CA1110792A - Destructible films for marking, process for their production, and their utilization - Google Patents
Destructible films for marking, process for their production, and their utilizationInfo
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- CA1110792A CA1110792A CA305,527A CA305527A CA1110792A CA 1110792 A CA1110792 A CA 1110792A CA 305527 A CA305527 A CA 305527A CA 1110792 A CA1110792 A CA 1110792A
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Abstract
Abstract of the Disclosure A destructible marking film having a thickness of about 30 to about 100 microns and a destructibility of not more than 150 kg.cm/mm, said film being composed of a resin composition comprising (A) 100 parts by weight of a vinyl chloride resin having a degree of polymerization of about 600 to about 1,600 and optionally containing not more than about 15% by weight of comonomer unit, (B) about 10 to about 100 by weight of a thermoplastic urethane resin, (C) about 2 to about 15 parts by weight of an ethylene/vinyl ester copolymer, and (D) about 10 to about 150 parts by weight of a pigment;
a process for preparing the marking film; and a method for marking by applying the same to the surface of a substrate.
a process for preparing the marking film; and a method for marking by applying the same to the surface of a substrate.
Description
~ his invention relates -to destructible films which are useful for a wide range of marking purposes, for example as certifying seals, sealing and o-ther labels, decorative or display stickers for motor vehicles and containers, advertisement display stickers used to mark figures and let-ters on signboards~ and various display stickers such as -traffic markings, road ~ markings, guide boards, danger warning markings and :: markings on commodity on the marketO
: 10 For use in the a~oresaid applications, marking films are required to have suitable destructibility ~hereby breakage which occurs partly in the films does not extend to the surrounding partO In addition, they : ~ desirably should possess good workability during adhesion to a substrate, thérmal stability, ease of manu~acturing operation, low costs, enviro~ental safetg durin~ manufacture7 productivity, surface smoothness, and reproducibillty o~ qualityO ~he present invention relates to destructible marking films having superior destructibility~ thermal s-tability~ surface smoothness d~t~
and ~ , and improved resistance to deter~o-ration b~ heat after adhesion, dimensional s~ability - :
~: and weatherabili-t~; and to a process for their produc-tion, and to their utilizationO
: 25 More specifically~ -the present invention rela-tes to a destructible marking film having a thick-ness of ~ 30 to ~e~t 100 microns and a destruc-- tibility of not more than 150 kgOcm/mm, said ~ilm being :
:~ - 2 -, composed of a composition consisting essent:i.ally of ~ A) 100 parts by weight of a viny:L chloride resin having a degree of polymerization of from 600 to 1,600 and containing from 0 to 15% by weighl: of a ;
comonomer unit, ~ B) 10 to 100 parts by weight of a thermo-plastic urethane resin, ~ C) 2 to 15 parts by weight of an ethylene/
vinyl ester copolymer, and ~D) 10 to 150 parts by weight of a pigment.
Destructible films for marking have heretofore been produced solely by a casting method ~coating method).
This is firstly because conventional destructible marking films are ultrathin films with a thickness of less than about 70 microns, usually up to about 30 microns. If -it is desired to form such a thin and substantially ~ .
unstretched film by a melt-extrusion method, there is no~choice but to adopt an extremely slow extruding speed. ~
As a result, there is considerable occurrence of thick- ~ ;
~ ~ .
: 10 For use in the a~oresaid applications, marking films are required to have suitable destructibility ~hereby breakage which occurs partly in the films does not extend to the surrounding partO In addition, they : ~ desirably should possess good workability during adhesion to a substrate, thérmal stability, ease of manu~acturing operation, low costs, enviro~ental safetg durin~ manufacture7 productivity, surface smoothness, and reproducibillty o~ qualityO ~he present invention relates to destructible marking films having superior destructibility~ thermal s-tability~ surface smoothness d~t~
and ~ , and improved resistance to deter~o-ration b~ heat after adhesion, dimensional s~ability - :
~: and weatherabili-t~; and to a process for their produc-tion, and to their utilizationO
: 25 More specifically~ -the present invention rela-tes to a destructible marking film having a thick-ness of ~ 30 to ~e~t 100 microns and a destruc-- tibility of not more than 150 kgOcm/mm, said ~ilm being :
:~ - 2 -, composed of a composition consisting essent:i.ally of ~ A) 100 parts by weight of a viny:L chloride resin having a degree of polymerization of from 600 to 1,600 and containing from 0 to 15% by weighl: of a ;
comonomer unit, ~ B) 10 to 100 parts by weight of a thermo-plastic urethane resin, ~ C) 2 to 15 parts by weight of an ethylene/
vinyl ester copolymer, and ~D) 10 to 150 parts by weight of a pigment.
Destructible films for marking have heretofore been produced solely by a casting method ~coating method).
This is firstly because conventional destructible marking films are ultrathin films with a thickness of less than about 70 microns, usually up to about 30 microns. If -it is desired to form such a thin and substantially ~ .
unstretched film by a melt-extrusion method, there is no~choice but to adopt an extremely slow extruding speed. ~
As a result, there is considerable occurrence of thick- ~ ;
~ ~ .
2~0 ~ ness unevenness. Furthermore, the film naturally undergoes heat decomposition for a long period of time, and its deterioration cannot be avoided. Such a method is never commercially feasible.
Secondly, when it is desired to form such an ultrathin and substantially unstretched film by a ~ -calender method, the separating force of the roll clearance increases. Hence, it is necessary to increase :,, l 3 ~
~' :
the roll pressure markedly9 and an extreme decrease in -the speed of production cannot be avoided~ I-t is actually impossible to obtain an ultxa-thin film having substantially no directionality and a uniform thickness by this method~
Accordingly, if it is desired to obtain an : ultrathin film by the melt-ex-truding or calendering ~;~` method, it is necessary to render the resulting film thinner by a stretching meansO ~he resulting films : ~ l0 are not acceptable as destructible marking filmsO
It was suggested in the past to blend 30 to 70% by weight of an ethylene/vinyl acetate copolymer with a vin~l chloride resin so as to provide a molding mater1al based on the vinyl chloride resin and having improved mechanical properties, especially impact strength (German Paten-t ~oO 1~ 544~ 803) o As will be shown hereinbelow in Compara-tive Examples 3 a~d 4~ such a blend doe$ not show favorable chracteristics as destructible marking filmsO ~h1s patent shows an example~of blending a thermoplastic urethane resin with a vinyl chloride resin for comparative purposesO ~his blend neither shows properties useful for destructible marking films, as will be shown hereinbelow in Compara-~: :: tive Examples l and 20 ~;~ 25 In an attempt to remove the aforesaid manufac-~: turing res-trictions7 and to provide a des-tructible marking film of superior quali-ty~ the presen-t inventors previously suggested a destruc-tible marking film, which ; ~
~`~
_ 4 --is an ultrathin calender ~ilm having a thickness of about 30 to about 60 microns and composed of 100 parts by weight of a vinyl chloride resin having a degree of polymerization of about 600 to abou-t 2,000, abou-t 5 to about 20 parts by weight of an alkyl methacryla-te ;: resin and about 5 to about 30 parts by weight of a liquid plasticizer (Japanese ~aid-Open Patent Publication oO 12394~/77)o On fur-ther investigation9the inventors of the present application found that the destructible film having the improved properties in the above patent, presumably because of the inclusion of a liquid plas-ticizer, is desired to be further improved in dime~sional ~---~
stabili-ty and resistance to;heat deterioration after 15 ~adhesion, ~he inventors therefore continued to work on:this subject in an attempt to provide a destructible marklng film which achie~es the desired improvements and has superior destructibility, thermal stability, ~ , surface smoothness and weatherability and is free from the manu~acturing restrictionsO
~hese investigations led to the discovery that a film having a thickness of about 30 microns to about 100 microns and comprising (A) 100 parts by weight of ~, : a vinyl chloride resin having a degree of polymerization of about 600 to about 1,600 and optionally containing not more than about 15% by weight of a comonomer unit, . , ; (B) about lQ to about 100 parts by weight of a thermo-. ~ .
plastic urethane resin and (C) about 2 to about 15 parts :~:
: - 5 ~
~ : . . . -by weight of an ethylene/vinyl ester copolymer with the omission of an alkyl methacrylate resin used as an essential ingredient in the a~oresaid proposa~ can be a destruc-tible marking film having superior des-truc~
tibility, thermal s-tability~ surface smoothness, dimen-sional stability and resistance to heab deterioration after adhesion~ It has also been ~ound that the afore ` ._ said manufacturing restrictions can be removed7 and the film can be formed no-t only by calendering but also by : 10 extrusion~
; The need to use a liquid plasticizer in the conventional destructible marking films can be obviated - -in the -present inven-tionO When an adhesive is applied : ~ to one surface of a destructible marking film7 for : 15: example when it is stored as adhered to a strippable base film9 the l1quid plasticizer migrates to the ad-hesive layer to reduce the adhesion strength of the adhesiveO ~urthermore~ there are many restrictions on : ~ the selec-ti:on of -the -type of adhesi.ve so as to prevent a reduction in -the performance of the destructible marking film itself~ and therefore~ its outdoor adhesion in the wintertime is difficul-to ~hese disadvan-tages ~; have been found to be conveniently overcome by -the present invention~ In addition~ the omission of a li~uid plas- -: 25 ticizer in the present invention can lead to -the preven--tion of the peeling of the destructible film from the adhesive layer which is caused by the migration and accumulation of the plas-ticizer to and in the interface , ~
..
