

The triols, TMP crosslinker and additives were mixed in an agitated flask at 100C for 30 min and then deaired in a vacuum oven. Then the catalyst and diisocyanate were added. The viscosity of the mixture was 380 cps (0.38 P. sec). The mixture was allowed to react for 5-7 min after which the liquid reaction product and unreacted diisocyanate were deposited by pouring directly onto the surface of TQ-178 sheet. The composition was allowed to gel until no longer flowable and then cured at 70C for 1 hr. Polyurethane thickness was about 6 mils (0.15 mm).
The resulting polymeric laminate of plasti-cized PVB sheet and polyurethane was subjected to the Boil Test and Tape Test. After the Boil Test no observable deterioration of adhesion between the layers could be observed from which excellent delamination resistance can be predicted when used in an ALS or bilayer application. A value of five was obtained in the Tape Test also indicating excellent adhesion. It was concluded that the layers were inseparably bonded as a result of chemical linkages formed by urethane groups (-O-CO-NH-) at the interface between the PVB and PU layers which were developed by reaction between vinyl alcohol groups of the PVB and diisocyanate molecules associated with the thermoset aliphatic polyurethane layer.

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Moreover, a glass laminate with the PVB/PU
laminate of this Example withstood 150C exposure for one hour with no visual yellowing of the PU layer or optical distortion of the laminate by the heat.
E~YAMPLE 7 This shows a chemical linkage of the type developed in Example 6 except with a polyurethane formed using a polyether glycol. The formulation was:
Component Char~e(q) Methylene bis(4-cyclohexylisocyanate) (Desmodur W) 92.65 Polytetramethylene ether glycol (PTMEG) 100.0 1,4 Butanediol 4.14 Trimethylol Propane 13.69 Dow Corning 193 0.21 Dimethyl Tin Chloride 200 ppm Terathane 650; mol. wt. 690 from E. I. dupont de Nemours & ~o., Inc.

The preparation procedure was the same as Example 6 in that the polyols and crosslinker were mixed at 100C and catalyst and diisocyanate then added; the TQ-178 sheet was coated, cured and adhesion checked after the Boil Test and the Tape Test. The quality of adhesion noted was the same as Example 6.

This shows a chemical linkage of the type developed in Example 6 except with a polyurethane cross-linked by curing exposure to ultraviolet radia-tion. The formulation was:
Component ~ (g) Methylene bis(4-cyclohexylisocyanate) 109.2 5Polytetramethylene ether glycol (PI~EG) 330.1 1Hydroxyethylacrylate ~HEA) 19.2 2Trimethylol propane triacrylate 183.4 ~Photoinitiator 16.1 4Dibutyl tin diacetate (catalyst)10 ppm - , . .

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1From Celanese corp.
2 Sartomer 351 from Sartomer company 3 2-hydroxy-2-methyl-1-phenyl-1-propan1-one, Darocur 1173 from EM Industries 4From Aldrich Chemical Co., Inc.
5Terathane lO00, mol. wt. 990.
The diisocyanate was charged to a 500 ml fluted resin pot equipped with an agitator, nitrogen inlet tube, thermometer and dropping funnel. The pot and contents were placed in an oil bath and heated to 90C. The PTMEG containing the catalyst was added dropwise over 30 min. The polyurethane reaction was allowed to continue for 30 min after which residual unreacted isocyanate groups were measured from an aliquot at 3.60% (theoretical was calculated at 1.6%
at reaction completion). The hydroxyethylacrylate was then added and the reaction allowed to continue for 1 hr. During this latter HEA reaction, terminal hydroxyl groups of HEA react with free isocyanate groups to form pendant terminal reactive double bonds available as cross-linking sites during curing. After one hour the free isocyanate concentration had been reduced to 1.80% which represents the isocyanate concentration available for reaction with hydroxyls of the partial PVB sheet. The HEA reation was terminated ieaving a very viscous, (approximately 15,400 cps (15.4 Pa.s)) cross-linkable liquid polyurethane prepolymer mixture.
A hydroxylated acrylate monomer in the form of trime-thylol propane triacrylate was then added to the prepolymer. This component functions i) to reduce the viscosity of the prepolymer to about lOQ0 Cp5 ~1. O
Pa.s) to facilitate handlin~ and ii) as an eventual reactive component during curing in that terminal double bonds of the acrylate moieties formed from the HEA as noted above are available as cross-link sites - - , ' 2 ~ 7 5 -19- 06-12(9859)A

