CA1082387A - Adhesion promoted block copolyester compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Thermoplastic segmented copolyester elastomer consisting essentially of a multiplicity of recurring short chain ester units and long chain ester units join-ed through ester linkages, said short chain ester units amounting to 15 to 75 percent by weight of said copoly-ester and being derived from dicarboxylic acid such as an aromatic acid, e.g., terephthalic acid or a mixture of terephthalic acid and isophthalic acid, and an organic diol such as butanediol, and said long chain ester units amounting to 25 to 85 percent by weight of said copolyester and being derived from dicarboxylic acid such as an aromatic acid, e.g., terephthalic acid, or a mixture of terephthalic and isophthalic acids, and a long chain glycol such as polytetramethylene ether glycol, said copolyester having a melt index of less than 150 and a melting point of at least 90°C., modified with 0.75 to 20 parts by weight, per 100 parts by weight of elastomer, of a multi-functional carboxylic compound taken from the group consisting of aromatic and alipha-tic anhydrides having at least two anhydride groups.
The modified elastomer possesses improved adhesion particularly at high temperatures and under high applied stress. A useful adhesive composition comprises (A) 1 to 99 percent by weight of the segmented copolyester elastomer, and (B) 99 to 1 percent by weight of a compatible low molecular weight thermoplastic resin.
The adhesive composition can contain stabilizers as well as other ingredients.

Description

:~i3Z3~7 a~
Field o~ the Invention mls invention relates to modifled thermopla~tic, segmented copolyester ela~tomer~ havlng improved adhesion propertie~, to blend~ of ~uch mudified ela~tomer~ with one or more compatible low molecular weight thermopla~tic resln~ and to a method ~or preparing ~uch blend~, -Description of the Prior Art . .
Segmented copolyester elastomers and thermo- :
pla~tic composition~ containlng ~uch ela3tomer~ and low molecular weight thermopla~tic re~ln~ are known.
In U. S. Patent 3,832,314 there are di~closed thermopla~tlc cvmpo~itions containing (A) 1 to 99 percent by weight oY thermoplastic segmented copolyester ela~tomer ;:
consisting e~sentially o~ a multiplicity o~ recurring 5hort chain ester units and long chain ester units ~oined :
through ester linkages, said short chaln ester unit~ ~ ;
amounting to 15 to 75 percent by weight o~ ~aid copoly-ester and being of the formula -CRC-ODO-and said long chain ester units amounting to 25 to 85 percent by weight of said copolye~ter and being of the ;
formula -CRC-OGO~
wherein R i~ the divalent aromatic radical remaining after removal of the carbo~yl group~ from aromatic di~
carboxylic acid having ~.molec~lar weight o~ es~ th~n 350, D is the divalent radical remaining a~ter remoYa ~2-.

3~

o~ the hydrox~l groups ~rom organic diol having a molecular weight o~ less than 250, and G is the dival~nt radical rem~ining a~ter removal of the terminal hydroxyl groups from long chain glycol having an average molecular weight of 350 to 6000, said copolyester having a melt index of les~ than 150 and a melting point o~ at least 125C(DTA), and (B) 1 ts 99 percent by weight o~ low molecular weight thermoplastic resin which ~orms compatible mixture~
with the segmented copolyester, ~s thermally stable at 150C., and has a melt viscosity o~ less than 10~000 centi-poi~es at 200C. Belgian Patent 811,307 teaches ~o~t thermoplastic segmented copolyester elastomer consist ing essenti~liy of a multiplicity o~ recurrlng short chain ester ~nits and long chain e~ter unit~ jolned through ester link~ges, said short chain e~ter unlts amounting to 15 to 50 percent by we~ght o~ said copolyester and being o~ the formula O O
-CRC-ODO-20 and said long chain ester units amounting to 50 to 85 ~ ~:
percent by weighk of said copolyester and being o~ the ~ormula OO
Il It . .
CRC~OGO-wherein R i~ the divalent aromatic rad~cal remaining after removal of the carboxyl groups ~rom aromatic dl-carboxylic acid having a molecular weight o~ le~s than 350, said aromatic dicarboxylic acid beinæ 55 to 95 per cent by weight terephthalic acid, D i3 the d~valent radical remaining a~ter removal o~ the hydroxyl groups .

-3- :
, ~ ~

--. -. . ~ . ~:
. . ,, ~, , ' ', ~3æ3~
` :
from butanedlol, ~nd G i5 the divalen-t radical remaining after removal of the terminal hydroxyl groups from polytetramethylene ether glycol having an average molecular weight of 1500 to 3500, said copolyester havlng a melt index -of les~ than 30 and a melting point of 90 to 160~C. (TMA).
The compositlons o~ U.S. Patent 3~832,314 have good bond s-trength as hot melt adhesives and the compositions of Belgian Patent 811,307 are partlcularly :
use~ul as pressure sensitive adhesives. In order to provide good adhesive properties, the viscosity of the ~ :
~dhesi~e blend must be maintained at a relatively constant level. It has been found that at elevated tempera- ;
tures, particularly in the range of 170 to 200C. 3 over a period of several hours the aforementioned adhesive composi-tions lose vi~cosity and hence their bo~ding properties are reduced.
In Canadian Patent 1,040,783, wh~ch issued October 17, 1978J Eastman teaches that the aforementioned segmented copolyester elastomers can contain a stabilizer mixture, 1.75 to 15.0 percent by welght, based on the weight of elas~omer, comprising (a) 0.25 to 2.5 percent by weight of ~;
a substantially linear polycarbodiimide having an average of at Least two carbodiimide groups per molecule, and at least one compound of (b) 0.5 to 2.5 percent by wei~ht of a `~
hindered phenolg nitrogen-containing hindered phenol or ~ ~ .
secondary aromatic amine, (c) 0.5 to 5.0 percent by weight of phosphorous acid esters and (d) 0.5 to 5.0 percent ~ :~
by welght of an amino acrylate, a homopolymer thereo~3 or a random copolymer of ethylene and 20 to 40 ~ -percent by weight of amino acrylate compound3 each of -4- :
,~ .

:

... .. . .
: .

3~7 compound3 (b), (c) and (d) b~ing compatible with each other and wlth (a). Such ~tabllized elastomer compositions do not ~uffer appreciable lo~ in v~cosity and have good pot li~e when heated to 170 to 200C~ Por extended period~
o~ time wlthln the period vf 12 to 24 hours.
Caldwell U. S. Patent 3,459,584 teaches that tetracarboxylic acid dianhydrides, pre~erably pyromellitic acid dianhydride, c~n be reacted wlth certain low ~olecular weight hydroxyl-terminated polyesters to provide a prime coating composltion~ me pol~e~ters are reacted with ~toichiometr~c amo~nt~ of acid dla~hydride~ me ~olye8ter-dianhydride adducts contain ab~ut 1.2 to 15 weight percent free ~;
carboxyl groups and have a molecular weight o~ 400 to 8000.
related Caldwell U.S. Patent 3,48~,339 teaches that the reactlon product of the tetracarboxylic acid dianhgdride and low molecular weight polyester can be blended with particular pQlymeræ to provide, a~ disclosed, composition~ with ~n improved degree o~ adhe~ion~ -_UMMARY OF THE_I~VE~TION
In accordance wlth this invention uperior adhesion-modl~ied thermoplastic segmented copolyester elastomers are provided which consist essentially o~ a multiplicity of recurring short chain ester units and long chain ester units Joined through e~ter linkages, said ~hort chain ester units amounting to 15 to 75 percent -~
by weight of sald copolyester and belng o~ the ~ormula -~
O O
Il ~1 .
-CP~-ODO-and sald long chain ester units amounting to 25 to 85 30 percent by weight of sald copolyester and being of the .

~82315~7 formula O O
~ tl -CRC~OGo-whereln R i8 the divalent radical~ eOg~ cycl~c, aroDlatic, allphatic, or mlxtures thereof, rem~lnlng after removal o~ the carb~xyl groups ~rom a dicarboxylic ::
acld having a molecular weight o~ less than 350~ D i8 t~e divalen~ radical remainlng a~ter removal of th~ h~droxyl gro~ps ~roDI organic dlol havlng ~ m~lecul~r weight o~ les~
thhn 250, and G i~ the divalent radlcal rema~ning a~ter removal o~ the l;erminal hydroxyl groups ~rom long ch~in glycol havlng an average molecular ~eight Or 350 to 6000, said copolye~ter having a melt ind~ of le88 than 150 and melting poînt of at lea~t 90C.(TMA), modi~ied wlth 0~75 to ;~:
~0 partB by welght, per 100 parts by weight of elastomer, of a ::
mult~-functional carboxylic co~pound taken from the gr~up consiBting o~ aromatie and aliphatlc anhydride~ havlng ~t least two ar~ydride group~
In a preferred embodiDIent the adhe~ion modi~ied ;.
ela~tomer i~ al~o stabi~ed wlt~ 1,75 to 15 part~ by ~ :
weight, per 100 parts by weight o~ elastomer, of a ~tabi~zer mixture comprislng (a) 0.25 to 2.5 partæ by ~elght of a ~ub~tantially linear polycarbodiimide ha~ing an average of a~ lea~t two carbodlimide grou~ per molecule; and at lea~t one c~mpourld taken from the gr~p consi~ting o~ (b) 0.5 to

2.5~part~ by w~ight o~ a con~pound taken from the group ;;
consisting o~ hindered phenols, nitro~en-containing hindered phe~ol~ and ~econdary arom~i~ amine~; (c) 0.5 to 5.0 parts by weight phosphorou~ acid ester~ of the ~ormula / O

wh~re Rl~ R2 and R3 re Cl 18 P ' 6 15 aromatic, and combinat~ ns th~reo~; and (d) 005 to 5.0 ~:
part~ by wei~ht o~ an amino compound tal~en ~r~m the æroup ~on~ting of amino acrylate o~ the ior~
R 0 ~Rl C~ C ~ C - O ~ CnH2n ~ N
\ R2 wherein R i8 hydro~n or methyl, Rl t8 hydrogen or a~yl of` 1 to 4 carbon at~m~, R2 1~ a~url o~ 1 to 4 carbon atams, ~d n i3 an i.nteger oi~ ~ to 4 inclu~lve, a homo-polymer O:e said a~no acrylat~, and ~ random copolymer of ethylene and 20 to 4~ percent by w~ight of 3aid amino acrylate compound, each o~ com~?ounds (b~, (c) and (d) being co~ible with each other a~d wlth (a)0 In an embodiment the ~tabillger mixture eompri es (a) and at lea~t tw~7 c~ the compoulldæ (b3, ~c) and (d).
20 Pre~er~bl~r the stablLtzer mlxture consists oi~ compound~
(a), (b), (c) and (d), each oP the compoun~s being con~patlble with one another. ~;
I2lpr~ved modi~iedJ ~tabiliæed ther~mopla~tlc `;~
con~@o~itions are provided whi¢h eo~prl~e, ba~d on the total thermopla~tlc components, (A3 1 to 99 percent by weight ~ thermoplast~ c se~3me~ed cop~lyester e~a~tomer consistlng es~enti~lly o~ a multiplicl~y o~ recurrin~
~hort chaln ester ur~t~ a~d lon~ chain e~ter unit3 ~oirl~d through e~ter Llnkages, said ~ort c~ain e~ter units amount-30 ing ~o 15 to 75 pereent by weight s~f` said copolye~ter and ~8~31~7 being o~ the formul~ ~ ;
O O
Il ,. ~
-CRC-ODO- `
and said long cha;ln ester units a;mounting to 25 to 85 per-cent by wei~ht of ~ald cop~Dlye~ter and being o~ the f'ormula ;
O ~
It "
-CRC-OGO~
wherein R i~ the d:~valent radlcal, e.g., cyclic, arc~matic or aliphatic, ~3r mixtures thereoi, remaining after ~ .
~emo~Jal Of the carbaxyl groups from a dlcarbo~ c ;~
a,-id ha~ng a molecular weight o~ le~s than 350, D i3 khe dir~lent radlcal remair~ng af~er removal o~ the hydrc~xyl .
group~ ~rom org~nic di~l ha~ring a molecular we~ght of less ~han 250, and ~ i~ the divalent radical rema;inirlg after removal of the te~nal hydro2c,yl group~ f~om long . ~:.
chaIn glycol h~ving an average molecular wei~ht of 350 to ~ `
6000, ~d cop~lyester h~ving a melt index o~ le~ than 150 and a melting polnt c)f at least 90C. (lMA); (B) 1 to 99 percent ; ~::
by wei~3ht o~ lo~ ~nolecular wel~ht thermoplastic resin wh:lch i~orm~ compatible mi~ctur~ with the segmented co-polye~ter, i8 thermally stable at 150C., and ha~ a melt viscositg of less than 10,000 centipoi~es at 200C., :~
modified with 0.3 to 8.0 parts by weight, per 100 part~ by weight oP ~la~tomer arld re~in, Qf` a multi i~ction~l s;
carboxg~ie compound ta~en from the group C0~18~:ti~1g O:
aromatic and aliphatic anhgdride~ having at lea~ two anh~dride gr~upa and stabilized with (~) 0.75 ts~ 600 part8 ~ :
~y we~ght, p~r 100 parts by weigh~o~ elastomer and resin, of a stabiLizer mixture compr~ing (a) 0.1 ~o 1.() ;

8_ i ~

~ 23~7 :

part by we~ght o~ a ~ubstanttally ~ne~r po3ycarbodilmide ha~lng an average of at lea~t two carbod~ de ~roup~ p~r molecule; and at least one con~pound taken from the gr~up con~i~tlng of (b) 0.2 to 1.0 part by welght or^ a c~mpound taken from the group con~1~3ting of hindered phenol~, nitrogen-contalnlng hindered phenol~ and ~econdary aromatlc amines; (c) 0.25 to 2.0 parts by welght phc~phorou~ acid e~ter3 o~ the ~ormul~:
R

~0~ , ' ' where Rl~ R2 and R3 are Cl to C18 ~liphatic, C6 to C15 aromatic, and combinakions thereof; and (d) 0.20 to 2.0 part~ by weight of an amin~ co~pound ta~en ~rom ~he .
group consisting o~ amino acrylate o~ the ~ormula: ~ :
R 0 / Rl C~2 ~ C - C ~ ~ ~ CnH2n ~ ~
\p~2 20 whereln R i8 hydrogen or methyl; Rl i~ hydroger~ OI` alkyl of 1 to 4 carbon~ atoms3 R i~ alkyl of 1 to 4 ~arbon atoms;
and n i~ an lnteger o~ 1 to 4 lnclu~ive, a homopol5rmer o~
sald am~no acrylate, and a random copo~rmer o~ ethylene and 20 to ~0 percent by weight o~ ~aid aD~no acrylate compound, each oP ~aid compounas tb~, (c~ and (d) belng compatible with each other and w~th (a~.