:
between the des-tructible film and -the adhesive layer at high temperatures in the summer-timeO
Provision of an undercoat or lamination of another film so as -to inhibit the migration of the A 5 liquid plasticizer ~e disadvanta~eous because ~
addS-to -the number of process steps and -to the cost of productionO Moreover, the solven-t in the undercoa-ting solu-tion or the solvent in -the adhesive used for laminat-~ ing is likely to deteriorate the properties of the : 10 destructible filmO
Furthermore9 the amount of the plasticizercarmo-t be reduced to such an exten-t as can eliminate the defects associated wi-th the migra-tion o~ the plasticizerO The use of a polymeric liquid plas-ticizer :causes a de-terioration in the suppleness of the destruct-:: 1ble fllm and in the opera-tion of adhering the film to a curved surface of a substrate9 and adversely affects the destructibility of the filmO
~ It has been found that according -to this :~ 20 invention, these difficulties can be conveniently over-: come by -the cooperative action of -the vinyl chloride resin, the thermoplas-tic urethane resin and the ethylene/
vinyl ester copolymer described aboveO
-~: As is well known9 the thermoplastic urethan resin has unsatisfactory weatherability and the urethane resin and the ethylene/vinyl ester copolymer both have unsatisfactory moldabilityO In view of this, it is quite unexpected that -the cooperative action of -these :
~ ~ 7 -~ 7 ~
three resins can afford with good procluctivi-ty a destructible marking film having bet-ter destruc-tib~lity, thermal stability, sur.tace smooth~ess~ dimensi.onal stability and weatherability than in the case of omit-ting either one of the urethane resin and the ethyl.ene/vinyl ester resin as shown in Compara-tive ~xamples 1 -to 4 to be given hereinbelow~
It has also been found that the Aforesaid improvements obtained by the cooperative action oX the three resins specified in -the present i.nvention cannot be achieved 4y the use of a blend of an ethylene/vinyl qr~f ~e~
ester-~at~ vinyl chloride resin and a thermoplastic urethane resin as shown in Comparative Example 5~ or ~ n t~ 7 by the use of a well known elastomer for i~eæRa~
plasticization such as chlorinated polyethylene, chlorinated polypropylene, ~R, chlorosulfonated poly-ethylene or chloroprene in place of the urethane resin mentioned above, as shown in Comparative ~xamples 6 to 80 It is an object of this invention therefore to provide a destructible marking film which is free from the disadvantages and defects of conventional destructible marking films and from manufacturing restrictions, and has improved properties such as superior destructibility, thermal stability9 surface smoothness7 dimensional stability~ resistance -to heat deterioration after adhesion, and weatherabil.ity~
~ he above and other objects and advantages of the invention will become more apparent from the _ 9 .
following descrip-tionO
The des-truc-tible fi~L1n of this invention has a des-txuc-tibility of not more than l50 kgo cm~mm~
preferably abou-t 2 to about 25 k ~ m/mm, more pre-ferably not more than about l5 kgocm/mmO
~ he i'des-truc-tibili-ty" of a film in the present application is measured substantially in accordance with JIS P8l~4O ~his test is an impact perfora-tion s-trength tes-t for paper board measured by a punching-type impact testerO In the present invention., the testing procedure of JIS P8134 is followed except that the des-tructible marking film is used instead o the paper board, and -the testing device and procedure are somewhat modified as follows.
;; 15 (l) A l inch ball is used as an impact headO
(2) A pendulum i.s used which can measure the amoun-t of work required for perforation to an extent of 0 to ~0 kgQ cmO
(33 The sample is cut to a size of l00 x l00 mm, and mounted on a stand with a diameter of 60 mmO
(4) The perforating position is registered , with the center of a c1rcleO
he measured value of the impac-t perforation strength is expressed in kgOcm/mmO
The destructible markin~ film of this invention ~; is composed of a blended resin composition containing (A) l00 parts by weight of a vinyl chloride resin having a degree of polymeriza-tion of about 600 to about 1,600 :
and optionally containing not more than about 15% by weight of a comonomer unit9 (B) about 10 to about 100 parts by weight of a thermoplas-tic urethane resin,(C) about 2 to about 15 parts by weight of an et~Jlene/
5 vinyl ester copol~ymer, and (D) about 10 to about 150 parts by weight of a pigmen-tO
In the destructlble film of -the invention having a thickness of about 30 microns to about 100 microns composed of the aforesaid resin composition, the amount of the pigment is about 10 -to about 150 parts by weight, preferably abou-t 10 to about 100 parts by weight, per 100 parts by weight of -the vinyl chloride resin (A~o Preferably the destructible marking film of this invention contains about 1 to about 10 parts, especially about 1 to about 5 par-ts, bY weight of a :lubricantO It may also contain up to about 10 parts by;weight of a s-tabllizer per l00 parts by weight of the vinyl chloride resinO ~he use of a liquid plastic-zer~oan be omitted in the marking film of this inven-~ 20 t~ion, but the lnclusion of a small amoun-t of, say, less : ~ than about 15 parts by weight, of a liquid plasticizer per 100 p OEts by weight of -the vinyl chloride resin is ; permissibleO
he use of such a small amount of plastici2er .~
in the mixture of the resins ~A), (B) and ~G) is possible without hampering the achievement of the improvements ~: ; by the cooperative action of t~e three resins9 and the various defects mentioned above which are caused by ' -the migration of the plasticizer can be fully avoided~
~ he vinyl chloride resin usecl for the destruct-ible marking film o:E this invention i.s a resin having a degree of polymeri~ation of about 60Q to about 1,600.
I.E -the degree of polymerization is less than about 600, -the dimensional stability of the resulting film is markedly reduced, and after application, the film shrinks and cannot adhere firmly and stablyO Moreover, the thermal stability o~ the film wi.ll also be affectedO
On the other hand, when the degree of polymeriza-tion exceeds about 1,600, the productivity of film manufac-: ture lS reduced, and it is impossible to produce the film :at a commercially feasible speedO
If desired, the vinyl chloride resin (A) may ; 15 contain not more than 15% b~ weight of a comonomer unit such as ethylene, propylene,~ butene, vinyl acetate, an acrylate ester, preferably a Gl-C18 alkyl ester of a:crylic acid, vinylidene chloride, a ~inyl ester or ; ~ ~ a vinyl ether ~he type of the thermoplastic urethane resin ~B) to be included in the resin composition in an amount of about 10 -to about 100 parts by weight, preferably about 10 to about 50 parts by weight~ more preferably about 20 to~about 40 parts by weight, per 100 parts by weight of the vinyl chloride resin (A) is properly selected according, f~r example, to the desired color to be imparted by the pigment (D)o ~he termoplastic urethane resin (B) may be ~::
3L~ 2 those which have little or no tendency to yellowing.
Preferably, non-yellowing thermoplastic urethane resins are used.
Preferred species are thermoplastic urethane resins obtained by addition-condensation between aliphatic or aromatic poly addition reaction and difunctional active hydrogen-containing compounds capable of reacting with the isocyanates.
Examples of the diisocyanates are hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, ~; xylylene diisocyanate, lysine diisocyanate methyl ester, trimethyl hexamethylene diisocyanate, isophorone di-isocyanate, hydrogenated tolylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate.
Examples of suitable difunctional active hydrogen-containing compounds are glycols having a relatively low molecular weight such as ethylene glycol, ~ -1,4-butanediol and propylene glycol, hydroxyl-terminated .
polyester diols and polyolefin glycols having a rela-20~ tively high molecular weight, diamines such as ethylene-diamine or propylenediamine, and aminoalcohols such as ethanolamine.
Especially preferred thermoplastic urethane ~; resins are those obtained by poly addition reaction , :~
between diisocyanates selected from hexamethylene diiso-cyanate, hydrogenated diphenylmethane diisocyanate and hydrogenated tolylene diisocyanate and diols selected ~-` from polyester diols and polyolefin glycols.
~;' :
These diisocyanates and dif~mctional active hydrogen-containing compounds may be used respectively as a mixture of two or more.
Compo~mds produced by the polycondensation of dibasic acids such as adipic acid or phthalic acid with glycols such as ethylene glycol, l,~-butanediol or propylene glycol are frequently used as the hydroxyl- ~ ~`
terminated polyester diols having a relatively high mo-lecular weight.
When the amount of the thermoplastic urethane resin is smaller than the specified limit, the mold- ~ :
ability of the resulting composition is markedly reduced~
and the productivity of film formation is extremely reduced. The resulting fi.lm will have unsatisfactory ~;
destructibility, and its applicability to substrates will be aggravated. On the other hand, when the amount of *he urethane resin exceeds the upper limit specified in the present inventionj the resulting film has poor surface smoothness and weatherability and non-uniformity in color and luster. Thus, the film will lose its :
practical applicability.
In the destructible marking film of this invention, about 2 to about 15 parts by weight of the ethylene/vinyl ester copolymer is further included per 100 parts by weight of the vinyl chloride resin (A).