for reaction with other double bonds in the prepolymer mixture. After adding photoinitiator, TQ-178 sheet, 6 in (15 cm) wide) having a roughness value (Rz) of 34 x 10-5 in (86.4 x 10-5 cm) was coated by pourin~ the S liquid mixture directly onto such surface. (Rz is measured in a known manner using a profilometer.) The coated sheet at a rate of 15 feet (4.6m) per min was exposed for reactive curing to W light in the form of two 12 in (30.4a cm) 200 watts/in mercury vap~r lamps (model 1202-AN RPC QC Processor from Radiation Polymer Co. of Plainfield, Illinois) and then to 70C for one hour. During such exposure, free radicals generated by the photoinitiator cause substantially all double bonds in the mixture to be consumed by reacting with one another resulting in an extensively cross-linked, clear, tough, thermoset polyurethane coating on and tenaciously bonded to plasticized PVB sheet by chemi-cal linkages formed at the interface by reaction between vinyl alcohol groups of the partial PVB and free diisocyanate groups associated with the polyure-thane reaction. This was confirmed by ~he Boil Test and subse~uently visibly observing no deterioration in adhesion between the layers. A value o~ five was obtained in the Tape Test.

This is a variant of Example 8 using a different cross-lirlking agent~ The formulation was:
Component Char~e ~g) Methylene bis(4-cyclohexylisocyanate~ 104.8 Polytetramethylene ether glycol (Terathane 650) 160.3 Hydroxyethylacrylate (HEA) 37.1 Isobornyl Acrylate 120.9 Photoinitiator (Durocur 1173) 10.6 Dibutyl tin diacetate 10 ppm . -~ . . . . , . , ~ .
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The procedure of Example 8 was rep~ated.
Residual isocyanate in the polyurethane prepolymer one hour after completion of PTMEG addition was g.41~
(theoretical was 5.1%). After the HEA reaction the acrylated prepolymer mixture contained 1.4% isocyanate available for reaction with hydroxyls of the plasticiz-ed PVB. Adhesion to the plasticized PVB after the Boil Test and Tape Test was excellent.

EXAM2LE }O
This is a dual cure polyurethane system formed solely from monomeric species. The formulation was:
Component Charge(g~
Methylene bis(4-cyclohexylisocyanate) (Desmodur W) 5.24 Photoinitiator 0-77 Terathane lO00 15.84 HEA 0.92 Hydroxylated Acrylate Monomers Isobornyl acrylate 2.3 Trimethylol propane triacrylate (Sartomer 351) 6.6 Dibutyl tin diacetate catalyst 1000 ppm The Desmodur W and photoinitiator were mixed at room temperature (container A). All remaining constituents were likewise mixed in container B. The contents of containers A and B were thoroughly mixed together at room temperature to start the reaction and immediately poured onto TQ-178 sheet. After mixing the viscosity was about 600 cps (0.6 Pa.s). Curing conditions were identical to Ex~nple 8. Adhesion properties are predicted to be essentially comparahle to those obtained in Example 8.

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' , 2 ~ 1 ~ 1 7 ~

-21- 06-12(9859)~

In addition to use in bilayer windshields and as an anti-lacerative shield, the polymeric laminates of the invention are also usable in vehicle side and rear windows as well as in architectural glazings in commercial and residential buildings where optical and other performance properties may be less critical.
The preceding description is for illustra-tion only and is not to be taken in a limited sense.
Various modifications and alterations will be readily suggested to persons skilled in the art. It is intended, therefore, that the foregoing be considered as exemplary only and that the scope of the invention be ascertained from the following claims.