D~:T~I~ D~SCRIPTION C~F T~ ~ON
.~ .
~ he ~tabilizea thelt~mopla~tlc ~eg~nted GOpO
e~ter elastomer~ used i~ the compositi on~ ~ thi~ ln~
3û ventlon consl~t e~entially o~ 15 to 75 p~rcent recurring _9_ short ch~ln ~ster UnitR and 25 to 85 percent long c h~ln e~ter units ~oined through ~ter linkagea. me term "cc) n~i~ting es~entially of ~ as used h~rein, i~ meant to include in the copolyester only those un~p~cifled pslymer unlt5 whlch do not materially a~rect the basic and ~;
~s~ntial chara~teri~ttic~ o~ the copolyester a~ it re-late~ to the composition~ of th:l s lnv~ntlon~, In other word~, thi~ term exe~ude~ unspeci~led polymeric unit~ in amounts which prevent the ad~rantage~ of the compo~iti~ns 10 o~ thi ~ 1 n~rention ~rom being realized . ~e term " ~hort chain ester unit~", a~ applied to unit~ ~n ~ pol~srmer chatn, refer~ to the reactlon products of low molecular weight diols ~rlth dlcarboxylic aclds to form repeat unit3 having molecular welght8 o~ le~s than about 550. me3e unit~
are also referred to herein a8 "hard segments". The term "long chain e~ter urlits", a~ aI~plied to unlt~ in a polymer chain, re~er~ to the reaction products of long chaln glycol~ with dicarboxyltc acid6. Ths~e units are al~o referred to herein a~ "~o~t segnents". ~re~erably 20 ~he copolyester coneist~ es~ntially o~ 15 to 65 percent hard segment~ ~nd 35 to 85 percent ~o~t ~egments.
T~e ~oft thermoplastic segmentea copolye~ter elastomer~ of this inventlon con~isk es~entially of about 15 to 50 percent recurrlng short chaln ~ter unit~ and about 50 ~o 85 p~rcent long chaln e~ter unit~ Joined throuB~ e3ter linkage~. In the~e ela~t~er~ the t~rm "short cha~n e~ter unit~", a~ applied to unit~ tn a ;;
polymer chain, refer~ to the reactlon o~ butanedlol (BD0) with dicarbo~y~c acid~. m~se u~lt~ are al~o reYerred 30 to herein as "hard ~eg~n~". In these elastomers ~8~3~7 the term "long chain e~ter units"9 a~ app~ed to unit~
in a polymer chain, re~ars ~o the reactlon products o~
polytetr~ethylene ether glycol (PTMEG) wlth di-carboxyllc acid~. ~rhe~e units are also referred to hereln a~ "soft segment~". Pre~erably, the copolye~ter consist~ e~sentially of' about 15 to 30 percent hard ~egment~ and about 70 to 85 perc6!nt 30:~t ~egment~.
q~e weight percent o~ long chain e~ti3r (I~CE~
unit~ specl~ied herein are calcul~tQd ~n accordance with 10 the ~ollowing equation in Which bo~h the r~umerator and d~nominator are expressed in gram~. . -Wt . ~ LCE = A~B-C

A = (Moles o~ PTMEG)x~Mole Wt. o~ PTNEG) B = (Total Mole~ of phthalate a8 Acld)x~Mole Nt. of phth~lic Acid Mixt~re ) C - (Mole~ EI20)x~Mole Wt. oi H20) In this equation the mole~ o~ phthal~te will be the ~ame a~ the mole~ of PTI~G s.nd the mole~ o~ water Trlll be twice ~hat of PTM~G. The ~le w~ight Or the ph~halic acid ~ixtur~ ehould be a wei~hted average reflectin~ the compo~itlon o~ the mixture. The theoretlcal polymer yield wlll be the gram~ o~ ingredient~ put tnto the reaction minus the gra~ o~ by-product and exce~s in~redient3 diatilled o~. When cycli~, aliph~tic or mlxbure of acid~ are u~ed in prep~ring the lo~g chain e~ter, B
above equals (total mole~ of cyclicJ aliphatic or mix-tures of acid~) ~ (wei~hted average mole wei~h~ of the ~otal acid o~ mi~tur~ o~ acid~).
The weight percent o~ ~hort chaln ester (SCE) - . . . ..

unit~ i9 de~ined in an ~nalogou~ manner:

Wt. % SCE = D~E-F
'IRieore~ical Flymer D = (Moles o~ BDO)x(Mole ~t. o~ BDO) -:
~S = (Tots,l Mole~ of phthalate a~ Acid)x(Mol~ Wt. of phthalic Acld Mixture ) F - (Mole~ H20)x(Mole Wt. o~ H20) Here the moles of butanediol do not lnclude any stoichiometric exces~. When c,yclic, allphatlc or mix-tur~ of a¢id~ are u~ed ln pre~aring the short chain esters E above iL~ calculated a~ de~crlbed ior 13.
The copolye8t~r~ u~ed ln accordance with t;hi8 :
invention are prepar~d by polymerizlng with each other (a) one or more dicarboxylic acl~ such a~ cyclic,l ,~
aromatic, al:lphatic dicarboxyllc acld~ or mixture of said acid~ ., preferably aromatic dicarboxsrlic ~cids , (b ) . ~:
one or more llnes,r long chain glycol~; and (c ) one or more lo~r molecular weight diols. me terJn "di- ~:
carboxylic acid", a~ u3ed herein, ~8 intended t~ inclu~
the equivalent3 o~ ~icarboxyllc acids, that i8, their : :
e~ter~ or e3teP-~orming derlvative~ ~uch a~ ~cid ~;
ehlorides and anhydrldes/ or oth~r derivatl~e~ which behave ~ub~tantially like dicarbox~rlic acid~ in a polymerization reaction wlth glycol. 13y the term "aromaltlc dic~rboxyJlc acid" i~ meant a dicarbox~
acid in which 0a~h carbox~l group iB atta~hed to a carbon atom in an isolated or fused benzene ring or a rlng which ls ltself ~used to a benzene ring. Specl~
call~, ~n preparlng the 80~t thermopla~tic ~egment~d ., .
30 copolyester el~tomers (a) a ~alxture o:e aroma~ic di-carbs~xylic acids conte.lning about 55 to 95 percent by weight of terephthalic acid, (b) polytetramethyleneether glycol and (c) butanediol are polymer~zed ~ith each other. -~ :
Th~ dlcarboxylic acld monomers useful here~n have ~ molecular weight o~ le~ than about 350.
Thi~ molecular welght requ:lre~ent pertain~ to the ~cid it.
sel~ and not to its e~ter or e~ter~formlng d~rlv~tive.
Thu~, tho ~6ter of a dicarboxyli~ acld having a molecular weight greater than 350 i8 l~cluded in thi~ inventlon provided the acid itsel~ has a ~olecular we~ght b~l~w about 350.
me dicarboxyllc acid3 u~ed in the prepara~ion o~ the ~gmented copolyester ar~ arom~tic, ~yclic (~yclo-aliphatlc), aliphatic dlcarbo~lic a~ids of law molecul~r weight, or ~ixturea of said acids and ¢an contain any ~ubstit~ent eroups or c~mbinatlon thereo~ which d~ not int2riere wlth the polgmerlzation rea~t~n. Representative ~ :
aromat,ic dlcarb~xyllc acids ~nclude terephthalic acid, is~phthalic ac~dy phthalic ac~d, bibenzoic acld, ~ub~ti;
tuted dicarboxy compounds with b~nzene nuclei ~uch as bis(p-carbo~yphengl) methane, ~-oxy(p-~arboxyphenyl~ ~ :
ben~oic acid, ethylene-bi~(p-oxybenzoic acid), ethylene-bis-(p-ben~olc acid), tetr~methylene bls(p-oxybenzoic .
acld)J 1,5-naphthalene dlcarboxylic acid, 2J6-naphthalene dicarboxglic acld, 2~7-naphthal2ne dicarboxylic acid3 phenanthrene dicarboxyllc acid, anthracene dicarb~xyli~
ac~d, 4J4'-sul~onyl dlbenzo~c acid, indene dicarboxylic ~:
acidJ and the likeJ aa well a~ rlng sub~tituted derivative~ :
thereof such a~ el-c10 alkgl, halo, alk~xy or aryl deri-vative~. Hydroxy acid~ ~ch a~ p~B-hydroxgetho~y~ benzoic

3~

acid ean al~o be used providlng an ar~m~tic dicarboxylie ac~d i~ al30 pres~nt.
Representatlve cycloaliphatic and aliphatic aeids lnelude ~ebae~e acid, 1,3-cyclohexane dlcarbox~li c acidJ
1,4-cyclohexane d~earboxylic acid, adipic acid~ glutaric aeid, ~uccinlc aeid, carbonic acld, oxalie aeld, ~z~lalc acld, diethyl-malo~ic acid, 2-ethylsuberie aeidJ 2,2,3,3-tetra~n~thyl~uccinic acid, cyc lopentanedlc~rb~xylic acid, deeahydro l95-naphth~lene diearbox~ie aeid, 4,4'~bieyclo-hex~l dicarboxylie ~eid~ dee~hydro-2,6-naphthylene di-carbox~lic acid,4,~ thylenebis-(cyclohexyl) carboxyl~¢
acid, 3,4-f`uran dlcarbox~llc acld, an~ cy~lobutane dicarboxylic acid. Pre~erred acid~ are cyclohexane-dl-carboxy~c acid~ and adipic acid.
q~he preferred dicarbox~rlic acids ~or prepa-ration of the ~egmented copolye~ter are the ~romatic acld~ o~ 8 to 16 c~rbon atoD~s~ partlcularly phenylene dl~
carboxylic acids ~uch a~ phthalic, terephthalic and i30-phthallc acids. The mo~t pre~erred a¢id~ are terephths7ic acid and mlxture~ o~ ~erephthalic and lsophthalic acid~.
In the ~o~t copolye~ter el~tomer9 preferably, the mixture o~ aromatic dicarboxylic acid~ contain~ about 6~ to 95 percent terephthallc acld.
me low molecular wel~ht diol~ use~ ~n the pre-paration ~r th~ hard segments o~ ~he copolye~ters ha~e molecular weight~ of les~ tha~ ~bout 250. The term "l~w molecular welght diol", a~ u~ed herein, should be c~nstrued to include equivalent eeter ~orming derivative#. In thi8 ca~e, however, the molecular weight requ~reme~t pertains to the dlol only and not to it~ der~vative~.

il23~7 Sultable low molecular weight dlols which react to rorm the short chain e~ter unlts o~ the c~polyesters ln-clude acycllc, alicyclic and aromatic dihydroxy compound~.
The pre~erred dlols are tho~e with 2 to 15 carbon atom~
such as ethylene, propylene, tetra~ethylene, i~obutylene, pent~ethylene, 2,2-dimethyltrimethylene, hexamethg lene and deca~ethylene glycol~, dihydroxy cyclohe~ane3 cyclo-hexane dimeth~nol, re~orcl~lol, hydroqulnone, 1, 5-dihydroxy ~:
naphthalene, and the like. Especially pre~erred are the 10 aliphati~ di ols o~ 2 to 8 carbon ~tQm~. Suitable bi~-phenols include bis(p-hydro~y) diphenylJ bis(p-hydroxy-phenyl) meth~ne, bis(p-hydroxyphenyl) ethane, bl~(p-hydrox~p~engl) prop~n~ and 2J2-bl~ (p-~dr~henyl) propane. Equivalent e~ter-~or~ng derivative~ of diols are al80 u3eful~ For e~ nple, ethylene o~cide or ethglene carbonate can be used in place o~ eth~rlene glycol.
me long chaln glycol~ u~ea to prepare the ~oft ~-:
segment~ of these copolyester~ have molecular weights o~
about 3~0 to 6000, and preferably about 600 to 3000~ Pre~
~0 erab:Ly the long chain gl~col~ have m~lting point~ o~ less than about 55C. 9 and carbon ~tom to oxygen atom ratio~
which are greater than about 2.5, th~t i8J greater than about 2.5:1. Long chain glycol~ having carbon ~o oxygen ratios ~ -greater than about 2.5:1 gener~lly hav~ le~s ~well in wat~r :
and greater resi3tance to hydrolysis,, ~rhe chemlcal structure of the long chaln polS~-merlc part o~ the long chaln glycol 18 not critical,, ~ :
Ar~y sub~tituent g:roups which do not ~nter~er~ ~rlth the polymerization reactlon t~ ~orm the copolyeater can be 30 pre~ent. Thuæ, the ~haln can be a ~ingle dlvalent acyclic, --15- :

allcyclic, or aromatic hydrocarbon group, poly(alk~rlene oxide) group, polye~ter group, a combinatlon thereo~9 or ;-~
the like. Arur of the~e group~ c~n contaln ~ub~tituents which do not lnterfera to any sub~tantial extent with the polymerlzation to ~orm the copolye3ter u~ed in accordance with thi~ invention. me hydroxy ~unct~onal groups o~ the long cha~n glycol~ u~ed to prepare the copolgest~r~ ~hould be terminal group~ to the extent posslb~e.
Suitable long chain glycol~ which can be used in preparing the ~o~t ~egment~ of the copolymers include polgtalkylene ether) glyc018 in which the alkylene groups are o~ 2 to 9 carbon a~oms 3uch a~ poly(ethylene ether~ -gly~ol~3 poly(l,2- and 1,3-pro~ylene ether~ glycol, ?
poly(l,2-butylene ether) glycol, poly(tetra~ethylene ~ther) glycol, polytpes~amethylene ~ther) gl~rcol, polythexa- ~ .
methylene ether) glycol, pol~(h~ptaalethylen~ ether) glycol, poly( 3cta1nethylene ether) glycol, poly(nonaanethylene e~her) ~lycol, and ra}~dom or block copolymers thereo~, ror ;
2û exa~pleJ glycol~ der~vea grom ethylerle oxid~ and 1,2~
propylen~ oxide. ~:
Glycol esters o~ poly(alkglene oxlde~ di-car~oxylic acid~ can al~o be used as the long chain glycol.
These glycol8 may be added to the pol~rmer~zation re~etlon `:
or may b~ formed _ ~itu by the reaction of a dicarboxy~
methyl acld of poly (alkylene o~dde ) such as HOOCCH2(0CH2CH2CH2CH2)XOCH2COoH with the 1QW molecular weight d~ol, which i8 alway~ present in a ~tolchiom~tric -;
ex~e~s. ~h~ re~ulting poly(alkg}ene oæide) eæt~r glycol :~
30 then pol9meri~e3 to ~orm G unitæ having the ~tructure .
`

-DOOCcH2(ocH2c~2cH2cH2)xoc~I2covD- ln which each diol c~p (D) may bs the ~ame or di~erent depending on whether more than one diol is used. These dlcarboxylic acîd3 may al~o react in situ wlth the long chain glycol, in whlch ca~e a mater~al 1~ obtained havin~5 a formula the ~ame a~ abotre except that the D ' s are replaced by G' ~, the polgmeric resldue o~ the long chain glycol. The ext~nt to which this react~on occur~ uite ~2nall, however, ~ince thQ
low molecular w~ight dlol i~ present ln con~lderable ex-ces~.
Polyester glycol~ can al~o be u~ed as th~ long chain gl~col. In uslng po~ye~ter g:Lycol~, care must generally be exerci~ed to con~rol the t~ndency t~ lnter-change during melt polsnnerlzation. Gert~n ~terically hindered polye~ter~J e~g., poly(2,2-dimethyl-1,3-propylene ad~pate), poly(292-dimethyl-1,3-propylene/2-~ethyl-2-ethyl-1, 3-propylene 2, 5-dlmethylterephthalate ), poly(2,2-d~methyl-1,3-propylene/2,2-di~thyl-1,3-propylene, 1,4-cyclohex~nedi¢arboxylate) and po~y(l,2-cyclohe~ylene-dimethylene/2,2-dimethyl-1,3-propylene, 1,4 cyclohexane~
dicar~xylat~) ca~ be utilized under n~rmal reactlon condition~, and other more reactive polye~ter glycol~
can be used i~ proper reaction condi~ions, ~ncluding a short re~ldence tlme, are employed.
Sultable long chain glycols al~o lnclude poly- -~ormal~ prepared by reacting ~ormaldehyde w~th glycol~
such a~ pentamethylene glycol or mlxtures of glycol~ ~uch as a mixture of tetramethyle~e and p~ntamethylene glycol8.
Polythioether glycol8 also provide u~ul products~ P~ly-butad~ene and polyi~opre~e glycol~, copolymer3 of these~

. ~ ` ' ` . ~ , -23~7 and ~aturated hydrogenatlon product~ of the~e mat~rl~l~
are al80 ~ati~actory long chain pol~nnerl c glycol~. In addltion, the glycol e~ters of dicarbo~yllc ~clds ~ormed by oxldation of poly~sobutylene-diene copolymers are u~e~ul raw m~terlal3. The preferred ong chain glYC ol~
are poly(alkylene ether) glycol~ and glycol e~ter~ of poly(alkylene oxide) dicarboxglic acld~.
Butanediol i~ u~ed in the preparation o~ the hard ~egment~ o~ ~opolyester el~tomer~ The term "but~nediol", a~ used hereinJ ~hould be con~trued to in~
clude equivalent ester-formlng derivative~ ~uch ~ tetra hydro~uran or buta~ediacetate. Th~ po~ytetramethylene ether glycols u~ed to prepare the ~oft ~egme~t~ of these copol,~ester ela~tomers mu~t have molecular wei~ht~ of ~ ::
about 600 to 3500, and preferably about 600 to 2100.
The relativ~ mole~ular wei~sht of the ~egmented copolye~ter i~ e~;pre~sed hereln in term~ o~ melt ~ndex, which i~ an empirical mea~urem~nt ~ in~ers~ melt ~;
co~ity. The ~egmented copolye$ter elg~tomer~ should have ~ m~lt index of` les~ than about 150, le~s th~n about ~ `~
30 ~or the so~t elastomers, ~n order to provid~ use~ul ~.
compo3itions. me lower melt indlce~ provide comp~9i~
tion3 having ~uperior pressure ~ensitive properties.
The melt indices ~pecified herein are determined by the :~:
Amerlcan Society ~or Testing and Materials ther~in ~:
abbrevlated "ASTM") *est method D 1238-65T using Condition L at 230G. (melt indlces of` soft ela~tomers were determined u~ng Condition E: at 19C)C) with a 2160 gram load.
The segmented copolye~ter~ in one embodim~nt~

-18..