The copolymer ~C) iSJ for example, a copolymer of ethylene `
with a vinyl ester of a C2-Cl7 aliphatic carboxylic acid such as vinyl acetate, vinyl propionate, vinyl :
` ;
~ - 13 - `' ~...... ' _ lL~ --butyrate or vinyl stearateO
The et.hylene content and -the degree of poly-meriza-tion of -the copolymer (C) are not critical in particularO Copolymers (~) having an ethylene content of ~0 to 70% by welght are preferredO ~wo or more vinyl esters may be used toge-therO ~he copolymer (C) may also include a small amoun-t of another copolymeriz-A able monomer such as an acryla-te or methacrylate ~ 0 Vinyl acetate is by far -the cheapes-t vinyl ester : 10 availableO
When the amount of -th.e ethylene/vinyl est~r copolymer (C) is smaller than the above-specified limit, the productivi-ty of film forma-tion becomes markedly low, : and the resulting film will have poor surface smoo-thness with color specksO If the amount of -the copolymer (C) exceeds the specified upper limit~ the film will lose its moderate toughness9 or have a rough surface with ~: non-uniformi-ty in color or lusterO ~he resin composition will become strongly tacky, and the produc-tivity of film `;: :
; 20 formation is not industrially satisfactoryO
~ he destruc-t:ible marking film of -this inven-tion also includes the pigment (D)o ~he amount of the pigment is not criticalO ~specially good results are ~: obtained by using i.-t in an amoun-t of, for examplej about 10 to about 150 parts by weight~ preferably about 10 to about 100 parts by weight~ per 100 parts by weight of the vinyl ~t~ chloride resin (~)O
~xamples of the pigment (~) include inorganic ::
. . : ~ . : ; . -pigments such as titanium oxide, zinc oxide, lead white, calcium carbonate, gypsum, precipitated silica7 carbon black7 red iron oxide, molybdenum red, cadmium yellow, yellow lead, -titanium yellow, chromium oxide green and ultramarine; and organic pigments such as Permanent Red 4R, Hansa Yellow 10G, Benzidine Yellow GR, Permanen-t Garmine ~B, Phthalocyanine Blue B7 and Phthalocyanine Green O
In addition to the vinyl chloride resin (A), the thermoplastic urethane resin (B), the ethylene/
vinyl ester copolymer (C), and the pigment (D), the destructible marking film of the invention may contain about 1 to about 10 parts by weight9 preferably about :: 1 to about 5 parts by weight~ of a lubricant per 100 --: 15 parts by weight of the vinyl chloride resin (A)o Almost all lubricants usually employed in the processing of vinyl chlorlde resins can be usedO Examples are poly-ethylene waxesg liqui.d paraffin, stearic acid, stear-amide~ bisamide, n-butyl stearate and aliphatic alcoholsO
~he use of lubricant serves to impart favorable : : luster to the destructible mar~ing film of this inventionO
:::
he destructible marking film of this inven-: tion may contain a small amount of a s-tabilizerO The amount of the stabilizer is preferably not more than 25 about 10 parts by weight per 100 parts by weight of the vinyl chlorlde resinO Examples of -the stabilizer include calcium stearate, barium steara-te, lead stearate, basic lead sulfite~ dibasic lead phosphite, dibutyltin dilaurate, :, :' dibutyltin dimaleate9 dibutyltin mercaptide9 dioctyl-tin maleate--type stabilizers 9 clioctyltin laurate-type stabilizers7 dioc-tyl-tin mercapto-type stabilizers9 and stannane-diol deriva-tives or complexes of theseO
Anti-haze agents such as nonionic surface-active agents9 polyoxyethylene, and glycerin monos-teara-te are al.so cited as such stabilizersO
~ he film of this inven-tion may a]so contain an anti-o~idant such as ~H~ (276-ditertiary-butyl p-cresol) and bisphenol A7 and an ultraviolet absorbersuch as 272'-dihydroxy-4--methoxybenzophenone9 and 2-(2'-hydroxy-~'95'-di-tertObutyl-phenyl)~5-chlorobenzo-tria~oleO
As stated hereinabove9 the destructible marking ~ : 15 film of the invention may contain not more than about : :~ : 15 par-ts by wei~ht of a plasticizer per 100 parts by , ~
: ~ weight: of the vinyl chloride resin (A)~ When the ~; ~ plastlcizer is used in a larger amount7 the adhesion s~tability and operability of the film are deterioratedO
When it is used in -the amount indicated, favorable re-sults can be obtained in improving the clarity and surface luster of the resul-ting ~ilmO ~he plastici~er ;~ may be selected from those which are commonly used for processing vinyl chloride resinsO Preferably9 it is : ~ 25 selected from epoxy derivatives having an oxirane oxygen con-tent o~ 2 -to ~ and a molecular weight of not more than 17000, and polyester-type plasticizers of the sebasic acid7 adipic acid7 ~zelaic acid9 and ~ 16 -~
.. : .. , ; ,. : .. , ~ ,. . .
~ 17 : phthalic acid type.sO
~ he destructible marking film of this inverl~
-tion can be prepared by molding the aforesa~d pigment-containing resin composition into a ~ilm having a thickness of about ~0 to abou-t 100 mlcronsO
Preferably9 the molding is carried ou-t by a calender methodO But when a film having a larger ~: ~ thickness below about 100 microns is to be produced, ~ an extrusion molding method can also be employedO
:~ ~ 10 : ~ilm forma-tion by the calender method is well ~: known in the art, and in the present inven-tion, it can be performed in the same mannerO Preferably, an as-formed film from a calender film-forming machine lS
: rapidl~ cooled at it necking portion with a:gaseous 15 ~cooling medium at a tempcrature of not more than about 30C, for example9 about ~10C to about ~0C9 such as alr, nitrogen or carbon dioxide gasO
Since the film of -this invention is a de~ :
structible~marking film9 it is necessary to avoid a stretching operation which will resul-t in an ultrathin film having a destructibility (impact strength) of more than~150 kg~cm/mmO Accordingl~9 the as-formed ~ilm from : t-he calender machine has a -thic~ness of about 30 microns to about 100 microns or soO Eve~ when a stretching action is exerted on -the film as formed, the extent of : stre-tching of the film should be-tter be such that the ~;~ percentage~ of the surface linear speed o~ a film take-~: up roll based on the surface linear speed of last roller ~, ~;:
~:
; ~ - 17 -, .~
- 1~3 --is not more than about l~O~ preferably not more than about 130%o l`he calender molding tempera-ture is abou-t 140 to about 190C9 and the -tempera-t-~re at the time of stre-tchlng is about 50 to about 140Co Film forma-tion by an extrusion methc)d Call also be performed by procedures well known in the production of unstretched films~ ~ilm forma-tion is possible by any of a ~-die me-thod and an inflation me-thodO The T-die method is preferred to secure des-tructibility sufficientlyO
~he processing temperature is determined properl~
according to the capabili.ty of a given machine while main-taining the temperatures at the cylinder por-tion7 the adapter portion and the die portion respectively at 140 to 220Co When it is desired -to obtain a substantially 15 unstretched film having a thickness of about 30 to 100 microns~ it is neces~sary to prescribe the die lip clear-ance at not more than 002 mmO Thus, this method is advarl-tageous for producing fi.lms having a rela-tively la ge thickness of 7 say, 100 micronsu ~he present inven-tion is free from the manufac-turing res-trictions and can afford at a low cost by an easy operation a destructible marking film having improved operabi.lity in adhering~ -thermal stability~ surface smooth-ness~ dimensional s-tabili-ty and weatherabili-~yO The f'ilm can be prepared with good produc-tivi-t-~ while securing the safety of the working environment and obviating the need to recover the solvent usedO According to this invention~ the destructibility of -the film can be ad-justed to the desired value~ and has good reproducibilityO
, . . . ... , . .. , , ~
f~
'~he composition of the destructible film ob-tained as a final produc-t can be determined by -the following me-thodO
The film is extrac-ted with e-thyl etherO r~e-tra-hydrofuran is added to the res1due [containing the resins(A), (B) and (C) ~ the pi.gmen-t (D)], and the mixture is stirredO ~he mixture is fil-tered to separa-te i-t into an insoluble portion and a soluble portionO r~he soluble portion contains -the resins (A), (B) and (C), and the : 10 insoluble portion contains only -the pigmen-t (D)~ he weight of the insoluble portion is measured to deter-mine the proportion of the pigment (D)o ~ etrahydrofuran is evaporated from the soluble portionO ~thyl acetate is added to the residue, and the 15 : mixture is stirredO ~he mix-ture is filteredO I`he fil-trate is evaporated to dryness and -then weighedO ~rom ;; : :; the IR spectrum of the product, this portion is iden-: ~ tified as an ethylene/vinyl acetate copolymer (C)O
`~: IR spectrum~ charac-teristic absor~tions at 2975 cm l an absorption band of vinyl aceta-te, -CE3 s-tre-tching 2850 cm l an absorption band of vinyl acetate and ethylene, -CH2 stretching ~ 1770 cm l an absorption band of vinyl acetate, : 25 C=0 stretching ~` 1240 cm l~ an absorption band of vinyl aceta-te, C-0 s-tretching ; 720 cm l~ an absorption band of ethylene, -CH2- skeleton stretching ~' - -The above e-thyl acetate~insoluble portion and a mixture of isopropyl alcohol and toluene (1:1) is s-tir-red~ The mix-ture is filtered, and methanol is added to the filtrate -to re~precipi-tate ito The precipitate is washed with rnethanol, dried~ and weighedO ~he product is identified as a ure-thane resin (B) from its lR spectrumO
~ __u~ haracteristi a 3300 cm 1. N-I-I stre-tching vibration 2940 cm 1 CH2 stretching vibration 101730 cm 1. a=o stretchin~ -vibration 1550 cm 1. a combined absorption band of ~H
angular displacement, CN stretching 'I'he portion insoluble in isopropanol/toluene : (1/1) is washed with methanol, dried, and weighedO The product is identified as a vinyl chloride resin (A) from its IR spectrumO
1 spectru~_ch racteristic absorptions a-t 2940-2915 cm 1~ -CH2- stretching vibration 2900-2880 cm 1 -CH- stretching vibration 201480-1440 cm 1 -CH2 angular displacement : vibration caO 1340 cm ~: -CH- angular displacement vibration 750- 650 cm 1 C-Cl stretching vibra-tion - 25The following ~xamples and Comparative ~xamples ~: illustrate the present invention in more detai.lO
'he various properties in these ~xamples were measured by the following me-thodsO
:
~:
... . . . .. . .. . .