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: " . ' ~ :

Claims (18)

1. A process for inseparably bonding layers of plasticized partial polyvinyl butyral and polyurethane which comprises chemically reacting hydroxyl groups of the partial polyvinyl butyral with isocyanate groups associated with formation of the polyurethane.

2. The process of claim 1 wherein the polyurethane is formed by reacting diisocyanate with one or more polyols containing two or more hydroxyl groups per molecule.

3. The process of claim 2 wherein said partial polyvinyl butyral contains about 17 to 25 weight % vinyl alcohol groups calculated as polyvinyl alcohol.

4. The process of claim 2 wherein said one or more polyols comprise one or more triols.

5. The process of claim 2 wherein a cross-linking agent is present with the diisocyanate and one or more polyols and including a curing step to cross-link and thermoset the polyurethane.

6. The process of claim 3 wherein the NCO/OH equivalent ratio of the composition reacting with the partial polyvinyl butyral is about 1.01:1 to 1.5:1.

7. The process of claim 5 wherein said one or more triols comprise a mixture of polyether triol and polyether capped triol.

8. A process for inseparably bonding layers of polyvinyl butyral and polyurethane which comprises coating a layer of plasticized partial polyvinyl butyral containing about 17 to 25 weight % vinyl alcohol groups, calculated as polyvinyl alcohol, with a reactive liquid polyurethane composition having terminal isocyanate groups on polyurethane chains whereby the hydroxyl groups of the partial polyvinyl -23- 06-12(9859)A

butyral and the isocyanate groups on the polyurethane chains chemically react to develop said inseparable bonding of the layers.

9. The process of claim 8 wherein said composition includes a cross-linking agent and includ-ing the step subsequent to coating of curing the composition to render the polyurethane thermoset.

10. The process of claim 9 wherein curing is at least partially accomplished by exposing the layers to elevated temperature sufficient to cross-link the polyurethane but not to cause deterioration of the polyvinyl butyral layer.

11. The process of claim 9 wherein said composition includes a photoinitiator and curing is at least partially accomplished by exposing the layers to ultraviolet light.

12. The process of any of claims 8, 9, 10 or 11 wherein the polyurethane is formed from one or more polyols and diisocyanate, the equivalent ratio of diisocyanate to polyol being at least about 1 to 1.

13. The process of claim 12 wherein the polyol is selected from polytetramethylene ether glycol, polyether triol, polyether capped triol and mixtures thereof.

14. A process for coating and inseparably bonding a layer of polyvinyl butyral to polyurethane which comprises:
i) combining one or more monomeric polyols, monomeric diisocyanate, one or more hydroxylated acrylate monomers, photoinitiator, cross-linking agent and catalyst to form a polyurethane reaction mixture having a viscosity of about 200 to 1000 cps;
ii) coating a layer of partial polyvinyl butyral containing about 17 to 25 weight % vinyl alcohol groups with the polyurethane mixture whereby isocyanate groups of the diisocyanate chemically react -24- 06-12(9859)A

with hydroxyl groups of the partial polyvinyl butyral layer and other isocyanate groups are incorporated into polyurethane chains to develop said inseparable bonding; and iii) curing the coating mixture on the partial polyvinyl butyral layer to crosslink the polyurethane.

15. The process of claim 14 wherein curing is at least partially accomplished by exposure to ultraviolet light.

16. The process of claim 14 or 15 where the polyol is selected from polytetramethylene ether glycol, polyether triol, polyether capped triol and mixtures thereof.

17. The process of claim 16 wherein the diisocyanate is an aliphatic diisocyanate.

18. The process of claim 17 wherein the hydroxylated acrylate monomers are a mixture of isobornyl acrylate and trimethylol propane triacry-late.