.. -.

h~ a melting po~nt of at le~t about 125C, and preferably a melting point of at ~ea~t about 140~(DTA). The 80~t elastomers having a melting point o~ about 90 to 160C., preferably 95 to 140C. (TMA). me hieh m~31ting ~egmented co-~polye3ter~ used herein maintain the~r high melting charact~ristic~ when blended with low molecular wei~ht ~hermopla~ti~ res~ns in accordance with thl~ lnventlon.
~he hi~h meltlng point of the ~egmented copoly-e~ter i~ obtained by providing the polyester Wlth crystallizable ~hort chain e~ter seg~ent~. Crystalllnity in the ~hort chain e~ter ~e~ments i~ incre~8ed by the u~e o:~ more l~near and 3ymmetrlcal d:Lacid illustrated with arom~t~c diacid39 By "linear" aromatic dl~cld i~ meant a dlacid in whlch each o~ the bond~ between the carboxyl carbons and their ad~acent carbons fall on a ~traight line drawn Prom one carboxyl carbon to the other. By "~gmmetri-cal" aromat~c diacld i~ meant ~ diacid which ls ~ ~ etrical with re~pect to a center llne drawn fr~m one carbox~l carbon to the other. ~or example, repeating ester unit~
such as tetrame~hylene terephthalate glve an e~peciallg high melting ~hort chaln e~ter ~egment. On the other hand, when a non-linear and unsymmetrical aromat~c diacidg ~uch as isophth~lic acid, i~ added to crystall~able short chain ester ~egments, thelr meltlng point i~ depre~æed. Small amounts of isophth~lic acid are, however, very u~e~ul ~r controlling the meltlng po~nt and improving the compatibility of segmen~ed copolyester~ wlth low molecular ~eight thermoplastic resins. In preparing the harder copolye~ter elastomer8 al:lphatic diba31c 30 acids 3hould be avolded since they giVÇ! low melting or .
: ~' . , .

non cry~talllne 3hort ~hain eRter ~eg~ents witho~t any s~gnificant beneficial erfects.
~ le melt~ng point~ 8peci~ied herein are determlned by di~eren~lal thermal or thermomechanical analysi~.
In dif~erentlal thermal ana~y~is (DTA) the melting p~l~t i~ read *rom the positlon o~ the endotherm ~eak ln a th~rmo~ram when the ~ample i5 heated from room temperatur~ ~t the range o~ 10C.~mln. The detall3 Or thi~ m~thod are de~ ;
cribed in ma~y publication~, for example, b~ C. B. Murphy ;~
10 in Di~er~ntial ~ , R. C0 Mackenzle, Edltor, :~
: :
Volume I, Pages 643 to 671~ Academic Pre~, Ne~ ~ork, 1970. In thermomechanlcal Qtlaly9i8 t~MA) the melting point i3 determlned by measuring penetration o~ a penetrometer type prob~ into a polymer ~ample a~ 10 grams load with the temperature programmed at 5C.~mln. me detalls of thi~ method are del3cribed in many publice.tion~, for exa~nple, in ~9Y9~9~L~9 Du Pont Co.~ Wllmington, . .
Delaware, October 1, 1968. -Pre~errea segmented copolyester ela~tcmer~ are those in which the aromatic dicarboxyl~lc a~id is oi 8 to 16 carbon at~ms, the low molecular ~eieht diol i3 aliphatic dlol o~ 2 to 8 carbon atom~, the long eha~n '.
glycol i8 poly(alkylene ether) glycol in which the . . ~
alkylene group ~9 of 2 to 9 carbon atom~, ~he ~hort chain ester unlts a;motmt to about 30 to 65 percent by weight of the copolyester, the long chain ester unit~ a~ount t~
about 35 to 70 percenk by wei~t oi the copolgest~r, and the copolye~ter haa a melt index of le~s tha~ about 50 and a meltlng poirlt o~ at least about 140&. (~A). ~; -~.

3~7 The copolye~ter ela3tomers prepared ~rom tere-phthalic acid, or a mixture o~ terephthalic and i~ophthalic aclds, 1,4-butanediol and polyt~tram~thylene ether glycol havlng a molecular welght of abou~ 600 ~o 3000 are particularly preferred in the composition~ o~ thi~ ln-ventlon. ~he raw m~terial~ ar~ readily avallable, and the adhesive and coating propertie~ o~ compo~lt~on~ obtain~d ~rom such polymer~ are out~tanding.
The copolyester ela~tomers us~d in ~he composi-10 t~ons o~ this invention can be made by conventlon~l conden~ation polymer~zatlon proced~rss, as ~or example, ~n buIk or in a solvent medium which dissolves one or more o~ the monomers. Ihey are convenlently prepared by a c~nventlonal eæter interchange reaction. A preferred pro-cedure invo~ve~ heating, ~or example, the dl~ethyl ester o~ terephthalic acld~ or a mlxture o~ terephthalic and iso- ;
phthalic acid~, with a long ch~in glycol which may be polytetramethylene ether glycol and an exeess of a short chain dlol whlch may be butanediol in the presence s:~ a ca~aly~t at 150 to 260C., ~ollowed by dl~til~ng o~ the methanol r~rmed by ~he ~nterchange. ~eating i~ continued until methanol evolution is complete. Depending on the temperature, catalgst and diol exces3, thi~ polymerlzation i~ complete within a ~e~ mlnutes to a ~ew hour~. m procedure result~ in t~e preparation of` a low m~lecular wei~ht prepolymer which can be converted to the high molecular welght segmented copolye~ter of thls invention.
m ese prepolymers can al~o be prepared by a number of alternate esteri~lcation or ester interchange procesxe3. For example, the long cha~ glycol can be ; -~

_21--reacted with a high or low mol~cular weight ~hort cha~n ester homopolymer or copolymer in the pre~ence o~
catalyst until randomizatlon occur~. The short chaln ester homopolymer or copolymer can be prepared by ester ~ ~:
interchange ~rom either the d~methyl e~ter~ and lsw molecular weight diols, a~ above, or ~rQm the ~ree aclds with the diol acetates. Alternatively, the ~h~rt ~:~
chaln ester copolymer can be pre~ared by d~rect e~teri~-cation ~rom appropriate diacld~, anhydride~, or acld 10 chloride~, ~or example, wlth diol~ or by otAer proce~3e3 ~uch as re~ction o~ the dlacid~ with cycllc ethers Qr carbonates. Obvlou~ly the prepolymer can also be prepared by carrying out the~e proces~es in the pre~ence of the long chain glycol.
The re~ulting prepolJtmer i8 then converted to the high molecular ~ei~ht segmented copo~ye~ter ela~tomer by dlstlllatlon of the exce83 of ~hort ch~iln d~Lol. Best re~ult~ are usually obtained if thi~ ~inal dl~tillat~on i5 carried out at les~ than 1 mm~ pressure and 240-260C.
20 ~or les~ than 2 h~urs in the presence o~ ~ antioxidant ~: :
such ~s ~ym-ai-bet~-naphth~l-p-phenylenediamine or 1,3,5-trimethyl-2,4,6-tr~s~,5-dltertlary butyl-4-hydroxy~
benzy~7 benzene.
M~3t practical polymerlzation technl~ues rely upon e~ter interchange to comælete the polgmerlzatio~ re- .
action. In order to avold exce~ hold time~ at h~gh temperatures with possible irreversible ~hermal de~rada- :
tion, it is advantageou~ to employ a cataly~t ~or the e~ter interchange rea¢t~n. Whi~e a w~ae variety o~ .
cataly~t~ can be u3ed, organic titanate~ such as tetra~

_22 ~1323~

butyl titanate, used alone or ln combtnation with magn~
or zinc acetate~, are preferred. Complex tltanate~g ~uch a~ Mg~HTi (oR)~72~ derived ~rom alkali or alkaline earth metal alkoxides and ~itanate ester~ are also very ef~ective. Inorganlc titan~te~ ~uch a~ lanthan~m titanate, calcium acetate/anti~nony trio~cide mixture~ and lith~um and magnesium alkoxlde~ are repre~entative of' other cat~ ts which can be used~
~7hile these conderlsat~<3n po~ riza~ion~ are 10 generall~ run in the melt without ~dded ~olv~nt, it 19 ~ometlmes advantageou~ to ru~ them in the pr~senc~ of inert ~olvent in order to ~ac~lltate removal of volatile product~
at lo~er than usual temperature~. mis technique i8 especially valuable during prepol~;ner prepar~tion, for ex~?le, by dlrect e~teri~icat~on. HaweYer, certaln low molecular wei~ht diols, ~or example, butanedlol in terpherurl, are convenient:Ly removed during hlgh polymerlz8,-tion by azeotrop~c di~tillat1on. Other 6pec~al polymer~za-tion techniques, Por example, ~nterfacial polymerization ; -20 o~ ~sphenol with bl~acylhalide~ and bi~acy~halide c~pped l$near diols, ~ay pro~e u~e~ul ~or preparation of ~peciflc polymer~. . .
The proces~es descrlbed above can be run both by ~ .
batch and contlnuous methods. The preferred method ~or ~ontinuous polymerization; n~mely, ester interchange w~th ;~
a prepol~ner, i~ a well-establi shed commercial process.
me segmented copolyester elastomers haYe high molecular we~ghts. ~el permeation ~hromatography methoas can be used to deterr~rle the nwnber a~erage and weight 30 average molecular ~elghts. One such method utl~izes a four colum~ :

23~7 ~y~t81n~ 10 J 105, 104, 1~3 Ang8trom units pore siz0 pack~d wlth Styrogel~. The ~y3tem i~ calibrated u~ing poly~t~rene ~ample~, the ~olvent being 1,2,4-trlchlorobenzene at 135 C., and the feed rate 1 mllliliter per minute. The number average molecul~r weight i$ in;exces~ of 10,000 and the weight average molecular weight i~ in exce~ o~ 25,0~0.
In addlt~on to the seg~ent~d copolye~ter, the composltlons o~ thi~ invention contain one or more l~w molecu}~r weight ~h~mopla~tic resin~ which for~ compatible mixtures with the ~egmented copo~ye8ter, are thermally ~table at about 150C., and ha~e melt visc~sitie~ of les~
~han about 10,000 centipoi~e~ at 200C. The term ~thermo : ;;
pla~tic re~in", aa used throughout the 3pecification and :~ , claim~, is ~ntended to include heat so~tenable re3in~
both natural and synthetic, a~ well a~ waxy types of material~, By the term 'tcompatible~ it i~ meant ~hat there i~ no separatlon ~nto dl~tinct layers between the segmented copolyester and the low molecular weight re~in or re~ins at the copolyester melt ten~perature. In some cases th~
compatibil1ty i~ achieved in multi~c~ ?onent blend~ even thou~h one of the lo~ molecular ~rel~ht thermopla~tic resin compo~ents may not be compatible with the . egmented copoly- :
e~ter el~tomer alone. By the phrase ~Ithermally ~table"~
it ~8 meant that there i9 no ~igniflcant permanent altera~
t~on in the propertie~ of ~he re~in a~ter heating ~t the specifie~ temperature ~or one hour in the presence o~ air.
me melt visco~ities specified herein are ~ea~ured w~th a Brookfleld riscometer by ASTM test method D 1824-66 at elev~t~d temperatures as indicated.
~uitable lcw ~olecular weight thermopla~tic 12~7 reslns include hydrocarbon resins, bitumlnou~ a~phalt~, coal tar pîtch~, rosin~, rosln ba~ed al}cyd re~ins, phenolic re~ins, chlorinated aliphatic hydrocarbon waxes, chlorinated polynuclear aromatlc hydrocarbon~J and the like.
The term "hydrocarbon resins" re~ers to hydro-c~rbon polymer~ deri~ed ~rom col~e-oven gas, coal-t~r fr~ctîon~, cracked and deeply cracked petroleum stock~
essentl~lly pure h~rdrocarbon feed~ and turpent~ne8.
10 Typical hydrocarbon rasin~ lnclude eoumarone-indene re~n~, ``
petroleum res~n~, ~tyrene polymers, cyclo~entadiene re~ln~, and terpene regins. These re~in~ ~re ~ully descrlbed in the Kirk-Othmer ~Encyclopedia o~ Chemical Tschnolog,~ ecc~nd Editlon, 1966, Inter~cience Publi~hera, New York, Volume 11, P~ge~ 242 to 255.
m e term "coumarone-indene re~in~" re~eræ to hydrocarbon resins obtain~d by polymeriza~ion of the resin formers recovered ~rom coke-~ven gas and ln the di~tilla-tion of coa~ tar ~nd derivative~ thereof such a~ phenol~
modi~ed coumarone indene re~in~. The~e re~ins are ~ully de~cribed in the Xirk Othmer Ehcyelopedia~ ~upra, Volume : ~:
11J R~es 243 to 2~7.
ffle term "petroleum re~in~" rerers to hgdrocarbsn resins obtalned by the catalytlc polymerization of deeply cracked petroleum stock8. mese petroleum stoc~ generally contain mixture~ o~ resin ~ormer~ such a~ styrene, methyl ~tyrene, vi~yl toluene, indene, methyl lndene, butadiene, i~opreneJ piperylene and pentylene~. mese re~in~ are ful~y de3cribed in the K~rk-Othmer Encyclopedia~ ~upra, Volu~e 11, Pages 248 to 250. m e ~o-called "polyalkyl-.
~25--- -:.

3~7 ~romatic re~in~" ~all into thl~ clas~ificatlon~, me term "styrene pol~er~" re~ers to low molecular weight homo3?o~gmers o~ ~tyrene a~ well a~ ~o-polym~rs containing ~tyrene and other comonomers 3uch as ;.
alpha-methyl-~tyren~, vln~l toluene, butadl~ne, and the ~ike when prepared ~rom ~ubstantially pure mon~mer.
me term "vinyl aroDIattc pol~rmer~" r~fer~ to low n~olecular weight homopolymers o~ v$nyl aromatic monomers such a~ ~tyrene, vinyl toluene, and alpha~
10 methyl styrene, cop~l~er~ of two 6~r more o~ these monomers with ea~h other, and copolgmer~ contai~n~ one or more o~ these monomer~ in combina~on with other mono~ers ~uch as butadlene, and the like. me~e polyMers are dlstingui6hed ~rom petroleum re~ins in that they are prepared ~rom ~ubstantially ~ure ~onomer.
me term "cyclopentadiene re~ins" refers to cyclopentadiene homopolymers and copolgmer~ der~ ved from coal tar ~ractlons or ~rom cracked petroleum stream~. me~e -resin~ &xe produced by holding a cyclopentadiene-cont~inlng stock at elevated tempera~ure for an extended perlod o~
time. The temperature~ a~ which lt ~8 held determines whether the dimer, trlmer, or higher polymer is obtalned.
The~e resins are ~ully described in the Kirk-Othmer Encyclopedia, ~upra, Volume 11, Page3 250 and 251 The term "terpene re~ln~" ref'ers to polymer~ o~
terpenes which are hgdrQcarbons of the general ~ormula CloH16 occurrlng in mo~t es3ential oils and oleoresins o~ plants, and phenol-m~di~ied terpene re ins. Suitable ~-terpene~ inclu~e alpha-pin~n~, beta-~n~ne, d~p~ntene, limonene, myrcene, bornylen~, camphene, ~nd the like.

. . . . . . .