~estructibili-t~
-Measured at 25C by a film impact -tester (capaci-t~ ~0 kgOcm, impact speed 202 km/sec~, impac-t ball with a radius of 1 i.nch) in accordance with -the punch-t-gpe impac-t tes-ting methodO
Operabilit~_in adher~
~ his is evaluated by -the height of the~ t of a rivet with a diameter of 10 mm to which the film coa-ted with an adhesive can be applied without breakage or rais-ingO
1: a height of more than 4 mm 2: a height of 4 to 3 mm
Secondly, when it is desired to form such an ultrathin and substantially unstretched film by a ~ -calender method, the separating force of the roll clearance increases. Hence, it is necessary to increase :,, l 3 ~
~' :
the roll pressure markedly9 and an extreme decrease in -the speed of production cannot be avoided~ I-t is actually impossible to obtain an ultxa-thin film having substantially no directionality and a uniform thickness by this method~
Accordingly, if it is desired to obtain an : ultrathin film by the melt-ex-truding or calendering ~;~` method, it is necessary to render the resulting film thinner by a stretching meansO ~he resulting films : ~ l0 are not acceptable as destructible marking filmsO
It was suggested in the past to blend 30 to 70% by weight of an ethylene/vinyl acetate copolymer with a vin~l chloride resin so as to provide a molding mater1al based on the vinyl chloride resin and having improved mechanical properties, especially impact strength (German Paten-t ~oO 1~ 544~ 803) o As will be shown hereinbelow in Compara-tive Examples 3 a~d 4~ such a blend doe$ not show favorable chracteristics as destructible marking filmsO ~h1s patent shows an example~of blending a thermoplastic urethane resin with a vinyl chloride resin for comparative purposesO ~his blend neither shows properties useful for destructible marking films, as will be shown hereinbelow in Compara-~: :: tive Examples l and 20 ~;~ 25 In an attempt to remove the aforesaid manufac-~: turing res-trictions7 and to provide a des-tructible marking film of superior quali-ty~ the presen-t inventors previously suggested a destruc-tible marking film, which ; ~
~`~
_ 4 --is an ultrathin calender ~ilm having a thickness of about 30 to about 60 microns and composed of 100 parts by weight of a vinyl chloride resin having a degree of polymerization of about 600 to abou-t 2,000, abou-t 5 to about 20 parts by weight of an alkyl methacryla-te ;: resin and about 5 to about 30 parts by weight of a liquid plasticizer (Japanese ~aid-Open Patent Publication oO 12394~/77)o On fur-ther investigation9the inventors of the present application found that the destructible film having the improved properties in the above patent, presumably because of the inclusion of a liquid plas-ticizer, is desired to be further improved in dime~sional ~---~
stabili-ty and resistance to;heat deterioration after 15 ~adhesion, ~he inventors therefore continued to work on:this subject in an attempt to provide a destructible marklng film which achie~es the desired improvements and has superior destructibility, thermal stability, ~ , surface smoothness and weatherability and is free from the manu~acturing restrictionsO
~hese investigations led to the discovery that a film having a thickness of about 30 microns to about 100 microns and comprising (A) 100 parts by weight of ~, : a vinyl chloride resin having a degree of polymerization of about 600 to about 1,600 and optionally containing not more than about 15% by weight of a comonomer unit, . , ; (B) about lQ to about 100 parts by weight of a thermo-. ~ .
plastic urethane resin and (C) about 2 to about 15 parts :~:
: - 5 ~
~ : . . . -by weight of an ethylene/vinyl ester copolymer with the omission of an alkyl methacrylate resin used as an essential ingredient in the a~oresaid proposa~ can be a destruc-tible marking film having superior des-truc~
tibility, thermal s-tability~ surface smoothness, dimen-sional stability and resistance to heab deterioration after adhesion~ It has also been ~ound that the afore ` ._ said manufacturing restrictions can be removed7 and the film can be formed no-t only by calendering but also by : 10 extrusion~
; The need to use a liquid plasticizer in the conventional destructible marking films can be obviated - -in the -present inven-tionO When an adhesive is applied : ~ to one surface of a destructible marking film7 for : 15: example when it is stored as adhered to a strippable base film9 the l1quid plasticizer migrates to the ad-hesive layer to reduce the adhesion strength of the adhesiveO ~urthermore~ there are many restrictions on : ~ the selec-ti:on of -the -type of adhesi.ve so as to prevent a reduction in -the performance of the destructible marking film itself~ and therefore~ its outdoor adhesion in the wintertime is difficul-to ~hese disadvan-tages ~; have been found to be conveniently overcome by -the present invention~ In addition~ the omission of a li~uid plas- -: 25 ticizer in the present invention can lead to -the preven--tion of the peeling of the destructible film from the adhesive layer which is caused by the migration and accumulation of the plas-ticizer to and in the interface , ~
..
:
between the des-tructible film and -the adhesive layer at high temperatures in the summer-timeO
Provision of an undercoat or lamination of another film so as -to inhibit the migration of the A 5 liquid plasticizer ~e disadvanta~eous because ~
addS-to -the number of process steps and -to the cost of productionO Moreover, the solven-t in the undercoa-ting solu-tion or the solvent in -the adhesive used for laminat-~ ing is likely to deteriorate the properties of the : 10 destructible filmO
Furthermore9 the amount of the plasticizercarmo-t be reduced to such an exten-t as can eliminate the defects associated wi-th the migra-tion o~ the plasticizerO The use of a polymeric liquid plas-ticizer :causes a de-terioration in the suppleness of the destruct-:: 1ble fllm and in the opera-tion of adhering the film to a curved surface of a substrate9 and adversely affects the destructibility of the filmO
~ It has been found that according -to this :~ 20 invention, these difficulties can be conveniently over-: come by -the cooperative action of -the vinyl chloride resin, the thermoplas-tic urethane resin and the ethylene/
vinyl ester copolymer described aboveO
-~: As is well known9 the thermoplastic urethan resin has unsatisfactory weatherability and the urethane resin and the ethylene/vinyl ester copolymer both have unsatisfactory moldabilityO In view of this, it is quite unexpected that -the cooperative action of -these :
~ ~ 7 -~ 7 ~
three resins can afford with good procluctivi-ty a destructible marking film having bet-ter destruc-tib~lity, thermal stability, sur.tace smooth~ess~ dimensi.onal stability and weatherability than in the case of omit-ting either one of the urethane resin and the ethyl.ene/vinyl ester resin as shown in Compara-tive ~xamples 1 -to 4 to be given hereinbelow~
It has also been found that the Aforesaid improvements obtained by the cooperative action oX the three resins specified in -the present i.nvention cannot be achieved 4y the use of a blend of an ethylene/vinyl qr~f ~e~
ester-~at~ vinyl chloride resin and a thermoplastic urethane resin as shown in Comparative Example 5~ or ~ n t~ 7 by the use of a well known elastomer for i~eæRa~
plasticization such as chlorinated polyethylene, chlorinated polypropylene, ~R, chlorosulfonated poly-ethylene or chloroprene in place of the urethane resin mentioned above, as shown in Comparative ~xamples 6 to 80 It is an object of this invention therefore to provide a destructible marking film which is free from the disadvantages and defects of conventional destructible marking films and from manufacturing restrictions, and has improved properties such as superior destructibility, thermal stability9 surface smoothness7 dimensional stability~ resistance -to heat deterioration after adhesion, and weatherabil.ity~
~ he above and other objects and advantages of the invention will become more apparent from the _ 9 .
following descrip-tionO
The des-truc-tible fi~L1n of this invention has a des-txuc-tibility of not more than l50 kgo cm~mm~
preferably abou-t 2 to about 25 k ~ m/mm, more pre-ferably not more than about l5 kgocm/mmO
~ he i'des-truc-tibili-ty" of a film in the present application is measured substantially in accordance with JIS P8l~4O ~his test is an impact perfora-tion s-trength tes-t for paper board measured by a punching-type impact testerO In the present invention., the testing procedure of JIS P8134 is followed except that the des-tructible marking film is used instead o the paper board, and -the testing device and procedure are somewhat modified as follows.
;; 15 (l) A l inch ball is used as an impact headO
(2) A pendulum i.s used which can measure the amoun-t of work required for perforation to an extent of 0 to ~0 kgQ cmO
(33 The sample is cut to a size of l00 x l00 mm, and mounted on a stand with a diameter of 60 mmO
(4) The perforating position is registered , with the center of a c1rcleO
he measured value of the impac-t perforation strength is expressed in kgOcm/mmO
The destructible markin~ film of this invention ~; is composed of a blended resin composition containing (A) l00 parts by weight of a vinyl chloride resin having a degree of polymeriza-tion of about 600 to about 1,600 :
and optionally containing not more than about 15% by weight of a comonomer unit9 (B) about 10 to about 100 parts by weight of a thermoplas-tic urethane resin,(C) about 2 to about 15 parts by weight of an et~Jlene/
5 vinyl ester copol~ymer, and (D) about 10 to about 150 parts by weight of a pigmen-tO
In the destructlble film of -the invention having a thickness of about 30 microns to about 100 microns composed of the aforesaid resin composition, the amount of the pigment is about 10 -to about 150 parts by weight, preferably abou-t 10 to about 100 parts by weight, per 100 parts by weight of -the vinyl chloride resin (A~o Preferably the destructible marking film of this invention contains about 1 to about 10 parts, especially about 1 to about 5 par-ts, bY weight of a :lubricantO It may also contain up to about 10 parts by;weight of a s-tabllizer per l00 parts by weight of the vinyl chloride resinO ~he use of a liquid plastic-zer~oan be omitted in the marking film of this inven-~ 20 t~ion, but the lnclusion of a small amoun-t of, say, less : ~ than about 15 parts by weight, of a liquid plasticizer per 100 p OEts by weight of -the vinyl chloride resin is ; permissibleO
he use of such a small amount of plastici2er .~
in the mixture of the resins ~A), (B) and ~G) is possible without hampering the achievement of the improvements ~: ; by the cooperative action of t~e three resins9 and the various defects mentioned above which are caused by ' -the migration of the plasticizer can be fully avoided~
~ he vinyl chloride resin usecl for the destruct-ible marking film o:E this invention i.s a resin having a degree of polymeri~ation of about 60Q to about 1,600.
I.E -the degree of polymerization is less than about 600, -the dimensional stability of the resulting film is markedly reduced, and after application, the film shrinks and cannot adhere firmly and stablyO Moreover, the thermal stability o~ the film wi.ll also be affectedO
On the other hand, when the degree of polymeriza-tion exceeds about 1,600, the productivity of film manufac-: ture lS reduced, and it is impossible to produce the film :at a commercially feasible speedO
If desired, the vinyl chloride resin (A) may ; 15 contain not more than 15% b~ weight of a comonomer unit such as ethylene, propylene,~ butene, vinyl acetate, an acrylate ester, preferably a Gl-C18 alkyl ester of a:crylic acid, vinylidene chloride, a ~inyl ester or ; ~ ~ a vinyl ether ~he type of the thermoplastic urethane resin ~B) to be included in the resin composition in an amount of about 10 -to about 100 parts by weight, preferably about 10 to about 50 parts by weight~ more preferably about 20 to~about 40 parts by weight, per 100 parts by weight of the vinyl chloride resin (A) is properly selected according, f~r example, to the desired color to be imparted by the pigment (D)o ~he termoplastic urethane resin (B) may be ~::
3L~ 2 those which have little or no tendency to yellowing.
Preferably, non-yellowing thermoplastic urethane resins are used.
Preferred species are thermoplastic urethane resins obtained by addition-condensation between aliphatic or aromatic poly addition reaction and difunctional active hydrogen-containing compounds capable of reacting with the isocyanates.
Examples of the diisocyanates are hexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, ~; xylylene diisocyanate, lysine diisocyanate methyl ester, trimethyl hexamethylene diisocyanate, isophorone di-isocyanate, hydrogenated tolylene diisocyanate, tolylene diisocyanate, and diphenylmethane diisocyanate.
Examples of suitable difunctional active hydrogen-containing compounds are glycols having a relatively low molecular weight such as ethylene glycol, ~ -1,4-butanediol and propylene glycol, hydroxyl-terminated .
polyester diols and polyolefin glycols having a rela-20~ tively high molecular weight, diamines such as ethylene-diamine or propylenediamine, and aminoalcohols such as ethanolamine.
Especially preferred thermoplastic urethane ~; resins are those obtained by poly addition reaction , :~
between diisocyanates selected from hexamethylene diiso-cyanate, hydrogenated diphenylmethane diisocyanate and hydrogenated tolylene diisocyanate and diols selected ~-` from polyester diols and polyolefin glycols.
~;' :
These diisocyanates and dif~mctional active hydrogen-containing compounds may be used respectively as a mixture of two or more.
Compo~mds produced by the polycondensation of dibasic acids such as adipic acid or phthalic acid with glycols such as ethylene glycol, l,~-butanediol or propylene glycol are frequently used as the hydroxyl- ~ ~`
terminated polyester diols having a relatively high mo-lecular weight.
When the amount of the thermoplastic urethane resin is smaller than the specified limit, the mold- ~ :
ability of the resulting composition is markedly reduced~
and the productivity of film formation is extremely reduced. The resulting fi.lm will have unsatisfactory ~;
destructibility, and its applicability to substrates will be aggravated. On the other hand, when the amount of *he urethane resin exceeds the upper limit specified in the present inventionj the resulting film has poor surface smoothness and weatherability and non-uniformity in color and luster. Thus, the film will lose its :
practical applicability.
In the destructible marking film of this invention, about 2 to about 15 parts by weight of the ethylene/vinyl ester copolymer is further included per 100 parts by weight of the vinyl chloride resin (A).
The copolymer ~C) iSJ for example, a copolymer of ethylene `
with a vinyl ester of a C2-Cl7 aliphatic carboxylic acid such as vinyl acetate, vinyl propionate, vinyl :
` ;
~ - 13 - `' ~...... ' _ lL~ --butyrate or vinyl stearateO
The et.hylene content and -the degree of poly-meriza-tion of -the copolymer (C) are not critical in particularO Copolymers (~) having an ethylene content of ~0 to 70% by welght are preferredO ~wo or more vinyl esters may be used toge-therO ~he copolymer (C) may also include a small amoun-t of another copolymeriz-A able monomer such as an acryla-te or methacrylate ~ 0 Vinyl acetate is by far -the cheapes-t vinyl ester : 10 availableO
When the amount of -th.e ethylene/vinyl est~r copolymer (C) is smaller than the above-specified limit, the productivi-ty of film forma-tion becomes markedly low, : and the resulting film will have poor surface smoo-thness with color specksO If the amount of -the copolymer (C) exceeds the specified upper limit~ the film will lose its moderate toughness9 or have a rough surface with ~: non-uniformi-ty in color or lusterO ~he resin composition will become strongly tacky, and the produc-tivity of film `;: :
; 20 formation is not industrially satisfactoryO
~ he destruc-t:ible marking film of -this inven-tion also includes the pigment (D)o ~he amount of the pigment is not criticalO ~specially good results are ~: obtained by using i.-t in an amoun-t of, for examplej about 10 to about 150 parts by weight~ preferably about 10 to about 100 parts by weight~ per 100 parts by weight of the vinyl ~t~ chloride resin (~)O
~xamples of the pigment (~) include inorganic ::
. . : ~ . : ; . -pigments such as titanium oxide, zinc oxide, lead white, calcium carbonate, gypsum, precipitated silica7 carbon black7 red iron oxide, molybdenum red, cadmium yellow, yellow lead, -titanium yellow, chromium oxide green and ultramarine; and organic pigments such as Permanent Red 4R, Hansa Yellow 10G, Benzidine Yellow GR, Permanen-t Garmine ~B, Phthalocyanine Blue B7 and Phthalocyanine Green O
In addition to the vinyl chloride resin (A), the thermoplastic urethane resin (B), the ethylene/
vinyl ester copolymer (C), and the pigment (D), the destructible marking film of the invention may contain about 1 to about 10 parts by weight9 preferably about :: 1 to about 5 parts by weight~ of a lubricant per 100 --: 15 parts by weight of the vinyl chloride resin (A)o Almost all lubricants usually employed in the processing of vinyl chlorlde resins can be usedO Examples are poly-ethylene waxesg liqui.d paraffin, stearic acid, stear-amide~ bisamide, n-butyl stearate and aliphatic alcoholsO
~he use of lubricant serves to impart favorable : : luster to the destructible mar~ing film of this inventionO
:::
he destructible marking film of this inven-: tion may contain a small amount of a s-tabilizerO The amount of the stabilizer is preferably not more than 25 about 10 parts by weight per 100 parts by weight of the vinyl chlorlde resinO Examples of -the stabilizer include calcium stearate, barium steara-te, lead stearate, basic lead sulfite~ dibasic lead phosphite, dibutyltin dilaurate, :, :' dibutyltin dimaleate9 dibutyltin mercaptide9 dioctyl-tin maleate--type stabilizers 9 clioctyltin laurate-type stabilizers7 dioc-tyl-tin mercapto-type stabilizers9 and stannane-diol deriva-tives or complexes of theseO
Anti-haze agents such as nonionic surface-active agents9 polyoxyethylene, and glycerin monos-teara-te are al.so cited as such stabilizersO
~ he film of this inven-tion may a]so contain an anti-o~idant such as ~H~ (276-ditertiary-butyl p-cresol) and bisphenol A7 and an ultraviolet absorbersuch as 272'-dihydroxy-4--methoxybenzophenone9 and 2-(2'-hydroxy-~'95'-di-tertObutyl-phenyl)~5-chlorobenzo-tria~oleO
As stated hereinabove9 the destructible marking ~ : 15 film of the invention may contain not more than about : :~ : 15 par-ts by wei~ht of a plasticizer per 100 parts by , ~
: ~ weight: of the vinyl chloride resin (A)~ When the ~; ~ plastlcizer is used in a larger amount7 the adhesion s~tability and operability of the film are deterioratedO
When it is used in -the amount indicated, favorable re-sults can be obtained in improving the clarity and surface luster of the resul-ting ~ilmO ~he plastici~er ;~ may be selected from those which are commonly used for processing vinyl chloride resinsO Preferably9 it is : ~ 25 selected from epoxy derivatives having an oxirane oxygen con-tent o~ 2 -to ~ and a molecular weight of not more than 17000, and polyester-type plasticizers of the sebasic acid7 adipic acid7 ~zelaic acid9 and ~ 16 -~
.. : .. , ; ,. : .. , ~ ,. . .