~B~

The~e product~ occur a~ by-products o~ t oking operation~
o~ petroleum refining and of paper manufac~ure. These resin~ are fully de~cribed in the Kirk Othmer Encyclopedla, supra, Volume 11, Page~ 252 to 254.
The term "bituminous a~phalt~ intended to include both nat~ve a~phalt and a~phaltites ~uch as Gil~onlte, Glance pitch and Grahanlte. A ~ul 1 description o~ bitumlnous a~phalt~ can be iound in Abraham's "A~phalts and Allled Sub~tance~"9 6th Edition, Volume 1, Chapter 2, Van No~trand Co., Inc., particularl~r Table III
on Page 60.
The term "coal tar p~tche~ refer~ to the residues obtained by the partial evaporation or di~tillatlon of coal tar obtained by remo~al o~ gaseou~ components ~rom bituminous coal. Such pitches include gas-work~ coal tar pitch, coke-oven coal tar pitch, bla~t-~urnace coal tar . -pitch, producer-ga~ eoal tar pitch, and the ~ike. These pitches are fully descrlbed in Abraham'~ "Asphalts and Allied Sub~tances", supra, porticularl~r Table III on Pag2 20 61.
The term "rosins" refers to the resinous material~ that occur naturally in the oleoresln of pine trees, as well as derivative~ thereof including rosin ester~, modi~ied rosin~ such a~ fractionated, hydrogenated, dehydrogenated and polymerlzed ro~in~, mod~ied rosin :~
esters and the l~ke. mese mat~riale are fully described :~
in the K:lrk-O~hmer Encyclo~edia, supra. Volume 17, Pa~;es -~
475 to 505. ~ :
The kerm l'rosin ~sed alkyd re~in~" re~er~ to 30 alkyd resins in which all ~r ~ portion o~ the monobasic -27- ~ .
... ~
,~ :

f'~tty acid i8 replaced by ro~in (a mixture o~ diterp~3ne resln ~cid~ and non-acidic comporlents). Unmodiiied alkyd resin~ are polyester product8 compo8ed of polyhydric alcohol, polyba~ic acid and monobas~c fatty acid. Ro~ln `
ba~ed alkyd re~ln~ are described in the K:lrk-Othn~er Encyclopedia, ~upra, Volume 1, Pages 851, 865 and 866" ~ .
The term "phenolic resins~' re~er~ to the product~ resultinæ from the reaction o~ phenol8 with aldehydes. In additiLon to phenol itself', cre~ol8, 10 xylenol~, p-tert.-butylphenol, p-phenylphenol And the like may be used ~ the phenol com~3on~3ntO Formaldehyde i~ the mo~t common aldehyde, but acetaldehyde, f'urfur- ~
aldehyde and the 3.ike may al~o ba used. These re~ins are ~ ~ .
~ully described ln the Klrk-Othmer Encyclopedia, suI)ra, ~olume 15~ Page~ 176 to 2a7.
me term 1lchlQrinat~3d allphatic hydrocarbon waxes" re~ers to thos~ w~ces which are commonly cs.ll~d "chlorinated waxeæ" such aæ chlorir~ated parar~ln waxe~.
These wa~ce3 typic~ r contair~ ab~ut 30-70 percent b~
20 weight of ch}orine.
The terEn "chlorinated polynuclear aromatlc hydrocarbon8" refers to chlorinated aromatic hydrocarbons containing two or more aromatic ring8 such as chlorlnated blphenyls, terphenyls, and the like, and mixture~ thereof.
These material~ l;ypieall5r contain 30 to 70 percent by :
weight ~ chlorine.
The compositlons Or thl~ inv~ntlon contain about 1 to 99 per~ent by weight of' therm~plaætlc s~gmented copolye~ter elastomer and about 1 to 99 percent by weighl;
30 of low molecular weight thermopla~tic res'ln. Pref`aræbly~

_28-3~

the compo~ltion contaln3 about 5 to 95 percent by weight of thermoplastic ~egmented copolyester ela~tomer and about 5 to 95 percent by weight of low molecular weight- .
thermopl~stic res~n.
Typically the composltions o~ thls inventlon contain more than one low molecular w~i~ht thermoplast~c resin. For example, low molecular weight vinyl aromatic polymers, e.g.J 3tyrene polymer~, have be~n found to lower the mel~ visco~ity of the~e compo~ltlons withou~
10 substan~ially lowering the ~oftening point. Since low~ . :
melt viscosity contribute~ improved wetting by the composition o~ tha surface Or the ~ubstrate, which re~ults in bekter adhe~ion, marU~ useful coD~position~ will contain some vlnyl aromatic polymer. Vinyl aromatic polymers such as styrene are al~o u~eful for in¢reas~ng the compatlbllity of other re~in~ with the segmented c~pol~ :
ester elastomer. Coumarone-indene resin~ Or hlgh soften-ing poink have been found to glve ~trength to the c~mpo5i-tions~ Phenol-~odi~ied coumarone-indene resins have been found to hare the ef~ect Or lowering the ~oftening polnt o~ the compo~ition~ In ~act, the ef~ect of phenol-modified coumarone-indene resin~ on the melting point i~
~o great that the desired melting point i3 generallg achieved by the addition Or only a ~mall amount of thi~
resin. Any comblnation of these desired properties can be ~ -achieved by mixing ~wo or more 1QW molecular weight thermoplastic resin~ with the copolyester ela3tom~r in a proper proportion. The ~o~ molecular weight therm~
pla8tic resin~ also have the e~ect of lowering the co~t o~ the compo~itlon.

-29- :

3Z3~7 `
To improve ~dhesion, partl~ularly at high te~per-ature and under high appl~ ed ~tre~, it has been found ~ha~
to the 3egmented copolyester ela~komer or the the~no$~1~stic compo~ition, as the case may be, there 1s added 0.75 to 20 parts by weightg pre~erably 1.,0 to 8.0 parts by wei~:ht per 100 parts by welght of ~egmented copolyesker or 0.3 ~o 8.0 parts by weight, pre~erably 0.4 to 3.2 part~ by wei~ht per 100 parts by we^lght o~ therm~lastic con~?o~ition, re~pec-tively, o~ the multi~ ctio~al carboxyllc cor~pound taken from the group consisting o~ aromatic and aliphatic anhy-drides having at lea~t two anhydri~de ~roups, Suitable multi~unctional anhyd:~des include pyromellitic dianh~r~de ~PMDA) (1,2,4J5-benze~etetracarbo~yl~c-1,2:4t5-dianhydrlde), 1,4,5,8-n~phthalenetetracarboxylic-1,8:4,5-dianhydride (~TCl~A), 3,3~,4,4~-~enzophenonetetracarboxylic-3,4:3~,4~- s dianhydride (BTCDA), 1,2,3~4,-cyclo$~en~anete~xacarboxyl~c 1,2:3,4-dia~yd~ide (CPTCDA), ~tyrene/maleic anhydride copolymer resins (e.g., "Arco" ~MA 2000A), 2,3,6,7-n~ph~ha-lenetetracarboxylic-2,3:6,7~diahydride, 2,2' ,3*3~ ~benzo-phenonetetracarboxylic-293,2~3~-dianhydride, 1,2,3,4-cyclobu~ane tet~acarboxylic-1,2:3,4 dlanhydride, 1,~,4,5-cyclohex~etet~acarboxylic-1,2:495-dianhydrid~s, etc~, as well as other isomers of ~aid anhydrldes. The adhesion promoter is incorporated in~o the elastomer or the thermo-plaætic composition by mel~ blendlng during compound~ng of the adhesive.
Preferably the a~hesion-modl~ed elastomer or the the~noplaætic co~position 15 stabili~ed by ~dding 1.75 to 15.0 p~r~æ per 1~)0 p~rts by ~eigh~
seg~n~n~ed copolyester or 0.75 to 6.o p~rts per 100 paxrt~ b~ of ~he~lastlc eo~positlon, re~pectively, a s~abil~zer m~xture co~ ing (a) ~ 23~

a sub~ntia]ly l~near polycarbodilmide having an average of at least two c~rbodiimlde groups per molecule; and at least one compound taken from the group consisting o~ (b) a compound taken rrom the group conæisting of hindered phenols, nitrogen-contRlning hindered phenol~, and ~econdary ~ -aromatic amine~; (c) ph4sphorous acid ester~ of the formula o ~2 ~ P
R3' "

where Rl, R~ and R3 are Cl to C18 allphatic, C6 to C~5 aromatic J and combinations thereof, and (d) an amino compound taken from the group con~lst~ng of amino acrylate o~ the ~ormula R 0 Rl CH2 C - C - 0 - CnH~n _ N
\ R~ ::
where R i~ hydrogen or methyl, R i~ hydrogen ~r alkyl of 1 to 4 carbon ~tom~, R2 is ~lk~l of 1 to 4 carbon atoms, and n ~s an ~nteger o~ 1 to 4 inclusive, a homo-polymer Or said amino acrglate, and a random copolymer Or :
ethglene and 20 to 40 percent by weight of the amino :~
acr~late compound, each of compounds (b), (c) and (d) being compatible with each other and wlth ta). At lea~t two of the compounds (b)y (c) and (d) can be present with ~ ;
(a) to form the stabilizer mlxture, or pre~erably all -:
four compound tgpes are pre~ent and are compatlble with ; ~:
~ne another. By compatible in ~his context i~ ~e~nt ~hat the varlou~ compounds of the ~tabi1~zer mixture retain their indlvidual identity when mixed and d~ not chemically ~31- ~ :

23~7 combine wlth one another.
Components (a), (b), (c) and (d~ are pre~ent, respectiveiy, in 0.25 to 2.5~ 0.50 to 2.5, 0.5 to 5.0, and 0.5 to 5.0 parts per 100 part~ by weight of segmentea copolyester elastomer. When based on 100 part~
by weight oY the thermo~la~tic compo~ition~ l.e., ~he segmented copolye~ter ela~to~er and r~1nt the part~ by weight o~ c~mponent~ (a), (b), (c) and (d) are 0.1 to lo~; 0~2 to 1~0; 0.25 to 200; a~d 0.2 to 2.0, respectively.
me llnear polycarbodiimide (a) o~ the ~tabili~r mixture 1~ represented by the formula 1 Rl~ = C = ~ - R ~ nN = C = N - R3~2 where Rl, R2, and R3 are Cl-C12 aliphatic, C6-C15 cyclo- .
allphatic, or C6-C15 aromatic divalent hydroc radical~, and combin~tion~ thereo~, Xl and X~ are H, , " , 4 , "
H 0 R5 -N-C-OR6 where ~4, R5~ and R6 are Cl-C12 aliphatic, C5-C15 cycloaliphatic and C6-G15 aromatic monovalent hydr~carbon r~dicals and co~bination~ thereor and additionally R4 or ~5 can be hydrogen; and n 1~ a number of at least 1, preferably 1 to 7. me usePul polycarbodiimide~ have an average of at Iea~t two carbodiimide groups (i.e., two -N- C = N~ groups) per molecule and an average molecular weight of le88 than ~ ~
about 500 per carbodiimide group. mese polycarbodiimide~ ~
can be aliphatic, cycloa}iphatic, or aromatic polycarbodi- :
imide~ The term~ aliphatlc, cycloaliphatlc~ and ~romatic as used hereln indlcate that the carbodiimide group i~
~0 attached dlrectly to an aliphatic group, a cycloal~phatlc -32~

3~7 group, or an aromatic nucleu~ respectively. For ex~mple, these carbodlimide~ ~n be illu~tr~ted by the formula 1 1 R ~nN C - N - R3-X2 wherein Rl, R
and R3 are independently al~phatic, cycloaliphatic, or aromatic divalent hydrocarbon radical~ and n 1~ at leas~
1 and preferably 1~7. Xl and X2 are defined a~ herein-be~ore. Polycarbodiimide~ uBe~ul ~or the compo~ltion~ o~
thls lnvention have more than two polycarbodlimlde groups and thu~ more than three divalent hydrocarbon group8 (i.e., Rl, R2, R3 . . . Rn) and each o~ the~e hyd~oc~rbon groups can be the ~ame or dif~erent ~rom the other~ ~o tha~ the polycarbodilmide8 can have ~liphatic, cyclo- -aliphatic~ and aromatic hydrocarbon groups in one poly~
carbodiimide molecule, Polycar~odiimides can be prepared for use in this invention by well known procedure3. Typical pro- ~.
cedure~ are de~cribed in U. S. Patents 3,450,562 to ~:
Hoe8chele; 2,941,983 to Smeltz; 3,193,522 to ~e ~ ann ;~
et al.; and 2,941,966 to Campbell.
Generall~, polycarbodiimides are prepared by poly~erlzatlon of org~c dii~ocganate~. ffle i~ocyanate ; .
group~ on a diisocyanate molecule polymerize with 180-cyanate groupæ on other dil~ocyanate molecules so that the re~ulting polycarbodlimide molecule is a linear polymer ; ~ .
of organlc radlcals (i.e., aliphatic, cycloaliphatic, aroma~ic, or combin~ion~ thereof) linked toeether by carbodiimide group~ (l.e., ~ - C - N-). The degree o~
polymerizatlQn and the speclfic dil~ocyanate determine the molecular welght Or ~he polycarbs)aiimide and the average molecula~r weight per ~arbodiimide group~

~z~

Man~ known organic i~ocyanates can be polym~rlzed to produce polycarbodiimide~ useful ~or at~billzed co~po~i-tion~ of thi~ inYention. I~ocyanate~ which can be polymerized to produce preferred aromatic polycarbodiimlde3 include, tolylene 2,4-dii~ocyanate, tolylene-2,6-dli~ocyanate, o~"4-tol~lene dii~ocyanate, 1,3- and 1,4-phenylene dil~ocyanates,

4,4~-methylenebl8(phenyl iSocyanate),

5-chlorotolylene 2,4-diisocyanate, .~:
1,5-naphthylene dlisocyan~te, 1,6-hexamethylene di~80cyanate, 434~-methylenebis(cyc~oh2xyl i~ocya~ate)~
1,3- and 1,4-cyclohexylene dii6ccyanate~, ~ 3-dlisopropylphenylene-2~4-diiBocyanate~
l-methyl-3,5-d~i 80propylphenylene-2,4-dii~ocyanate~
1,3,5-triethylphenylene-2,4-diisocyanate, tritsopropylphenylene-2,4-(2,6-)di~socyanate.
Diiso~y~nate~ such ~8 tolylene-2,4-aii~ocyan~te or mix-ture~ there~f wlth mlnor amount3 o~ ~olylene-2,6-dii~o-cyanate ~nd 4,4'-methylenebi~(~henyl 180cyanate)~ can be u~ed to produce prePerred unhindered aromatic polycarbodi-imides whlch have only partial ortho ~ubstitutlon on the aromatic nuclei to which polycarbodiimide group~ are attached. Diisocyan~tes ~uch as triisopropylphenglene-1~3-dlisocyanate yleld preferred hindered aromatic polycarbodi-imide~.
Polymerizatlon of diisocyanate~ to produce polycarbodiimides of a given degree o~ polymerizat~on -34 :

- .