~ 17 : phthalic acid type.sO
~ he destructible marking film of this inverl~
-tion can be prepared by molding the aforesa~d pigment-containing resin composition into a ~ilm having a thickness of about ~0 to abou-t 100 mlcronsO
Preferably9 the molding is carried ou-t by a calender methodO But when a film having a larger ~: ~ thickness below about 100 microns is to be produced, ~ an extrusion molding method can also be employedO
:~ ~ 10 : ~ilm forma-tion by the calender method is well ~: known in the art, and in the present inven-tion, it can be performed in the same mannerO Preferably, an as-formed film from a calender film-forming machine lS
: rapidl~ cooled at it necking portion with a:gaseous 15 ~cooling medium at a tempcrature of not more than about 30C, for example9 about ~10C to about ~0C9 such as alr, nitrogen or carbon dioxide gasO
Since the film of -this invention is a de~ :
structible~marking film9 it is necessary to avoid a stretching operation which will resul-t in an ultrathin film having a destructibility (impact strength) of more than~150 kg~cm/mmO Accordingl~9 the as-formed ~ilm from : t-he calender machine has a -thic~ness of about 30 microns to about 100 microns or soO Eve~ when a stretching action is exerted on -the film as formed, the extent of : stre-tching of the film should be-tter be such that the ~;~ percentage~ of the surface linear speed o~ a film take-~: up roll based on the surface linear speed of last roller ~, ~;:
~:
; ~ - 17 -, .~
- 1~3 --is not more than about l~O~ preferably not more than about 130%o l`he calender molding tempera-ture is abou-t 140 to about 190C9 and the -tempera-t-~re at the time of stre-tchlng is about 50 to about 140Co Film forma-tion by an extrusion methc)d Call also be performed by procedures well known in the production of unstretched films~ ~ilm forma-tion is possible by any of a ~-die me-thod and an inflation me-thodO The T-die method is preferred to secure des-tructibility sufficientlyO
~he processing temperature is determined properl~
according to the capabili.ty of a given machine while main-taining the temperatures at the cylinder por-tion7 the adapter portion and the die portion respectively at 140 to 220Co When it is desired -to obtain a substantially 15 unstretched film having a thickness of about 30 to 100 microns~ it is neces~sary to prescribe the die lip clear-ance at not more than 002 mmO Thus, this method is advarl-tageous for producing fi.lms having a rela-tively la ge thickness of 7 say, 100 micronsu ~he present inven-tion is free from the manufac-turing res-trictions and can afford at a low cost by an easy operation a destructible marking film having improved operabi.lity in adhering~ -thermal stability~ surface smooth-ness~ dimensional s-tabili-ty and weatherabili-~yO The f'ilm can be prepared with good produc-tivi-t-~ while securing the safety of the working environment and obviating the need to recover the solvent usedO According to this invention~ the destructibility of -the film can be ad-justed to the desired value~ and has good reproducibilityO
, . . . ... , . .. , , ~
f~
'~he composition of the destructible film ob-tained as a final produc-t can be determined by -the following me-thodO
The film is extrac-ted with e-thyl etherO r~e-tra-hydrofuran is added to the res1due [containing the resins(A), (B) and (C) ~ the pi.gmen-t (D)], and the mixture is stirredO ~he mixture is fil-tered to separa-te i-t into an insoluble portion and a soluble portionO r~he soluble portion contains -the resins (A), (B) and (C), and the : 10 insoluble portion contains only -the pigmen-t (D)~ he weight of the insoluble portion is measured to deter-mine the proportion of the pigment (D)o ~ etrahydrofuran is evaporated from the soluble portionO ~thyl acetate is added to the residue, and the 15 : mixture is stirredO ~he mix-ture is filteredO I`he fil-trate is evaporated to dryness and -then weighedO ~rom ;; : :; the IR spectrum of the product, this portion is iden-: ~ tified as an ethylene/vinyl acetate copolymer (C)O
`~: IR spectrum~ charac-teristic absor~tions at 2975 cm l an absorption band of vinyl aceta-te, -CE3 s-tre-tching 2850 cm l an absorption band of vinyl acetate and ethylene, -CH2 stretching ~ 1770 cm l an absorption band of vinyl acetate, : 25 C=0 stretching ~` 1240 cm l~ an absorption band of vinyl aceta-te, C-0 s-tretching ; 720 cm l~ an absorption band of ethylene, -CH2- skeleton stretching ~' - -The above e-thyl acetate~insoluble portion and a mixture of isopropyl alcohol and toluene (1:1) is s-tir-red~ The mix-ture is filtered, and methanol is added to the filtrate -to re~precipi-tate ito The precipitate is washed with rnethanol, dried~ and weighedO ~he product is identified as a ure-thane resin (B) from its lR spectrumO
~ __u~ haracteristi a 3300 cm 1. N-I-I stre-tching vibration 2940 cm 1 CH2 stretching vibration 101730 cm 1. a=o stretchin~ -vibration 1550 cm 1. a combined absorption band of ~H
angular displacement, CN stretching 'I'he portion insoluble in isopropanol/toluene : (1/1) is washed with methanol, dried, and weighedO The product is identified as a vinyl chloride resin (A) from its IR spectrumO
1 spectru~_ch racteristic absorptions a-t 2940-2915 cm 1~ -CH2- stretching vibration 2900-2880 cm 1 -CH- stretching vibration 201480-1440 cm 1 -CH2 angular displacement : vibration caO 1340 cm ~: -CH- angular displacement vibration 750- 650 cm 1 C-Cl stretching vibra-tion - 25The following ~xamples and Comparative ~xamples ~: illustrate the present invention in more detai.lO
'he various properties in these ~xamples were measured by the following me-thodsO
:
~:
... . . . .. . .. . .
~estructibili-t~
-Measured at 25C by a film impact -tester (capaci-t~ ~0 kgOcm, impact speed 202 km/sec~, impac-t ball with a radius of 1 i.nch) in accordance with -the punch-t-gpe impac-t tes-ting methodO
Operabilit~_in adher~
~ his is evaluated by -the height of the~ t of a rivet with a diameter of 10 mm to which the film coa-ted with an adhesive can be applied without breakage or rais-ingO
1: a height of more than 4 mm 2: a height of 4 to 3 mm
3: a heigh-t of 3 to 2 mm
4: a heigh-t of 2 -to 1 mm ~: : 15 5: a height of less than 1 mm ~ r~he larger the height, -the be-t-ter the oper-:~ abilityO
: r~he film coated with an adhesive is applied to an alumlnum plate (an aluminum plate of A5052P stipulated in JI~ E4000), and allowed to stand at 25C and 70C -~
:~ for 168 hoursO lhen, a peeling test is performed at 25C at a peeling angle of 180 and a peeling speed of : : 200 mm/minO r~he degree of peeling between the film and ~ 25 the adhesive and the transfer of the adhesive to the ; aluminum plate is observed~
A r~he adhesive was transferred to the aluminum plate; or only the adhesive :
:~
\
layer was brokenO
a l'he adhesive was completely transferred -to the aluminum plate A condition between these .A and C is expressed ~ 5 as l/nC according to the extent of transfer~
:~ When the transfer begins~ the adhesion strength : ~ is not effectively exhibited, and the surface film peels while leaving the adhesive on the adherendO A film ;:: whose adhesive layer is transferred with time is dif-ficult to use in appli.cations which will be placed under rigorous temperature conditions9 for e~ample in marine containers, signboards, and autoMobiles however excel-: lent weatherability the surface layer film hasO
hermal stabilit~
. . ~
'lhe white film stuck to an aluminum plate is allowed -to stand in a Geer's oven at 150C for 40 minutesO Then, it is taken ou-t of the oven, and its : color is évaluated on a scale of 1 to 4 as follows:
. ~ :
: 1: no change i.n color 2: changed to light pink : 3: changed to light violet :: : 4: changed to violet 'his change in color is especially impor-tan-t when the film is intended -to be applied to parts reguir-ing thermal stability, for example to an en~ine room of an automobile~
~: Surface smoothness The surface condition of the film is visually ' "
~,, _ 22 -`~`
observedl and evaluated on a scale of 1 -to 4 as followso 1: rl`he surface is smooth, and its luster is great n 2: 'l`he surface is nearly srllooth, but its 5degree of luster is ~omewhat lowO
3. '~he surface is sornewha-t roughened, and the degree of luster is lowerO
4. The surface is greatly roughened, and no luster exis-tedO
P~oduct]~rit~
rl'his is evaluated by the maximum speed at whicl thc f lm can be produced without -the occurrence of any d~fec-u.
n -~n~L~ al stabilit~
~he filrn coated with an adhesive~ in a sguare shape with each side measuring 20 cm~ is applied to the same aluminum plate as used in testing resistance to heat deterLoration after adhesionu l'he film is heated at 70~ for 16~ hoursO Changes in its lengthwiPe and cross-20 WlS~ dimensions are measured tc e~ .ate its dimensional `~ stability~
Weatherabi]~
l'he film coated with an adhesive is applied to an alurninurl plate (A-5052P aluminum plate stipulated in JIS ~4000), and irradiated for a prede-termined perlod of .ime by a~Sunshine Weather-Ometer (a product of Suga l`est:ng i~lachine CoO~ L-tdu; in accordance with JIS K7102;
~blac` panel -temperature 63 + ~C; spray cycls 18 min.
:, -, _ 23 ~
min.). The time which elapses until the surface oF the film is whitened is measured, and defined as the weatherability of the film.
Example 1 ~o'rm'ul'ationParts by Weight Polyvinyl c'hloride having a degree of polymerization of ; 1600 100 ~ .
Urethane resin resulting from the condensation of hexamethylene diisocyanate and adipic acid/-ethylene glycol ester 40 Ethylene/vinyl acetate copolymer having an ethylene content o 55% 8 Titanium oxide 50 Tin-type stabilizer 2 Tinuvin P* (2-(2'-hydroxy-5'-methylphenyl)benzotriazole; a product of Ciba-Geigy) 0.2 ,`
Polyethylene wax ~lubricant) 2.0 A composit~on of the above formula~ion was shaped by a calender method under the following conditions, and cooled with air at 25VC to form a film having a thickness of 50 microns.
The temperatures of the various rolls in the calender method were as follows:
Mixing roll: 175C
Warming roll: 175 , Calend'er rolls ' Rl: 175 R2: 170 : .
~, *Trademark .
~' - 24 -.-.~ ..... . . , . . I
~ ~5 -R3: 165 ~: 160 : ~he streuching ratio of -t;he film was 15%o Polyvinyl chlorlde having a degree of polymerization of 100 . ~ 1100 Same urethane resin as in20 ~xample 1 ,, ~
~ ame ethylene,/vinyl ester15 '~ ~ copolymer as in ~xample 1 tanium oxide ~ 10 ~``~
~ Lead~type stabillzer 3 ~Stearamide " ~poxidized soybean oiI 5 : (plasticizer) composltion of -t;he above formulatlon was formed into:a film having a thickness of 70 microns by 15:~ ~tbe~same method as in Example 1 except that the tempera-A~ ;tureS~of -the calen:der roll Rl and R3 were changéd to 17G
and 160e respectively, the s~tretching ratio was changed to l~/o~ and the film was cooled with air at 10 Go ~ ~ormulation ; ~PartE b weig~
Gopolymer of vinyl chloride : and vi~yl acetate~,having a '~ ` vinyl acetate content of100 l~/o and a ~egree of poly-~ merization of ~00 '' Urethane resin derived from hydrogenated diphen-~lmethane 10 diisocyanate and adipic: acid/
: propylene glycol ., ~':
.,.:,::
. , . ~ ~
~ 25 ~
.
:
Copolymer of ethylene and vinyl propionate having an ethylene content of 45% 3 Phthalocyanine Blue 5 Llght calcium carbonate 10 Barium zinc-type stabilizer Polyethylene wax Butylstearate 2 .
A composition of the above formulation was formed into a film having a thickness of 30 microns in the same way as in Example 2 except that all the rolls were kept at 170C, and ,, the stretching ratio was changed to 30%.
''Example 4 `:
''Formulation Par`t's by` We`i`ght Polyvinyl chloride having a degree of polymerization of Urethane resin derived from Hexamethylene diisocyanate and polypropylene glycol 90 .