3~7 can be controlled by introducing agent~ which w~ll cap the termins.l i~ocyana;~e group~ Thesç agents Include monoisol~yanate~ and active hydrogen compound~ such a~
alcohols or amine~. Pol~l~ocyanates and other agents which will produce cro~s-llnking of the polycarbodiimide generally should be avoided a~ cro3~-linking can reduce ~olubllity and lead to blendin~ problem~ with the copoly~ :
ester. Pre~era~ly, lsocyanate polymerizatlorl ~hould be : :
~topped to produce polycarbodiimlde~ having average molecular weight~ in the range of about 600-2500 and 2-8 carbodiimide linlcages. Polycarboditmide~ ln thi8 pre- -~erred range can be readil~ mixed with copolyester and are suf~ic~ently nonvolatile to prevent 1083 by vaporization.
The ~verage number o~ carbodiimide group~ per molecule can be e~timated for a giren polycarbodilmide from the proportlons of the reactant~ employed 1~ its prepæration. A~ described elsewhere~ the degree of ~:~
~olymerization of the polycarbodiimide can be controlled O by employing capping agents~ Alterna~ivelg, the average number o~ carbo~ilmlde ~roup~ per molecule in a gi~en polycarbodiimlde can be calculated ~rom it~ molecular weight (obtained by vapor pha~e o~mometry or ebulliæcopic procedures) and it~ a~say ~or carbodli~ide group~
~determined by the method o~ Ca~pbell and Smeltz, J. Org.
Chem., ~ 2069-2075 (1963)~7.
A particularly pre~erred polycarbodi~mide 3B
sold under the tradename Stabaxol~ PCD by Mobay Chemical, ; ,~
Pitt~burgh~ Penn~yl~nl~.
Component (b) o~ the ~tabil~zer mixture can ,, . , . --.. , . , . -be ~ither a hlndered phenol, a nltro~en-containing hindered phenol or ~ ~econdary amine. U3eful hindered phenols include: 2,6-ditertiary butyl-p-cresol;
4,4'-bi 8 ( 2,6-d~tertiarybutylphenol); 4,4'~4"_(2,4,6_ trlmethyl-5-phenyl) trimethylene) tris 2,6-di-tert.-but~l phenol; l,3,5-trimethy1-2,4,6~tri 8~,5-ditertlary-butyl-4-hydroxybengy~7 benzenej 4,~'-butylidene bi~(6-tertiaxy-butyl-m-cresol); ~, ~-oxybi~(2,5-dl-~ert.~
butyl-p-cre~ol; 2,6-di tert,-butyl-~-methoxyYp-cresol;
2,6 bis(5,tert.-butyl-4-hydroxy-m-to yl) me~tol (Plastano~ 80); 4,4~-methylene-bis(2,6-di-tert~-b~tyl-phenol) ~Ethyl~ A0 702, Ionox~ 22Q7; 2~2'-methyl0ne-bis-(6-tert.-butyl 4-methyl) phen~l; 4,4'-(tetramethyl-p-phenylene) dimethylene-bis-2,6-di-tert.-butyl phenol;
2,2',6,6'-tetra-tert.-butyl-p,p' b1phenol; 3,5'dltert.-bu~yl-4-hydroxy benzyl alcohol; 4,4'-i~opropylidine-bis-butylated phenol, 2,5-ditert.-butyl hydroquinone, 2,2~-methylenebis(6-tert-butyl-4-methyl phenol), 2,2'-methylenebls(6-tert-butyl-4-ethyl phenol)3 2,2'-~e~hylenebis ~-methyl-6-(1,1,3,3-tetramethyl)butyl pheno~7; 4~4Jbi 8 (2-tert-butyl-5-methyl phenol) sulfide;
4,4~-butylidene-bl~(2-tert-butyl-5-methyl phenol); 2,2'-methylenebis(~,6~dimethyl phenol); 2~ter~-butyl-4(4-tert-butyl phenyl)phenol; 2-tert-butyl-4-phenyl phenol, 2,6-dl-benzyl-4-methyl phenol3 2-benzyl-4-methyl phenol; 2-benzyl-6-tert-butyl-4-methyl phenol; 2-benzyl-6-tert-butyl-4-ethyl phenol; 2,4-dlmethyl-6~ methyl-l-cycloh0xyl) phenol, 2,6-diisopropyl-4-methyl pheno~; 2,4 di~thyl;6-i~opropyl phenol; 2-tert-butyl~;~4,6-dimethyl phenol; 2-tert-bu~yl-4-methyl phenol; 2~(1,1,3,3-t~tra-methyl butyl)-4-- :

38~7 methyl phenol; 2~4,6-trimethyl phenol, 2,6-di-tert-bu~yl-4-methyl phenol; ~,6-di~tert-butyl-1~-ethyl phenol; 4-phenyl phenol; 2,6-diisopropyl phenol; 2,6-di-tert-butyl-4-phenyl phenol; 2,6-di-tert-butyl-4(4-tert-butyl-phenyl)phenol;
2~5-di-tert-butyl-hydroquinone; 2,5-di-teYt-amyl-hydroqui-none, and alpha-conidendr:ine Mixtures o~ the ~oregoing may be used. The pre~erred hindered phenol is tetra-kisCmethylene-3-(3~5~-ditertiary-butyl-4~-hydroxy-phenyl) propionate] methane.
Suitable nitrogen-containing hindered phenols include ~,6-di-~ert-butyl- ~-dimethylamino-p-cresol; 4-hydroxydodecananilide; 4-hydroxy butyranalide; p-butyl-aminophenol~ 2,4-bis~n-octylthio3 -6[4~-hydroxy-3,5' di-tertiary butyl anilino~ -1,3,5-triazine. A pre~erred com-pound is CHA 1014* sold by Ciba-Gelgy, Ardsle~, New York.
Use~u1 secondary amine compounds are 4,4'-dioctyl diphenylamine; diethyl di~onyl diphenylamine, 4-isopropoxy diphenylamine; N,N'-diphenyl-1~2-propane-diamlne, octylated diphenylamine; p-isopropoxydiphenyl-amine; phenyl- ~-naphthylamine; phenyl ~ na~hthylamine;
N,N' diphenylethylene diamine; N',N' di-o-tolylethylene diamine; Nl3N~-diphenyl-1,2-propylene diamine, N,N'-diphenyl-p-phenylene diamine. A pre~erred secondary amine is N~N'-di-2-naphthylparaphenylenediamine sold by Vanderbilt Chemical Co., Nashville, Tennessee.
Component (c) o~ the stabilizer mixture is a phosphorous acid ester including trioctyl phosphlte, pentol triphosphite, trilauryl phosphite, triisodecyl phosphi-teS diphenyl isooctyl phosphite~ (2-ethylhexyl)-*denotes trade mark 23~7 oct~l-phenyl pho~phite, tr~(2-ethylhexyl) pho~phite, trlphenyl pho~phite, trimethyl pho~phltel trlethyl pho~phite, diphenyl-p (~-methylbenzyl) phenyl pho~phite, tributyl phosphite, phenyl-di(l~odecyl) phosphite, tri-tetr~hydro-fur~uryl phosphite, dl(i~od2cyl~-2-ethylphenyl phosphite, tri-secondarybutyl phosphite, tri-tertlarybutyl pho~phiteJ
trihex~l phosphite, trlcyclohexyl phoaphite, dlphenyl-lauryl phosphite, ph~nyl-dilauryl ph~sphite, trinaphthyl pho3ph~te.
A pre~erred compound is tri(nonylphenyl phosphite) ~old by 10 Argus Chemlcal Corp., Brooklyn New York u~der the trade-name Mark~ 1178.
Component (d) of the ~t~bllizer mixture is either an amino acrylate, a homopolymer of the ~mlno acrylate, or a random copo~y~er ffl ethylene and the am~no acrylat~. Suitable amino acrylate~ include N,N-dimethyl-aminoethyl acrylate, aminoethyl acrylate) N-methylamino-ethyl acrylate, N,N-butylaminoethyl acrylate, ~,N-dl~n-butylaminoethyl acrylate, N,N-dimethylaminobutyl acr~late, .
dimethylamino propyl acryla~e, N,N'-dli~opropy~aminoethyl acrylate. The methacrylate~ o~ these compound~ can als~
be used. N,N-dlmethylaminoethyl methacrylate i~ preferred.
When the copolymer i8 u~ed, ethylene is pre~ent i~ an amount of 60 to 80 p~r~ent by weight and the amino acrylate or methacrylate in an amount o~ 4~ to 20 percent by weight.
A preferred ratio o~ eth~lene to amino acrylate i~ 70:30 ;~
percent by weight.
me properties o~ the composltions o~ this in-vention can be modifled by the incorporation o~ various conventlonal inorganlc fillers ~uch a~ wood flour, s~licates, ~ilica gel, alumina, clay~, chopped ~iberglas~, ;

~23~7 ~itanlum dioxide, carbon bl~ckJ and the llke~ In general, filler~ have the effect o~ increaslng the mel~ V~CQ~ity and the modulu8 or stlffne~ of the composition at variou~ elongatlons.
The propertle~ o~ the compo81tion~ of this ln-ventlon can be ~urther modified by the incorporation o* ~-thermally stable thermopla~tic polymers of ethylenically unsaturated monomers including homopolymer~ of vi.nyl ester~ euch a3 vinyl acetate, copolymer~ o:~ these vlnyl ester~ with other vinyl monomer~ such a~ ethyl~ne, vinyl chloride and the like, and polymers o~ alkgl acrylate~
and methacrylates, or thermally stable condensatlon polymers ~uch a~ polye~ter~ and polyamides, and the like.
For example, the addition of a copolymer of ethylene and vinyl ~cetate ~ten ~ncrease~ the tackine~ o~ pre~ure sen~itivs adhe~ive compo~itions of thiæ lnvention. The~e modifying polymers typicallg have melt ~l~cosities abo~e about 10,000 centipol~es at 200C. and thus are not low , molecular weight thermopla~tic res~n~ as de~ined here~n.
The co~ ltions can ælso be colored by the addition o~ organlc or inor~;anlc pigment~ or organic dyes where their e~fect i8 desired. Suitable inorganic pigments lnclude rutile and anatase titanium dio~de3, alumin~
powder, cadmium sul~lde~ and sul~o~elenides, lead anti~
mon~te, mercury cadmium~, chromates o~ n'lckel, tin and lead~ ceram~c green3 ~uch a~ chromium, cobalt$ tltanlum : . ;
and nlcke~ oxides, ceramic black~ such as chromium, cobalt and lron oxide~, carbon black, ul~ramarlne bl~e, ~d the l~ke. Su~table organic pigEn~nt~ include phthalocyan~ne blue~ and greens, quinacrldone~, and the like~. Su~table -39~
~- ' ,, ~ . .

dyes lFlclud~ perse dye~ such as Colour Ind~x Dl~perse Blue~ 59, 63 and 64. Optic~l brigh~ener ~uch as UVITEX*
CF, ~old by Clb~ Corp., and TD~OPAL* AM, æold by Geigy ~hemical Co~p., may also be inco~porated where their eff~ct is de~lred.
Plastlciæers i~cluding ph~halate e~ter~ ~uch as d~octyl phthalate, and aryl phosph~tes such as t~cre~
~ho~phate, and subs~ituted sul~c>namides such as N-cyclo-hexyl~p-tolu~ne-sulfon~nide and the like, may be added lû ~or appllcat:lon~ wher~ their e~fect i~ de~ired. Fl~e retard~nt ~d~ti~es, ~uch a~ zi~c bora~e, an~imon~ tri-o~de~ tr~s(2,3~chlor~?ropy~) phosp~a~e~ trls(2,3-dibromo~ pyl) pho~phE~e, chlorinated waxee, a~d the like may be added, i~ desired. Other minor addltive~ :
such a~ ~ur~actant~ or llibricanl;g may ~lso be added.
~ ne o~ the ~o:~an~ advan~ages of the thermo~
plastlc co~po~itions of this inventlon is that the copoly-ester elastomers and the low molecular weigh~ ~hel~mo-plastic resins are ~asy to blend together due to the 20 r~l~ti~ely low melt visco~ity of the~e c6~position~ ~t elevated teE~per~ure~ a~ e~n~pare~ l;o co~positi~næ o~ the prior a~t having con~parable bond ~trength. The co~ponent~
o~ the co~poa~tion~ of thi~ inve~ti~n can be blended by ~ariou~ly we~ own procedure such as, for exa~le,, blending in m~lten f'orm, blending in a sol~re~, ~r mixin~;
aqueou~ disp~r~ion~ of the co~po~nt~Q Blendi~g in the mel~ r be carried o~ by ~ir~ melt~ng the a~h~sion-modi~ed, ~tabil~zed ~egmented c~olye~ter el~stomer and then addlng 1QW moleeular wei~ht ~he~mopl~ætic resin to the 30 melt, b~ ~irst melting th~ r molecu~r weight the~
*den~teæ tra~ m~rk :: .
.
. .

3~7 plaætlc re~in and then adding adhes~lorl-modified, ~t~zad ~
~egmented copolyester elastomer to the melt, or by rirst ~ :
blending the segmented copolye~ter elastomer and the l~w molecular wei~ht thermopla~tic re~ln together in finely divlded form and then melting the blend, for exa~nple; on a hot roller mill or by slmultaneou~lg feedlng the components to an extruder. The ~tabilizing compound~ and/or adhe~ion-promoter can be pre~ent prior to blending or can be added with the other components indi~idually or ~8 a m~xture.
In addltlon to the~e blendlng procedures, ~t 1 also po~3ible to talce the copolyeæter ~rom the ~nthesis ~tep ~nd, while it i~ ~till molten, blend solid, premelted, or liquid low molecu~ar ~rei~ght therrnopla~tic re~in with it~
The adhes~on modifying compounds a~ well as other ~n-gredlent ~ such a~ stabilizers, antioxidantæ, fillers, pla3ticizer~, and the llke c~n al~o be added at this time.
Thi8 blending procee~ can be carried out with an in-line mixer or with a ~eparate mixing vessel, and ha~ the advantage th~t it doe~ not require lsolatton Or the copolye~ter~
me therm~plastic compo~itions of thlæ invent~on :
can al~o be blended by dis~olving the segmented copolye3ter : ~
and t~e low molecular weight thermopla3tic re~in ~n a . .
~olvent. Suitable solvents ~or preparing these ~olutlons include chlorinated hydrocarbon~ such as methylene chloride, chloroform, trichloroethylene, ~olvent mixture~ such as ~;
mixtures o~ trichloroethylene and i~opropanol, and the llke.
Aqueou~ d~spersions of the thermopl~t~c composl~
tions of thi~ invention can be prep~red by di3solvlng the segmented copoly~ter and the l~w molecul~r weight thermo~

! .

~æ3~

plastic resin together in ~ suitable water-imml~cible or~Janic solvent, emuls~fy~ng the organic solvent con~alning the segmented copolyester and the low molecular weight thermoplastic resin in water, and removing the organic -solvent a~ described by Funck and Wol~ in U. S0 Patent NoO 3,296,172. Di~per~ions can æl~o be prepared by dissolving the segmented copolye~ter in a ~ultab}e water-immiacibl~ organic solvent, dls~lving th~ low molecular weight thermoplastlc resin in a di~erent water-immiscibl~
orgar~c ~olvent, emul~ ing BUCh orga~i¢ ~olvent ~olutlon .
in water, remo~rlng the organic ~olvent from each em~l~ion, thereby forming ~eparate di~per~ion~, and mixlng the di~per~ions together in proper a~nounts.
Compositions containing about 50 percent ~y weight or more of ~egmented copolye~ter elastomer can be u3ed as concentrates for further compounding wlth the same or other lo~ molecular weight thermoplastic reæin~
and modifiers~ as well aæ being u~e~ul as ~uch~ Such concen~rated compos~tions have the advantage of being 20 processab~e with additton&l com~onent~ at lower tempera- .
tures and shear requirements than the ~egmented copoly-ester ela~tomer itself. For ex~mple, a mixture containing an equal weight of 3egmented copolye~ter ela~tomer and lo~
molecular weight, thermopl~tic ~tyrene homopolymer is typically blended at a mlnimum temperature o~ about 170C~
However, addltional low molecular weight thermopla~tic reslns can be mixed with this concentrate a~ a minlmum blending t~mperature of about 140C. Moreover, addition~l l~w molecular weight thermoplastie re~ins whl~h have limdted compa~ibility with the segmented copolye~ter 23~7 ela~tomer alone tend to be more compatlble with such concentrates.
The composition~ of thi~ inventlon are u~eful a~ adhesive~ and as co~ting composition~. The~e compo itlon~ can be aFplied in the ~orm of a dry blend~
a solution, an aqueous di~persion, or a molten :Eorm.
lhe ~ofter composition~ are use~ul a~ pre~ure ~en~itive adheslve~ which can be appl~ed in the ~orm of a ~olution, an aqueous di~persion, or i~ rnolten rorm. The method 10 o~ application does not appreciably ai~fect the per~ormance of the compo~ition.
Conventional app:~ication equipment can be used for applylng the co~po~ition~ o:E thi~ invention in the variou~ form~. ~or applicatic~n o~ ~olution~ or dispers~s~n~, a~ in the ca~e o~ heat sealing and pre~sure sen~itive adhesive~, various known appllca~ion technique~ can be u~ed including bru~hing, dlpping~9 roll coating, wire~
wound rod applica~;ion~ do~toring~ printing, and the likeD ~;
Sprayin~; or c~rtain coatlng ~echnique~ are als~ applicable 20 to these forms c~f~ the compoæltion~.
For appLtcation of these compositions in the melt ~orm, dipping, roll coating, calendarlng, curta~n co~tlng, ~ -extruding, hot spraylng, and other hot melt application techniques can be uged. Powder coating6 of approprlate nontacky compositions can al~o b~ applied by known ~ idized b~d ~echniques, electro~tatic powder spray application3 or ~:
pla~ma spraying. ~ ~:
In u~ing the composltis3n~ o~ thi~ invent~on a~
hot melt adhesive~, the Joînlng step can be accompli~hed .-by applylng the molten composi~ion to one ~urface, brlnging ;

. .