Copolymer of ethylene and vinyl acetate having an ethylene content of 65% 8 .~;
Cinquasia Red 20 Heavy calcium carbonate 15 ~:;
Tin-ty-pe stabilizer 2 Calcium zinc type stabilizer TinuvIn 327* ~2-~2~-hydroxy-3',5'-di-tert-'butylphenyl3-
: r~he film coated with an adhesive is applied to an alumlnum plate (an aluminum plate of A5052P stipulated in JI~ E4000), and allowed to stand at 25C and 70C -~
:~ for 168 hoursO lhen, a peeling test is performed at 25C at a peeling angle of 180 and a peeling speed of : : 200 mm/minO r~he degree of peeling between the film and ~ 25 the adhesive and the transfer of the adhesive to the ; aluminum plate is observed~
A r~he adhesive was transferred to the aluminum plate; or only the adhesive :
:~
\
layer was brokenO
a l'he adhesive was completely transferred -to the aluminum plate A condition between these .A and C is expressed ~ 5 as l/nC according to the extent of transfer~
:~ When the transfer begins~ the adhesion strength : ~ is not effectively exhibited, and the surface film peels while leaving the adhesive on the adherendO A film ;:: whose adhesive layer is transferred with time is dif-ficult to use in appli.cations which will be placed under rigorous temperature conditions9 for e~ample in marine containers, signboards, and autoMobiles however excel-: lent weatherability the surface layer film hasO
hermal stabilit~
. . ~
'lhe white film stuck to an aluminum plate is allowed -to stand in a Geer's oven at 150C for 40 minutesO Then, it is taken ou-t of the oven, and its : color is évaluated on a scale of 1 to 4 as follows:
. ~ :
: 1: no change i.n color 2: changed to light pink : 3: changed to light violet :: : 4: changed to violet 'his change in color is especially impor-tan-t when the film is intended -to be applied to parts reguir-ing thermal stability, for example to an en~ine room of an automobile~
~: Surface smoothness The surface condition of the film is visually ' "
~,, _ 22 -`~`
observedl and evaluated on a scale of 1 -to 4 as followso 1: rl`he surface is smooth, and its luster is great n 2: 'l`he surface is nearly srllooth, but its 5degree of luster is ~omewhat lowO
3. '~he surface is sornewha-t roughened, and the degree of luster is lowerO
4. The surface is greatly roughened, and no luster exis-tedO
P~oduct]~rit~
rl'his is evaluated by the maximum speed at whicl thc f lm can be produced without -the occurrence of any d~fec-u.
n -~n~L~ al stabilit~
~he filrn coated with an adhesive~ in a sguare shape with each side measuring 20 cm~ is applied to the same aluminum plate as used in testing resistance to heat deterLoration after adhesionu l'he film is heated at 70~ for 16~ hoursO Changes in its lengthwiPe and cross-20 WlS~ dimensions are measured tc e~ .ate its dimensional `~ stability~
Weatherabi]~
l'he film coated with an adhesive is applied to an alurninurl plate (A-5052P aluminum plate stipulated in JIS ~4000), and irradiated for a prede-termined perlod of .ime by a~Sunshine Weather-Ometer (a product of Suga l`est:ng i~lachine CoO~ L-tdu; in accordance with JIS K7102;
~blac` panel -temperature 63 + ~C; spray cycls 18 min.
:, -, _ 23 ~
min.). The time which elapses until the surface oF the film is whitened is measured, and defined as the weatherability of the film.
Example 1 ~o'rm'ul'ationParts by Weight Polyvinyl c'hloride having a degree of polymerization of ; 1600 100 ~ .
Urethane resin resulting from the condensation of hexamethylene diisocyanate and adipic acid/-ethylene glycol ester 40 Ethylene/vinyl acetate copolymer having an ethylene content o 55% 8 Titanium oxide 50 Tin-type stabilizer 2 Tinuvin P* (2-(2'-hydroxy-5'-methylphenyl)benzotriazole; a product of Ciba-Geigy) 0.2 ,`
Polyethylene wax ~lubricant) 2.0 A composit~on of the above formula~ion was shaped by a calender method under the following conditions, and cooled with air at 25VC to form a film having a thickness of 50 microns.
The temperatures of the various rolls in the calender method were as follows:
Mixing roll: 175C
Warming roll: 175 , Calend'er rolls ' Rl: 175 R2: 170 : .
~, *Trademark .
~' - 24 -.-.~ ..... . . , . . I
~ ~5 -R3: 165 ~: 160 : ~he streuching ratio of -t;he film was 15%o Polyvinyl chlorlde having a degree of polymerization of 100 . ~ 1100 Same urethane resin as in20 ~xample 1 ,, ~
~ ame ethylene,/vinyl ester15 '~ ~ copolymer as in ~xample 1 tanium oxide ~ 10 ~``~
~ Lead~type stabillzer 3 ~Stearamide " ~poxidized soybean oiI 5 : (plasticizer) composltion of -t;he above formulatlon was formed into:a film having a thickness of 70 microns by 15:~ ~tbe~same method as in Example 1 except that the tempera-A~ ;tureS~of -the calen:der roll Rl and R3 were changéd to 17G
and 160e respectively, the s~tretching ratio was changed to l~/o~ and the film was cooled with air at 10 Go ~ ~ormulation ; ~PartE b weig~
Gopolymer of vinyl chloride : and vi~yl acetate~,having a '~ ` vinyl acetate content of100 l~/o and a ~egree of poly-~ merization of ~00 '' Urethane resin derived from hydrogenated diphen-~lmethane 10 diisocyanate and adipic: acid/
: propylene glycol ., ~':
.,.:,::
. , . ~ ~
~ 25 ~
.
:
Copolymer of ethylene and vinyl propionate having an ethylene content of 45% 3 Phthalocyanine Blue 5 Llght calcium carbonate 10 Barium zinc-type stabilizer Polyethylene wax Butylstearate 2 .
A composition of the above formulation was formed into a film having a thickness of 30 microns in the same way as in Example 2 except that all the rolls were kept at 170C, and ,, the stretching ratio was changed to 30%.
''Example 4 `:
''Formulation Par`t's by` We`i`ght Polyvinyl chloride having a degree of polymerization of Urethane resin derived from Hexamethylene diisocyanate and polypropylene glycol 90 .
Copolymer of ethylene and vinyl acetate having an ethylene content of 65% 8 .~;
Cinquasia Red 20 Heavy calcium carbonate 15 ~:;
Tin-ty-pe stabilizer 2 Calcium zinc type stabilizer TinuvIn 327* ~2-~2~-hydroxy-3',5'-di-tert-'butylphenyl3-
5-chlorobenzotriazole; a product of cib.a-GeIgr) B~samide* (methylene-bis-stearamide) 2 Polyethylene wax `, Adipic acid-type polyester ~plasticizer) 3 *Trademarks ::: ,: .
ta~z :
h composition of the above formulatlon was formed into a fi.lm having a thickness of 90 microns by the same method a9 in Example 1 except tha-t the stre-tching ratio was changed to 10%~ the film was cooled wi-th air at 0C, and the various rolls were kep-t at the following tempera-tures ~lixing roll: 170G
Warming roll: 170 : Calender rolls : 10 Rl: 170 X2: 170 R~: 175 RL~: 180 :Ex~ e~$
15 ~ .A composition of the same formulation as in : ~xample 1 was shaped by a '~'-die extrusion ~e-thod under t~
fol:lowinG method -to form a film having a thickness of 90 micronsO
emperature of -the cylinder portion: 170 to 180C
Temperature of the adapter portion: 1~0 ~emperature of the die portion: 170 Stretching ratio: 50~/0 Cooli~g: with a take-off roll at 30C
G~ ara-tive ~x~le 1 'r'he procedure of ~xample 1 was repeated except that the urethane resin was not usedO hS shown in 'l'able ` 1~ the film obtained had a poor ~uali-tyO
'.' ~ C m ara-tive :Ex~_ ~ The procedure of ~xample 2 was repeated except :
, . - 27 -v~
_ 28 --that -the urethane resirl was not usedO
~3~
'~he procedure of ~xample 1 was repeated ex-cept that -the ethylene/vinyl ace-tate copolymer was not usedO
Comparative ~ample 4 rlhe procedure of ~xample 4- was repeated ex-cept that -the ethylene/vinyl acetate copolymer was not used~
Comparative_~xample ~
rrlhe procedure of ~xample 1 was repeated ex-cept that -the ethylene/vinyl aceta-te copolymer was no-t used, and ins-tead of the polyvinyl chloride~ a vinyl chloride-grafted copolymer of ethylene and vinyl acetate obtained by grafting vinyl chloride to an e-thylene/vinyl acetate copolymer having an ethylene content of 55% and ~ ; ~ an in-trinsic viscosity of 0O7 in a ratio of 15:1 was :: usedO
Compara-tive ~xample 6 ;; 20 ~'he procedure of ~xample 1 was repeated ex-cept that chlorinated polyethylene having a chlorine ~: content of 3~% and containing methylene isocyana-te (with a specific viscosity of 1088 at 180C) was used instead of the ure-thane reicin was usedO
~: 25 Comparative ~xample_7 he procedure of ~xample 1 was repea-ted ex-cept that NBR having an acrylonitrile content of 30%
and a Mooney vii~cosity of 40 was used instead of the . .
:
. ~ .;
3L ~ 2 - 2~ -urethane resinO
Comparative ~xample 8 '~he procedure of Example 1 was repeated ex-cept that chlorosulfonated polyethylene having a Mooney viscosity of 30 was used instead of -the urethane resinO
Comparative ~xample 9 ormulationParts by wei~ht Polyvinyl chloride having a degree of polymeriza-tion of lO0 Polypentyl me-thacrylate lO
Polymethyl me-thacrylate 5 r~itanium oxide 50 '~in-type stabilizer 2 Polyethylene wax 2 Di-(2-ethylhexyl)phthalate 15 (plasticizer) A composition of -the above formulation was formed into a film having a thic~ness of 50 microns by : the same calender method as described in ~xample lo Comparative ~xample lO
he procedure of Comparative ~xample 9 was re-peated excep-t that the film was prepared by a casting method instead of the calender me-thod. In the casting : process, a solution of the composition in a solvent con-sisting of methyl ethyl ketone and toluene in a ratio of 80:20 was cast on a stainless steel belt having a length of 80 meters, and dried in an atmosphere held at 80 to 160Co 'l'he stretching ra-tio was 5%~ and the , .:
- 2'~ -- ~o film was cooled at 15Co Com ara-tive Exam le 11.