3~

the other sur~ac~ to contact wi:th the mol~en con~po~ition9 and allolYing the bond to cool~. Coatin~;~ o~ these con~posi-tions can be bonded to other surface~ or them~elves b~r heat or solve~ act~vation of the coating~ and contactirlg the acti~ated coating with the ~econd ~ur~ac~ ~nd allowing the bond to cool or the solvant to evaporate. Eeat activa-tion of the coatlng i8 typically carrled out in an oven or using an in~rared lamp. Simul~aneou~ applic~tion ~ heat and pres~ure. or hea~ sealing, can be used wl~h ~hese eon~po-~0 sitions to acc~r~pllsh bollding. Go~unercially availabïe, edge banding and sur~ace laJnin~ting machinery can also be en~?loyed to ~pply adhes~v~æ de~eribed herein and to prepare lamln~tes therewith. H:igh frequency dielectric and u~ onic waves c~n al80 b~ used ~o acti~a~e these c~mpositions to effect bonding.
The cor~positlons of this invention are characteriæed by an outstanding comb~nation o~ properties. l~ese con~po~
tions have demonstrate~ lmproYed a.~hesio~ to m~ny s~bst~ate~
incluaing dif~cul~ly adh~able substra~e~ su~h as me~ne-~o~ldehyde laminated pla~tics (FORMICA*~o T~ey have high te~perature bond strength&, ~r exa ~ le~, as show~ by failure temperatures hi~her than about 70C. as me~sured by the programmed te~perature cleavage test descsibed below. They have good low temperature ~lexibility5 that is, resi~tance to breakage on im~aet.
Due to the presence o~ the stabili21ng mix~ure the compositions have good pot ll~e when he~ted to 170 to 200C~ for extended periods of time within the pe~lod o~ ~
12 to 24 hours. ~ ~ -The compositions containing up to 50 perc~nt by *denotes trade mark ~æ~7 w~ight of ~egm~nted copolyester ela~tomer are particularly use~ul a~ hot melt adh~lv0~ ln a wlde varlety o~ adhe~ive use applications, speclfically for ~dgc banding and ~urface lamination, for example, in furniture m~nufacture, vinyl lamin~tlon, ~ole attachment and box-toe con~truction ~-~
in shoe a~embly, Compositions containing about 50 percent or more by weight of thermopla~tlc ~egmented copolyester ela~tomer are particularlg u~e~ul in the preparation o~ molded, ~;
~xtruded, and di~ped good~, coating~, binders, ~xtruded adhe~ives, sealants, and the llke~ Film~ can b0 prepared ~rom these compo~ition~ by molding, extrusion and ca~endaring te~hnlgues. The~e eompo~itions typlcally con~
ta~n about 50 to 99 percent by weight o~ ~egmented copoly-e~ter elastomer and about 1 to 50 percent by welght of low molecular welght thermoplastic resin. Prererably they contain about 50 to 95 percent by weight o~ segmented copolyester elastomer and about 5 to 50 percent by ~eight ~:
of low molecular welght thermoplastic resin~
E~MPLES 0~ THE INVE~TION
~ . .
The following examplea lllu~trate the invention. ~:
Ring and ball ~o~tening points can be determined by AST~
method E 28-67. Bond Preparation of Particle Board/
Melamine Formaldehyde Laminate3 :: - , Test ~ample~ used in the example~ axe prepared ~rom precut pleces of particle board, 2.54 cm. wide x 2.54 cm. thick x 10.16 cm. long, and precut strlps o~
melamine-formaldehyde laminate, 1.9 cm. wide x 0.16 cm.
thick x 5~o8 cm. long~ Adhe~lve is melted under an :
infrared lamp or on a temperature-regulated hot plate, . . . . . . .
: . . . . . ..

~8~3~
.

~nd approximately 0. 5 g. i8 applled to a 1.9 cm. x 1.9 cm. area at one end of the partic le board strip, and laminate i8 formed whlle hot to the room temperature mel~ne strip ln the form of a lap Jolnt. Depending on the intended end use, the adhe~ve ls applled either to the cut edge or ~urface o~ the partlcle board. Laminatlon is accomplished with the application of pres~ure to provide intimate contact and to achleve the goal adheslve thickne~
of 0.13 ~ 0.025 mm on the surface and 0.254 ~ 0.025 mm on the edge. The exces~ adhe~ive ~illet is care~ully trimmed ~rom the test sample, which 1~ allowed to age at least overnight be~ore testing.
Shear aL~d Clea~age te5t8 were per~ormed follows:

This test i~ an adaptation of test method WPS-68 described by W. Schnelder and D. Fabricius ln the German perlodical "Adhae~ion", ,J~nuary, 1969, Pages 28 37.
Thermal te~tlng of the bonded ~ample is carried out by suspending it ln she&r conff guration ln a circulating alr oven he~d at 50C. (122F.). A weight of 0.45 kg. is ~. .
applied to the end o~ the melamine ~tr~p after the ~ample ha~ been heated ~or 0.5 hour. The temperature of the oven i8 program~ed to increase linearlg ~rom 50C~ (122~F.) at a rate o~ lO~C. (18F. ) per hour. me ~ailure temperature i~ recorded when the weight :t~all~. qhe method i~ adapted to an automated procedure by incorporatlon o:e a temperature programmer and a temperature record~r ~or the oven; and ~ .
for eaeh ~ample~ ELn elapsed time indicator which is ~wit~h~d off by the ralllng ~eight. ;; ~ :
.
--46;

3~7 Pro~rammed Temperature Cleavage Samples for thls test are prepared in a manner identical to that for the Programmed Temperature Shear Test.
Thermal testing of the aged sample is again carried out in a circulating air oven, with the adhesive-bonded area in a horizontal con~iguration and the melamine laminate on the bottom. A 0.45 kg. weight is suspended ~rom the melamine strip 0.45 kg. from the edge o~ the bonded area. The oven temperature is again programmed linearly, but this time from room temperature at a rate of L0C. (18F.) per hour, and the failure temperature is ~aken when the weight falls.

A semistructural adhesive blend was prepared by blendlng the following materials at 175C. with vigorous stirring for approximately 1 hour until homogeneous~
Segmented Copolyester40 g.
Piccovar~ L-30 20 g.
Piccolastic~ A-50 20 g.
Piccoumaron~ 410HL 20 g. `
Pyromellitic Dianhydri~e (PMDA) 1 g. -Naugar ~ 445 o.5 g.
The segmented copolyester material was a block copolyester prepared as follows:
Into a 3000 ml. resin kettle ~itted for distillation was placed:
Polytetramethylene Ether Glycol (PTMEG), Number Average Molecular Weight 1000 446.o g.
1~4-Butanediol (BD0)296.9 g. (50~ Excess) ..

Z3&17 Dimethyl Terephthalate (DMT) 399. 3 g.
Dimethyl Isophthalate (DMI)115.9 g.
Naugar ~ 4l~5 9.9 g Tyzor6~ TBT ~Tetrabutyltitanate, 5% Solution in BD0) 1.0 g.
The reaction kettLe was heated to 150C. at atmospheric pressure at which time the catalyst was charged.
The reaction was then heated to 250C. under a nitrogen atmosphere over a period of 1 hour. Methano} distillation started almost immedlately. When the temperature reached 250C., a vacuum o~ 160 mm. was applied and held ~or 5 minutes, after which the pressure was further reduced to 80 mm. for 5 minutes, 40 mm. for 5 minutes, and finally to full vacuum (0.5 mm. of ~g or less) and distillation was continued at full vacuum at 250C. for 1 hour. The resulting viscous molten product was scraped from the flask in a nitrogen ~H20 and 2 free) atmosphere and allowed to cool.
The segmented copolyester so obtained is charac-terized by a melt index (2160 g./200C.) of 6-8, a TMA S.P.
of 144C. and a DTA crystalline M.P. of 15~C. The 1,4-butanediol/PTMEG mole ratio is 5.0 and the dimethyltere-phthalate to total phthalate ratio is o.78.
Piccovar~ L-30 is a polyindene petroleum resin having a softening point of 30C. sold by Hercules~ Inc. - -"Piccolastic" A-50 is a low molecular weight styrene homo- ~ -polymer having a ring and ball so~tening point of about 50C. ~ ~ -and a melt viscosity of 29 centipoises at 190C. ~old by Hercules~ Inc. "Piccoumaron" 410HL is a highly aromatic i~823~

polyindene type hydrocarbon re~in ha~ing a ring ~nd ball ~oftening point of 110C. and a melt vi~coslty o~ 158 centipoi~es at 190C. sold by Hercule~, Inc. Pyromellitlc dianhydride ~g ~upplled by E. I. du Pont de Nemour~ and Company, Inc. "Nhugard" i~ an antloxidant ~old by Naugatuck Chemical Comparly, a division o~ Uniroyal Company.
"Tyzor" T~T i~ tetrabutyltltanate 301d by E. I. du Pont de Nemour3 and Company, Inc.
Particle board/melamlne-~ormaldehyde laminate~
were prepared a8 de~cribed above. Shear and cleavage ~:
results are recorded in Table I. Fa~lure mode wa~ cohe~ve.
A 25.4 cm. x 25.4 cm. partlcle board/"Formica" (0.16 cm.
thlck) laminate prepared rrom the adhes~ve compo~ltion of this example curv~ved greater than two week~ at 70C. with~
out substrate delamlnation wherea~ a lamlnate prepared from an adhe~ive compo#ition not contalning an adhe~lon promoter : ~ -delaminated in le~s than 1 hour at 70 C.
h~MPIE 2 ~ ~ ~
A composition ~imllar to th~t de~cribed in : ~ .
Example 1 was prepared sxcept that onlg 0,5 g. o~ PMDA
was added, Naugard~ 445 ~a8 omltted, and the following stabilizer~ were added:
Stabaxol~ PCD 0.25 g.
E/DMAEMA Resin 1.0 g.
Irganox~ 1010 1.0 g.
Mark~9 1178 1, 0 g.
Stabaxol~ PCD i~ a mlxture of hindered aromatic polycarbodiimides having an averag~ molecular weight o~
~bout 1000 containing unitæ of -49- .

N-C3~-~CH(CH3) ~n where n ha~ an average value o~ about 3 sold by Naftone, Inc., New York, New York; Irganox~ 1010 i~ ~ tetraki~-rethylene-3-(3',5'-ditertlary-butyl-4l-hydroxyphenol) propionat~7 methane high melting phenolic antloxidant ~old by Geigy Chemlcal CO-3 Mark~ 1178 i9 tri~ nonyl phenyl phosphlte ~old by Argu~ ~hem~cal Corporation, Brooklyn, New York.
E/DMAEMA reæin i~ a copolymer o~ ethglene (70~) and N,N-dimethylaminoe~hyl ~ethacrylate (30%).
Cleavage te~t value for a laminate using the adhes~ve compositlon ie listed ln Table I. Failure mode was cohe~lve.
~ .
A composltion similar to that de~crlbed in Example 2 wa~ prepared except that 1.0 g., of cyclopentane- :
tetracarboxyLic dianhydride, CPTCDA, wa~ added ln place of the PMDA, and 1.0 g. S~abaxol~ PCD wa3 u~ed. : :
Cleavage test value ~or a laminate u~ing the - . ~
adhedve con~position is li~ted ln Table I. Failure mode ~ ~ -wa~ c ohe sl ve .

A composition ~lmilar to that de~cribed in ~xample 3 was prepared except that loO g~ naphthalene tetracarboxyllc dianhydrideg ~TCDA, wa~ added in place o~
CPTCDA.
Cleavage test value for a laminate u~ing the adhesive co~po~itlon i~ ted ln Table I. Failure ~ode 30 was cohesive. ~ --50~

- ;~, ~7 :~

. .
A compo~it~on 3im~1ar to that de~cribed in Example 3 was prepared except that 1~0 g. o~ benæoph~none tetracarboxylic dlanhydride, BTCDA, wa3 u~ed in pl~ce o~
CPTCDA.
Cleavage test value ior a laminate using the ;~
adhei3~ve compositlon is listed ln Table Io Fa;ilure m~de was cohe~i ve. `~
EXAMPlæ 6 .
A composition ~imilar to that described in , Exanple 3 wa~ prepared exc2pt that 2.0 g. of benzophenone tetracarboxylic dlanhydride was u~ed in place o~ CPTCDA. .
Cleavage te~t valu~ ~or a l~minate uslng the adhe~ive compositlon i8 li~ted in Table I. FaillLre mode wa~ cohesive .
': '`: '~' A composition slmilar to that described in Exa~ple 2 was prepared except that 5.0 g. o~ Arco0 SMA
lOOOA resin (a ~tyrenejmæleic ~nhydrlde copol~rmer available 20 frol~ Atlan~lc Richrield Company) was ~dde~ in place of the PMDA" and 1.5 ~. oP the E/D~E~ resin was ~dded ~ :
instead o~ 1. 0 g.
Cleavage and ~hear test value~ ror laminate~ :
using the adhesive composition are listed in Table I.
Failure mode was cohesive.
' A compo~ltion similar to that de~cribed in Exa~nple 7 ~ag prepared except that 5.0 g. of Arco(~ SMA ~ ;
17352A resln (a styrene/maleic anhydride copolymer : -3Q available from Atlantic Rich~ield Company) wa~ added in ~ .

--51-- ~

- . . . .

~lace of the anhydrLde copolymer of Example 7.
Cleavage and shear test value~ for laminates using the adhesive composltlon are listed ln Table I.
Failure mode was cohesive.

~ .
A semistructural adhesive blend was prepared by blending the f Q llowing material~ at 175~C. wLth vigorous stirring for a~proximately 1 hour until homogeneous:
Segmented Copolyester (prepared according to Exam~le 1)40 g.
Nevillac~3 X-66 13.3 g-Nevillac~ $H 13.3 g-Piccoumaro ~ 410HL 6.7 g.
BaS04 27 g-Pyromellitic Dianhydride (PMDA) 1.0 g.
Stabaxol~ PCD 0,25 g.
E/~AEMA Resin 1.0 g.
Mar ~ 1178 2.0 g.
Irgano ~ 1010 1.0 g.
Nevillac~ X-66 (softening point 10C.) and Nevilla ~ SH (softening p~int 100-110~.) are both phenol modified coumarone indene resins available from Neville Chemical Company.
Cleavage and shear test values for laminates using the adhesive composition are listed in Table I.
Failure mode was cohesive.

A composition similar to that described in Example 9 was prepared except that 2.5 g. of the E/DMAEMA
resin and 1~.0 g. Mar ~ 1178 were used.

Cleavage and shear kest values for laminates using the adhesive composltion are Listed in Table I.

Failure mode was cohesive. - ~

,XAMPLE 11 ~ -A composition similar to that described in Example 9 was prepared except that 3.5 g. of the E/DMAEMA

resin and 2.5 g. of Mark~ 1178 were used. ~ ;~

Cleavage and shear test values for laminates ;

using the adhesive composition are listed in Table ~.

Failure mode was cohesive.

EXAMPL$ 12 ~ . _ . .
A semistructural adhesive blend was prepared by blending the following mater~als at 175C. with vigorous st~rring for approximately 1 ~our until homogeneous:

Segmented Copolyester (prepared according to Example 1)35 g.
piccovar~ L-30 35 g.
Piccolasti ~ A-50 30 g.

Pyromellitic Dianhydride - ~PMDA) 1.0 g.
Stabaxol~ PCD 0.25 g.
E/DMAEMA Resin 1.5 g-Mar ~ 1178 1.0 g.
Irgano ~ 1010 1.0 g.
Cleavage test value for a laminate using the adhesive composition is listed in Tab}e I. Failure mode ;
was cohesive.

_ A semistructural adhesive blend was prepared by blending the following materials at 175C. with vigorous stirring for approximately 1 hour until homogeneous.

. . .

~ . ., . . . . ~ : -Segmented Co~ol~ester (prepared according to Example 1)45 g.
Nevillac~ X-66 25 g.
Piccoumaron~) 410HL 30 g.
Pyromellitic Dianhydride (PMDA) 1.0 g.
Stabaxol~ PCD 0.25 g.
E/DMAEMA Resln 1.5 g-Mar ~ L178 1.0 g.
Irgano ~ 1010 1.0 g.
Cleavage test vàlue ~or a laminate u~ing the adhesive composition is listed in Table I. Failure mode was -~
cohesive.
EXAMPLE _14 A composition similar to that described in Example 2 was prepared except that 1.5 g. of the E/DMAEMA
resin was used. Adhesive was applied and laminates were prepared by means of a Salgo (Stiles Manu~acturing) Surface -~
Laminator. Cleavage and shear test values for laminates using the adhesive co~position are listed in Table I, shear being extremely high. Failure mode l~as cohesive.

Into a 1000 ml. resin kettle ~itted ~or dis-tillation was placed:
PTMRG 348.0 g.
1,4-Butanediol (BD0) 213.0 g.
Dimethyl Terephthalate (DMT) 316.0 g.
Dimethyl Adipate (DMA)80.0 g.
Naugard~ 445 3.45 g.
Tyzo ~ TBT (tetrabutyl~
titanate, 5~ ~olution in ~-BD0) o.69 g-~;: :

8~23~7 The reactlon kettle wa3 heated to 190C. at :
atmospheric pressure ~t whlch time the cataly~t wa~
chargedO The reaction was then heated to 260C. under a nitrogen atDlosphere over a perlod o~ 1 hour. Methanol distillation ~tarted almo~t i~medlately. ~hen the temperature reached 260C. vacuum wæ~ reduced ~lowly to about 0~2 mm o~ mercur~ and di~ti}latlon wa~ con-tinued at ~ull vacuum at 260C. ~or about 4 hours. The resulting viscou3 molten product was ~craped ~rom the flask in a nltrogen (H20 and 2 ~ree) atmo~phere and allowed to cool. me polymer wa~ chara~terlzed by a melt index (2160 e. at 190C.) o~ 3.6, a TMA S.P. o~ 145 C~, and a DTA crystalline meltlng point o~ 157C. me 1,4-butanediol/PTMEG ratio wa~ 5.0 and the dimethyl- , terephthalate to total-d~methyl e~ter ratio ~a~ 0.78.
An adhesive as de~cribed ln Example 2 waB pre-pared except that 1.0 g. of PMDA, 1~5 g. of E/bMAEMA re~in ; :
and an additional 4~75 g. oi Plccoumaron~ 410 HL w~re ad~ed.
Particle board/m~lamine~ormaldehyde lamlnate~
were prepared a~ de~cribed ln Example 1. Shear andCleavage re~ult~ are recorded in Table I. Fail~re mode was cohesire.
EXAMP~E 16 (Control) A compo~l tion slmilar to that descr$bed in Example 1 wa~ prepared except that pyromellitic dianhydride tP~mA) was anittea. Cleavage te~t value oP the adhesive blend not containing an adhe~ion promoter i8 listed in :
Table I. Cleavage failure was ex~remely low. Failure mode was adhe~ive.

~%~7 EXAMPLE 17 ( Control ) A compo~it~on similar to th~t de~cribed ln Example 2 wa~ prepared except that 1. 5 e o~ E/DMAEMA re~ln was added and pyromellitic dianhydride (PMDA) wa~ omitted~

Cleavage and ~hear test values f~l3r lami nate~
using the adhe~lve compo~ition are ~ted ln T3.ble I.
Cleavag~ ~ailure temperatur~ wa~ extremely l~w. Failure mode wa~ adhe3ive.
TAI~E I

Clèavage Shear V~lue V~lue '"C. C.
106 ~136

6 122

7 107 13~ :
~3 110 1~
9 llo 136 lo 104 13 1~ 81 1~ 87 145 121 148 ~ -(Control) 16 65 ~Control) 17 57 122 ;~ ~:

-56- :

Claims (86)

The embodiments of the invention in which an exclu-sive property or privilege is claimed are defined as follows:

1. An adhesion-modified thermoplastic segmented copolyester elastomer consisting essentially of a multi-plicity of recurring short chain ester units and long chain ester units joined through ester linkages, said short chain ester units amounting to 15 to 75 percent by weight of said copolyester and being of the formula and said long chain ester units amounting to 25 to 85 per-cent by weight of said copolyester and being of the formula wherein R is the divalent radical remaining after removal of the carboxyl groups from a dicarboxylic acid having a molecular weight of less than 350, D is the divalent radical remaining after removal of the hydroxyl groups from organic diol having a molecular weight of less than 250, and G is the divalent radical remaining after removal of the terminal hydroxyl groups from long chain glycol having an average molecular weight of 350 to 6000, said copolyester having a melt index of less than 150 and a melting point of at least 90°C., modified with 0.75 to 20 parts by weight, per 100 parts by weight of elastomer, of a multi-functional carboxylic compound taken from the group consisting of aromatic and aliphatic anhydrides having at least two anhydride groups.

2. The elastomer of Claim 1 in which the adhesion modifier is pyromellitic acid dianhydride.

3. The elastomer of Claim 1 in which the adhesion modifier is benzophenone tetracarboxylic di-anhydride.

4. The elastomer of Claim 1 in which R is selected from the group consisting of a divalent cyclic, aromatic, aliphatic radical or mixtures of said radicals remaining after removal of the carboxyl groups from a cyclic, aromatic, aliphatic dicarboxylic acid or mixture of said acids.

5. The elastomer of Claim 4 in which r is a divalent aromatic radical remaining after removal of the carboxyl groups from an aromatic dicarboxylic acid.

6. The elastomer of Claim 4 in which R is a mixture of divalent cyclic and aromatic radicals re-maining after removal of the carboxyl groups from the mixture of cyclic and aromatic acids.

7. The elastomer of Claim 1 stabilized with 1.75 to 15.0 parts by weight, per 100 parts by weight of elastomer, of a stabilizer mixture comprising (a) 0.25 to 2.5 parts by weight of a sub-stantially linear polycarbodiimide having an average of at least two carbodiimide groups per molecule;
and at least one compound taken from the group consisting of (b) 0.5 to 2.5 parts by weight of a compound taken from the group consisting of hindered phenols, nitrogen-containing hindered phenols and secondary aromatic amines;
(c) 0.5 to 5.0 parts by weight phosphorous acid esters of the formula where R1, R2 and R3 are C1 to C18 aliphatic, C6 to C15 aromatic, and combinations there-of; and (d) 0.5 to 5.0 parts by weight of an amino compound taken from the group consisting of amino acrylate of the formula where R is hydrogen or methyl, R1 is hydrogen or alkyl of 1 to 4 carbon atoms, R2 is alkyl of 1 to 4 carbon atoms, n is an integer of 1 to 4 inclusive, a homopolymer of said amino acrylate, and a random copolymer of ethylene and 20 to 40 percent by weight of said amino acrylate compound, each of compounds (b), (c) and (d) being compatible with each other and with (a).

8. The elastomer of Claim 7 in which the adhesion modifier is pyromellitic acid dianhydride.

9. The elastomer of Claim 7 in which the adhesion modifier is benzophenone tetracarboxylic di-anhydride.

10. The elastomer of Claim 7 in which the stabilizer mixture comprises (a) and at least two of the compounds (b), (c) and (d).

11. The elastomer of Claim 7 in which the stabilizer mixture consist of (a), (b), (c) and (d), each of said compounds being compatible with one another.

12. The elastomer of Claim 1 in which the short chain ester units amount to 15 to 65 percent by weight of the copolyester, the long chain ester units amount to 35 to 85 percent by weight of the copolyester, and the long chain glycol has a melting point of less than 55°C. and a carbon to oxygen ratio greater than 2.5.

13. The elastomer of Claim 1 in which the short chain ester units amount to 15 to 50 percent by weight of elastomer, the long chain ester units amount to 50 to 85 percent by weight of elastomer, the dicarboxylic acid being 55 to 95 percent by weight terephthalic acid, D is the divalent radical remaining after removal of the hydroxyl groups from butanediol, and G is the divalent radical remaining after removal of the terminal groups from polytetramethylene ether glycol having an average molecular weight of 600 to 3500, the elastomer having a melt index of less than 30 and a melting point of 90 to 160°C.

14. The elastomer of Claim 13 in which the dicarboxylic acid is a mixture of terephthalic acid and isophthalic acid.

15. The elastomer of Claim 14 in which the poly-tetramethylene ether glycol has a molecular weight of 600 to 2100.

16. The elastomer of Claim 15 in which the short chain ester units amount to 15 to 30 percent by weight of the copolyester and the long chain ester units amount to 70 to 85 percent by weight of the copolyester.

17. The elastomer of Claim 16 in which the mixture of terephthalic acid and isophthalic acid contains 70 to 95 percent by weight of terephthalic acid.

18. The elastomer of Claim 7 in which the poly-carbodiimide of the stabilizer mixture is represented by the formula:
where R1, R2 and R3 are C1-C12 aliphatic, C5-C15 cyclo-aliphatic, or C6-C15 aromatic divalent hydrocarbon radi-cals, and combinations thereof; X1 and X2 are hydrogen, or where R4, R5 and R6 are C1-C12 aliphatic C5-C15 cycloaliphatic, and C6-C15 aromatic monovalent hydrocarbon radicals and combinations thereof;
and additionally R4 or R5 can be hydrogen; and n is a number of at least one.

19. The elastomer of Claim 18 in which component (b) of the stabilizer mixture is tetrakis[methylene-3-(3', 5'-ditertiary-butyl-4'hydrocyphenol)propionate]
methane.

20. The elastomer of Claim 7 in which component (b) of the stabilizer mixture is a hindered phenol.

21. The elastomer of Claim 7 in which component (b) of the stabilizer mixture is a nitrogen-containing hindered phenol.

22. The elastomer of Claim 7 in which component (b) of the stabilizer mixture is a secondary aromatic amine.

23. The elastomer of Claim 19 in which component (c) of the stabilizer mixture is tri)nonylphenyl phosphite).

24. The elastomer of Claim 23 in which component (d) of the stabilizer mixture is a copolymer of ethylene, 60 to 80 percent by weight, and dimethylaminoethylmeth-acrylate, 40 to 20 percent.

25. An adhesion-modified thermoplastic composi-tion which comprises, based on the total thermoplastic components, (A) 1 to 99 percent by weight of thermoplastic segmented copolyester elastomer consisting essentially of a multiplicity of recurring short chain ester units and long chain ester units joined through ester linkages, said short chain ester units amounting to 15 to 75 percent by weight of said copolyester and being of the formula and said long chain ester units amounting to 25 to 85 per-cent by weight of said copolyester and being of the formula wherein R is the divalent radical remaining after removal of the carboxyl groups from a dicarboxylic acid having a molecular weight of less than 350, D is the divalent radical remaining after removal of the hydroxyl groups from organic diol having a molecular weight of less than 250, and G is the divalent radical remaining after removal of the terminal hydroxyl groups from long chain glycol having an average molecular weight of 350 to 6000, said copolyester having a melt index of less than 150 and a melting point of at least 90°C.; (B) 1 to 99 percent by weight of low molecular weight thermoplastic resin which forms compatible mixtures with the segmented copolyester, is thermally stable at 150°C., and has a melt viscosity of less than 10,000 centipoises at 200°C., said composition being modified with 0.3 to 8.0 parts by weight, per 100 parts by weight of elastomer and resin, of a multi-functional carboxylic compound taken from the group consisting of aromatic and aliphatic anhydrides having at least two anhydride groups,

26. The composition of Claim 25 in which the adhesion modifier is pyromellitic acid dianhydride.

27. The composition of Claim 25 in which the adhesion modifier is benzophenone tetracarboxylic di-anhydride.

28. The composition of Claim 25 in which R
is selected from the group consisting of a divalent cyclic, aromatic, aliphatic radical or mixtures of said radicals remaining after removal of the carboxyl group from a cyclic, aromatic, aliphatic dicarboxylic acid or mixture of said acids.

29. The composition of Claim 25 in which R
is a divalent aromatic radical remaining after removal of the carboxyl groups from an aromatic dicarboxylic acid.

30. The composition of Claim 25 in which R
is a mixture of divalent cyclic and aromatic radicals remaining after removal of the carboxyl groups from the mixture of cyclic and aromatic acids.

31. The composition of Claim 25 stabilized with (C) 0.75 to 6.0 parts by weight, per 100 parts by weight of elastomer and resin, of a stabilizer mixture comprising (a) 0.1 to 1.0 part by weight of a sub-stantially linear polycarbodiimide having an average of at least two carbodiimide groups per molecule, and at least one compound taken from the group consisting of (b) 0.2 to 1.0 part by weight of a compound taken from the group consisting of hindered phenols, nitrogen-containing hindered phenols and secondary aromatic amines;
(c) 0.25 to 2.0 parts by weight phosphorous acid esters of the formula:

where R1, R2 and R3 are C1 to C18 aliphatic, C6 to C15 aromatic, and combinations thereof;
and (d) 0.20 to 2.0 parts by weight of an amino compound taken from the group consisting of amino acrylate of the formula:

where R is hydrogen or methyl;
R1 is hydrogen or alkyl of 1 to 4 carbon atoms;
R2 is alkyl of 1 to 4 carbon atoms;
and n is an integer of 1 to 4 inclusive, a homopolymer of said amino acrylate, and a random copolymer of ethylene and 20 to 40 percent by weight of said amino acrylate compound, each of said compound (b), (c) and (d) being compatible with each other and with (a).

32. The composition of Claim 31 in which the adhesion modifier is pyromellitic acid dianhydride.

33. The composition of Claim 31 in which the adhesion modifier is benzophenone tetracarboxylic di-anhydride.

34. The composition of Claim 31 in which the stabilizer mixture comprises (a) and at least two of the compounds (b), (c) and (d).

35. The composition of Claim 31 in which the stabilizer mixture consists of (a), (b),(c) and (d), each of said compounds being compatible with one another.

36. The composition of Claim 31 in which the low molecular weight thermoplastic resin is selected from the group consisting of hydrocarbon resins, bituminous asphalts, coal tar pitches, resins, rosin based alkyd resins, phenolic resins, chlorinated aliphatic hydrocarbon waxes, and chlorinated polynuclear aromatic hydrocarbons.

37. The composition of Claim 36 in which the thermoplastic composition comprises 5 to 95 percent by weight of segmented copolyester elastomer and 5 to 95 percent by weight of low molecular weight thermoplastic resin.

38. The composition of Claim 36 which comprises 5 to 50 percent by weight of segmented copolyester elastomer and 50 to 95 percent by weight of low molecular weight thermoplastic resin.

39. The composition of Claim 36 which comprises 50 to 95 percent by weight of segmented copolyester elastomer and 5 to 50 percent by weight of low molecular weight thermoplastic resin.

40. The composition of Claim 37 in which the dicarboxylic acid is of 8 to 16 carbon atoms, the low molecular weight diol is aliphatic diol of 2 to 8 carbon atoms, and the long chain glycol is poly(alkylene ether) glycol in which the alkylene group is of 2 to 9 carbon atoms.

41. The composition of Claim 40 in which the short chain ester units amount to about 30 to 65 percent by weight of the copolyester, the long chain ester units amount to about 35 to 70 percent by weight of the copoly-ester, and the copolyester has a melt index of less than 50 and a melting point of at least 140°C.

42. The composition of Claim 41 in which the dicarboxylic acid is selected from the group con-sisting of terephthalic acid, and mixtures of terephthalic and isophthalic acids, the low molecular weight diol is butanediol, and the long chain glycol is polytetramethylene ether glycol having a molecular weight of 600 to 3000.

43. The composition of Claim 42 which comprises 15 to 45 percent by weight of segmented copolyester elastomer and 55 to 85 percent by weight of low molecular weight thermoplastic resin.

44. The composition of Claim 43 in which the low molecular weight thermoplastic resin is a mixture of at least two low molecular weight thermoplastic resins.

45. The composition of Claim 44 in which one of the low molecular weight thermoplastic resins is a styrene polymer.

46. The composition of Claim 44 in which one of the low molecular weight thermoplastic resins is a coumarone-indene resin.

47. The composition of Claim 44 in which one of the low molecular weight thermoplastic resins is a bituminous asphalt.

48. The composition of Claim 44 in which one of the low molecular weight thermoplastic resins is a rosin.

49. The composition of Claim 44 in which one of the low molecular weight thermoplastic resins is a terpene resin.

50. The composition of Claim 36 in which the dicarboxylic acid is a mixture of terephthalic acid and isophthalic acid.

51. The composition of Claim 50 in which the polytetramethylene ether glycol has a molecular weight of 600 to 2100.

52. The composition of Claim 51 in which the short chain ester units amount to 15 to 30 percent by weight of the copolyester and the long chain ester units amount to 70 to 85 percent of the copolyester.

53. The composition of Claim 52 in which the mixture of terephthalic acid and isophthalic acid contains 60 to 95 percent by weight of terephthalic acid.

54. Method of preparing an adhesion-modified thermoplastic composition which comprises blending in molten form, based on the total thermoplastic components, (A) 1 to 99 percent by weight of thermoplastic segmented copolyester elastomer consisting essentially of a multiplicity of recurring short chain ester units and long chain ester units joined through ester linkages, said short chain ester units amounting to 15 to 75 percent by weight of said copolyester and being of the formula:
and said long chain ester units amounting to 25 to 85 per-cent by weight of said copolyester and being of the formula:
where R is the divalent radical remaining after removal of the carboxyl groups from a dicarboxylic acid having a molecular weight of less than 350, D is the divalent radical remaining after removal of the hydroxyl groups from organic diol having a molecular weight of less than 250, and G is the divalent radical remaining after re-moval of the terminal hydroxyl groups from long chain glycol having an average molecular weight of 350 to 6000, said copolyester having a melt index of less than 150 and a melting point of at least 90°C., (B) 1 to 99 percent of weight of low molecular weight thermoplastic resin which forms compatible mixtures with the segmented copolyester, is thermally stable at 150°C., and has a melt viscosity of less than 10,000 centi-poises at 200°C., modified with 0.3 to 8.0 parts by weight, per 100 parts by weight of elastomer and resin, of a multi-functional carboxylic compound taken from the group consist-ing of aromatic and aliphatic anhydrides having at least two anhydride groups.

55. The method of Claim 54 in which the adhesion modifier is pyromellitic acid dianhydride.

56. The method of Claim 54 in which the adhesion modifier is benzophenone tetracarboxylic dianhydride.

57. The method of Claim 54 stabilized with (C) 0.75 to 6.0 parts by weight, per 100 parts by weight of elastomer and resin, of a stabilizer mixture comprising (a) 0.1 to 1.0 part by weight of a sub-stantially linear polycarbodiimide having an average of at least two carbodiimide groups per molecule;
and at least one compound taken from the group consisting of (b) 0.2 to 1.0 part by weight of a compound taken from the group consisting of hindered phenols, nitrogen-containing hindered phenols and secondary aromatic amines;
(c) 0.25 to 2.0 parts by weight phosphorous acid esters of the formula:

R1, R2 and R3 are C1 to C18 aliphatic, C6 to C15 aromatic, and combinations thereof;
and (d) 0.20 to 2.0 parts by weight of an amino compound taken from the group consisting of amino acrylate of the formula:

wherein R is hydrogen or methyl;
R1 is hydrogen or alkyl of 1 to 4 carbon atoms;
R2 is alkyl of 1 to 4 carbon atoms; and n is an integer of 1 to 4 inclusive, a homopolymer of said amino acrylate, and a random copolymer of ethylene and 20 to 40 percent by weight of said amino acrylate compound, each of said com-pounds (b), (c) and (d) being compatible with each other and with (a).

58. The method of Claim 57 in which the adhesion modifier is pyromellitic acid dianhydride.

59. The method of Claim 57 in which the adhesion modifier is benzophenone tetracarboxylic dianhydride.

60. The method of Claim 57 in which the stabilizer mixture comprises (a) and at least two of the compounds (b), (c) and (d).

61. The method of Claim 57 in which the stabilizer mixture consists of (a), (b), (c) and (d), each of said com-pounds being compatible with one another.

62. The method of Claim 57 in which the short chain ester units amount to 15 to 65 percent by weight of the copolyester, the long chain ester units amount to 35 to 85 percent by weight of the copolyester, and the long chain glycol has a melting point of less than 55°C. and a carbon to oxygen ration greater than 2.5.

63. The method of Claim 57 in which R is a divalent aromatic radical remaining after removal of the carboxyl groups from an aromatic dicarboxylic acid.

64. The method of Claim 62 in which the low molecular weight thermoplastic resin is selected from the group consisting of hydrocarbon resins, bituminous asphalts, coal tar pitches, rosins, phenolic resins, chlorinated aliphatic hydrocarbon waxes, chlorinated polynuclear aromatic hydrocarbons and rosin based alkyd resins.

65. The method of Claim 64 in which the modified, stabilized segmented copolyester is first melted and the low molecular weight thermoplastic resin is added to the melt.

66. The method of Claim 64 in which the low molecular weight thermoplastic resin is first melted and the modified, stabilized segmented copolyester is added to the melt.

67. The method of Claim 64 in which the segmented copolyester and the low molecular weight thermoplastic resin are blended together in finely divided form and melted together and the modifying and stabilizing compounds are present prior to blending.

68. The method of Claim 64 in which the segmented copolyester and the low molecular weight thermoplastic resin are blended together in finely divided form and melted together, the modifying and stabilizing compounds being added with the other components individually or as a mixture.

69. Method of preparing an aqueous dispersion of a modified, stabilized thermoplastic composition which comprises (A) dissolving the thermoplastic composition of Claim 31 in a water-immiscible organic solvent, (B) emulsifying the organic solvent solution in water, and (C) removing the organic solvent, thereby form-ing a dispersion.

70. The method of Claim 69 in which the short chain ester units amount to 15 to 65 percent by weight of the copolyester, the long chain ester units amount to 35 to 85 percent by weight of the copolyester, and the long chain glycol has a melting point of less than 55°C. and a carbon to oxygen ratio greater than 2.5.

71. The method of Claim 70 in which the low molecular weight thermoplastic resin is selected from the group consisting of hydrocarbon resins, bituminous asphalts, coal tar pitches, rosins, phenolic resins, chlorinated aliphatic hydrocarbon waxes, and chlorinated polynuclear aromatic hydrocarbons.

72. Method of preparing an aqueous dispersion of an adhesion-modified thermoplastic composition which comprises (A) dissolving adhesion-modified thermoplastic segmented copolyester elastomer consisting essentially of a multiplicity of recurring short chain ester units and long chain ester units joined through ester linkages, said short chain ester units amounting to 15 to 75 percent by weight of said copoly-ester and being of the formula and said long chain ester units amounting to 25 to 85 percent by weight of said copolyester and being of the formula wherein R is the divalent radical remaining after removal of the carboxyl groups from dicarboxylic acid having a molecular weight of less than 350, D is the divalent radical remaining after removal of the hydroxyl groups from organic diol having a molecular weight of less than 250, and G is the divalent radical remaining after removal of the terminal hydroxyl groups from long chain glycol having an average molecular weight of 350 to 6000, said copolyester having a melt index of less than 150 and a melting point of at least 90°C., modified with 1.3 to 20 parts by weight, per copolyester having a melt index of less than 100 parts by weight of elastomer, of a multi-functional carboxylic compound selected from aromatic and aliphatic anhydrides having at least two anhydride groups and stabilized with 1.75 to 15.0 parts by weight, per 100 parts by weight of elastomer, of a stabilizer mixture comprising (a) 0.25 to 2.5 parts by weight of a substantially linear polycarbodiimide having an average of at least two carbodiimide groups per molecule;
and at least one compound selected from (b) 0.5 to 2.5 parts by weight of a compound taken from the group consist-ing of hindered phenols, nitrogen-containing hindered phenols and secondary aromatic amines;
(c) 0.5 to 5.0 parts by weight phosphorous acid esters of the formula:
where R1, R2 and R3 are C1 to C18 aliphatic, C6 to C15 aromatic, and combinations thereof;
(d) 0.5 to 5.0 parts by weight of an amino compound taken from the group consisting of amino acrylate of the formula where R is hydrogen or methyl;
R1 is hydrogen or alkyl of 1 to 4 carbon atoms;
R2 is alkyl of 1 to 4 carbon atoms; and n is an integer of 1 to 4 inclu-sive, a homopolymer of said amino acrylate, and a random copolymer of ethylene and 20 to 40 percent by weight of said amino acrylate compound, each of compounds (b), (c) and (d) being compatible with each other and with (a), in a water-immiscible organic solvent, (B) dissolving low molecular weight thermo-plastic resin which forms compatible mixtures with the segmented copolyester, is thermally stable at 150°C., and has a melt viscosity of less than 10,000 centi-poises at 200°C., in a different water-immiscible organic solvent, (C) emulsifying each organic solvent solution in water, (D) removing the organic solvent from each emulsion, thereby forming separate dis-persions, and (E) mixing the dispersions together in such amounts that the final dispersion contains, based on the total thermoplastic components, 1 to 99 percent by weight of thermoplastic segmented copolyester elastomer and 99 to 1 percent by weight of low molecular weight thermoplastic resin.

73. The method of Claim 72 in which the stabilizer mixture comprises (a) and at least two the the compounds (b), (c) and (d).

74. The method of Claim 72 in which the stabilizer mixture consists of (a), (b), (c) and (d), each of said compounds being compatible with one another.

75. The method of Claim 72 in which the short chain ester units amount to 15 to 65 percent by weight of the copolyester, the long chain ester units amount to 35 to 85 percent by weight of the copolyester, and the long chain glycol has a melting point of less than 55°C. and a carbon to oxygen ration greater than 2.5.

76. The method of Claim 75 in which the low molecular weight thermoplastic resin is selected from the group consisting of hydrocarbon resins, bituminous asphalts, coal tar pitches, rosins, phenolic resins, chlorinated aliphatic hydrocarbon waxes, and chlorinated polynuclear aromatic hydrocarbons.

77. In the method of joining two surfaces using an adhesive therebetween, the improvement which comprises using as the adhesive a thermoplastic composition in accordance with Claim 25.

78. In the method of joining an edge banding layer to a substrate using and adhesive, the improvement which comprises using as the adhesive a thermoplastic composition in accordance with Claim 38.

79. In the method of shoe manufacture in which parts of the shoe are joined by use of an adhesive, the improvement which comprises using as the adhesive a thermo-plastic composition in accordance with Claim 38.

80. In the method of laminating a surface layer to a substrate using an adhesive, the improvement which comprises using as the adhesive a thermoplastic composition in accordance with Claim 38.

81. In the method of applying a coating to a substrate, the improvement which comprises using as the coating a composition in accordance with Claim 25.

82. In the method of adhering two surfaces together by heat sealing in which an adhesive coating is applied to one surface, the coating is activated by heat and a second surface is applied to the coating, the improve-ment which comprises using as the adhesive coating a composition in accordance with Claim 25.

83. In the method of adhering two surfaces together by heat sealing in which an adhesive coating is applied to one surface, a second surface is applied to the coating thereby forming a composite and the composite is heated to provide heat sealing, the improvement which comprises using as the adhesive a composition in accordance with Claim 25.

84. Method of preparing an adhesion-modified thermoplastic composition in a form selected from the group consisting of a molten blend and an aqueous dispersion which composition comprises, based on the total thermoplastic components, (A) 1 to 99 percent by weight of thermoplastic segmented copolyester elastomer consisting essentially of a multiplicity of recurring short chain ester units and long chain ester units joined through ester linkages, said short chain ester units amounting to 15 to 75 percent by weight of said copolyester and being of the formula and said long chain ester units amounting to 25 to 85 percent by weight of said copolyester and being of the formula wherein R is the divalent radical remaining after removal of the carboxyl groups from a dicarboxylic acid having a molecular weight of less than 350, D is the divalent radical remaining after removal of the hydroxyl groups from organic diol having a molecular weight of less than 250, and G is the divalent radical remaining after removal of the terminal hydroxyl groups from long chain glycol having an average molecular weight of 350 to 6000, said copolyester having a melt index of less than 150 and a melting point of at least 90°C; (B) 1 to 99 percent by weight of low molecular weight thermoplastic resin which forms compatible mixtures with the segmented copolyester, is thermally stable at 150°C; and has a melt viscosity of less than 10,000 centipoises at 200°C, said composition being modified with 0.3 to 8.0 parts by weight, per 100 parts by weight of elastomer and resin, of a multi-functional carbox-ylic compound taken from the group consisting of aromatic and aliphatic anhydrides having at least two anhydride groups, said method being selected from the group consisting of (a) blending said components (A) and (B) and said multi-functional carboxylic compound of the thermoplastic compo-sition in molten form, (b) dissolving said components (A) and (B) and said multi-functional carboxylic compound of the thermoplastic composition in a water immiscible organic solvent, emulsifying the organic solvent solution in water, and removing the organic solvent, thereby forming a dispersion, and (c) dissolving said component (A) modified with said multi-functional carboxylic compound in a water immiscible organic solvent, dissolving said component (B) in a dif-ferent water immiscible organic solvent, emulsifying each organic solvent solution in water, removing the organic solvent from each emulsion thereby forming separate disper-sions, and mixing the dispersions together.

85. In the method of joining two surfaces using an adhesive therebetween or by applying a coating to a substrate, the improvement which comprises using as the adhesive or respectively as the coating composition, the thermoplastic composition in accordance with Claim 25.

86. Method of use of an adhesion-modified thermo-plastic segmented copolyester elastomer selected from the group consisting of (i) preparing an adhesion-modified thermoplastic composition in a form selected from the group consisting of a molten blend and an aqueous dispersion which composition comprises, based on the total thermoplastic components, (A) 1 to 99 percent by weight of thermoplastic segmented copolyester elastomer consisting essentially of a multiplicity of recurring short chain ester units and long chain ester units joined through ester linkages, said short chain ester units amounting to 15 to 75 percent by weight of said copolyester and being of the formula and said long chain ester units amounting to 25 to 85 percent by weight of said copolyester and being of the formula wherein R is the divalent radical remaining after removal of the carboxyl groups from a dicarboxylic acid having a molecular weight of less than 350, D is the divalent radical remaining after removal of the hydroxyl groups from organic diol having a molecular weight of less than 250, and G is the divalent radical remaining after removal of the terminal hydroxyl groups from long chain glycol having an average molecular weight of 350 to 6000, said copolyester having a melt index of less than 150 and a melting point of at least 90°C; (B) 1 to 99 percent by weight of low molecular weight thermo-plastic resin which forms compatible mixtures with the segmented copolyester, is thermally stable at 150°C, and has a melt viscosity of less than 10,000 centipoises at 200°C said composition being modified with 0.3 to 8.0 parts by weight, per 100 parts by weight of elastomer and resin, of a multi functional carboxylic compound taken from the group consisting of aromatic and aliphatic anhydrides having at least two anhydride groups, said method being selected from the group consisting of (a) blending said components (A) and (B) and said multi-functional carboxylic compound of the thermoplastic compo-sition in molten form, (b) dissolving said components (A) and (B) and said multi-functional carboxylic compound of the thermoplastic compo-sition in a water immiscible organic solvent, emulsifying the organic solvent solution in water, and removing the organic solvent, thereby forming a dispersion, and (c) dissolving said component (A) modified with said multi-functional carboxylic compound in a water immiscible organic solvent, dissolving said component (B) in a different water immiscible organic solvent, emulsifying each organic solvent solution in water, removing the organic solvent from each emulsion thereby forming separate dispersions, and mixing the dispersions together, and (ii) in the joining of two surfaces using an adhesive therebetween or by applying a coating to a substrate, the improvement which comprises using as the adhesive or respectively as the coating composition, the thermoplastic composition prepared according to (i) above.