~P ~
~ composi-tion having -the same formula-tion as in ~xample 1 was cast into a fil~l having a thickness 5 of 50 microns by the same me-thod as in Comparative Ex-ample 10 excep-t -that -tetrahydrofuran was used ins-tead of the methyl ethyl ketone/-toluene mixtureO
Comparative Example 12 The procedure of Example 1 was repeated ex-cept that the amount of the ethylene/vinyl acetate co-polymer was changed -to 20 parts by weigh-tO
Compara ive Example 1-~
The procedure of ~xample 1 was repeated ex-cept that polyvinyl chloride having a degree of poly-15 merization of 400 was used ins-tead of the polyvinyl chloride used in Example lo Com arative Exam le 14 The procedure of Example 1 was repeated ex-cept that polyvinyl chloride having a degree of poly~
merization of l:L00 was used instead of the polyvinyl chloride used in ~xample 1, and the amount of -the urethane resin was changed to 120 parts by weightO
:~ The various properties o-f` the films obtained in the above Examples and Comparative Examples were mea-sured, and the results are shown in Table 1~
~' ..~
__ h h^ ~ O o 0 O 0 a) ~ a2 a~ O I ~ O ~ O I r-lr~l 0 r-l ~ O O O O ~ ~ i~~ I O O O i-~3: 0 ~--~ r~ (\1 r~lr-l r-l .
Q ~
a2 r~~ ~ Ll~ cO O Lr\ O ~ - Lr\ cO C~ ~O r~ ~~ O ~ O r~ I 00 ~ N~ ~~ O
r~ ~ O O O O O 1~ r-l ~ ~~J r-l u2 ._ ~ ~ r~ O O 0 15\ 0 I tf ) L~ \
rd ~ ~ ~ 1~ ~ N-~ ~) r~l h r-l ~
1~ , .~
(V,s~
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r~ r~
r-l ~ r~ r~ r~l r--l r~ r~l I N~ ~ ~ ~ 1~ N~
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r~ _ _ .
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cS ~ r o -1~ h ~$ $ ~$ $ ~ I ~ ~I V
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.~ r~ rl rd 1, _ ~,, .
I
Ul ,a I O ~ co c-- ~ I r-l 1~ 0 0 r-l ~ r1 ~) .~ h i ~
r-lh r~ ~ r~ (~J ~ ~ r~ 01 ~ ~ Ll~ ~ ) C~
o p ~ ~
_ 32 . _ ooooooo l o o o o o o o h p~ ~ J (\~1 O O
~ 1~ U~ r i r-l r-l r~ r~ r-l s~ . r~ F l 1~ r-l ~O O O O O O O
~U r~l O O O O O O O O
a) ,~ ~ ~t O O O O cO IX) 3: ~ ~ r I r-l r~ r-l _ .
~lS
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rl rl u~ r~ ~co 1~ 0 r~
r I rl ~ r~ co C~ 0~ [i--a) o, O O , O O O O
::i r-l O O O O r rl ~
Pl u~ ~
, - . . _____ ~-1~ r ~ O O LO O 11~ 0 O ~ 1~ (U r-l 1 h~ ~1 __ . . ...
c~ ~1 ~1 ~1 0 ul~t r-l ~d h o u~
~>
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rl _ ~ _ +~
r~ 0 r~
C) ~3 rl h D 1~ r~ r ~ r-l r~
r~ ~-1 u a) . ~ -- ~
r~ a) I
r9 ~ I r~
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-1 ~ O r~
u~ (D r1 F~ u~ V V ~
r~ rd ~ a) (DL~ g cq 4 u~ 1 Q~ O h ~ rd ~ ~ r-l p:~ ~ O ~ O
_ ____~____ r~ ~ O
C:I r rl ~01 r-l (~1 r~ r~ ~1 Q~ rl rd Or~ 0 _ I h ~3 :' C~ ~ El ~` . r~ ~1~ (~Lr~ :~ O ~ O
-1~ rl O
u~ Q I r~ r~ r~
Q) r~
~4 :: ~
. ~
a~ o 0 ~ o r-l(~
,~ hr~l ~ a)(~r~ r-l r~r~r~
,C~--0 pl O
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p ~ r ~ o rl ~C V 1 .~ ' ~ ~
_ 32 --
ta~z :
h composition of the above formulatlon was formed into a fi.lm having a thickness of 90 microns by the same method a9 in Example 1 except tha-t the stre-tching ratio was changed to 10%~ the film was cooled wi-th air at 0C, and the various rolls were kep-t at the following tempera-tures ~lixing roll: 170G
Warming roll: 170 : Calender rolls : 10 Rl: 170 X2: 170 R~: 175 RL~: 180 :Ex~ e~$
15 ~ .A composition of the same formulation as in : ~xample 1 was shaped by a '~'-die extrusion ~e-thod under t~
fol:lowinG method -to form a film having a thickness of 90 micronsO
emperature of -the cylinder portion: 170 to 180C
Temperature of the adapter portion: 1~0 ~emperature of the die portion: 170 Stretching ratio: 50~/0 Cooli~g: with a take-off roll at 30C
G~ ara-tive ~x~le 1 'r'he procedure of ~xample 1 was repeated except that the urethane resin was not usedO hS shown in 'l'able ` 1~ the film obtained had a poor ~uali-tyO
'.' ~ C m ara-tive :Ex~_ ~ The procedure of ~xample 2 was repeated except :
, . - 27 -v~
_ 28 --that -the urethane resirl was not usedO
~3~
'~he procedure of ~xample 1 was repeated ex-cept that -the ethylene/vinyl ace-tate copolymer was not usedO
Comparative ~ample 4 rlhe procedure of ~xample 4- was repeated ex-cept that -the ethylene/vinyl acetate copolymer was not used~
Comparative_~xample ~
rrlhe procedure of ~xample 1 was repeated ex-cept that -the ethylene/vinyl aceta-te copolymer was no-t used, and ins-tead of the polyvinyl chloride~ a vinyl chloride-grafted copolymer of ethylene and vinyl acetate obtained by grafting vinyl chloride to an e-thylene/vinyl acetate copolymer having an ethylene content of 55% and ~ ; ~ an in-trinsic viscosity of 0O7 in a ratio of 15:1 was :: usedO
Compara-tive ~xample 6 ;; 20 ~'he procedure of ~xample 1 was repeated ex-cept that chlorinated polyethylene having a chlorine ~: content of 3~% and containing methylene isocyana-te (with a specific viscosity of 1088 at 180C) was used instead of the ure-thane reicin was usedO
~: 25 Comparative ~xample_7 he procedure of ~xample 1 was repea-ted ex-cept that NBR having an acrylonitrile content of 30%
and a Mooney vii~cosity of 40 was used instead of the . .
:
. ~ .;
3L ~ 2 - 2~ -urethane resinO
Comparative ~xample 8 '~he procedure of Example 1 was repeated ex-cept that chlorosulfonated polyethylene having a Mooney viscosity of 30 was used instead of -the urethane resinO
Comparative ~xample 9 ormulationParts by wei~ht Polyvinyl chloride having a degree of polymeriza-tion of lO0 Polypentyl me-thacrylate lO
Polymethyl me-thacrylate 5 r~itanium oxide 50 '~in-type stabilizer 2 Polyethylene wax 2 Di-(2-ethylhexyl)phthalate 15 (plasticizer) A composition of -the above formulation was formed into a film having a thic~ness of 50 microns by : the same calender method as described in ~xample lo Comparative ~xample lO
he procedure of Comparative ~xample 9 was re-peated excep-t that the film was prepared by a casting method instead of the calender me-thod. In the casting : process, a solution of the composition in a solvent con-sisting of methyl ethyl ketone and toluene in a ratio of 80:20 was cast on a stainless steel belt having a length of 80 meters, and dried in an atmosphere held at 80 to 160Co 'l'he stretching ra-tio was 5%~ and the , .:
- 2'~ -- ~o film was cooled at 15Co Com ara-tive Exam le 11.
~P ~
~ composi-tion having -the same formula-tion as in ~xample 1 was cast into a fil~l having a thickness 5 of 50 microns by the same me-thod as in Comparative Ex-ample 10 excep-t -that -tetrahydrofuran was used ins-tead of the methyl ethyl ketone/-toluene mixtureO
Comparative Example 12 The procedure of Example 1 was repeated ex-cept that the amount of the ethylene/vinyl acetate co-polymer was changed -to 20 parts by weigh-tO
Compara ive Example 1-~
The procedure of ~xample 1 was repeated ex-cept that polyvinyl chloride having a degree of poly-15 merization of 400 was used ins-tead of the polyvinyl chloride used in Example lo Com arative Exam le 14 The procedure of Example 1 was repeated ex-cept that polyvinyl chloride having a degree of poly~
merization of l:L00 was used instead of the polyvinyl chloride used in ~xample 1, and the amount of -the urethane resin was changed to 120 parts by weightO
:~ The various properties o-f` the films obtained in the above Examples and Comparative Examples were mea-sured, and the results are shown in Table 1~
~' ..~
__ h h^ ~ O o 0 O 0 a) ~ a2 a~ O I ~ O ~ O I r-lr~l 0 r-l ~ O O O O ~ ~ i~~ I O O O i-~3: 0 ~--~ r~ (\1 r~lr-l r-l .
Q ~
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r~ ~ O O O O O 1~ r-l ~ ~~J r-l u2 ._ ~ ~ r~ O O 0 15\ 0 I tf ) L~ \
rd ~ ~ ~ 1~ ~ N-~ ~) r~l h r-l ~
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cS ~ r o -1~ h ~$ $ ~$ $ ~ I ~ ~I V
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_ 32 . _ ooooooo l o o o o o o o h p~ ~ J (\~1 O O
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_ ____~____ r~ ~ O
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-1~ rl O
u~ Q I r~ r~ r~
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p ~ r ~ o rl ~C V 1 .~ ' ~ ~
_ 32 --
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A destructible marking film having a thickness of from 30 to 100 microns and a destructibility of not more than 150 kg.cm/mm, said film being composed of a resin composition comprising (A) 100 parts by weight of a vinyl chloride resin having a degree of polymerization of from 600 to 1,600 and containing from 0 to 15% by weight of a comonomer unit, (B) 10 to 100 parts by weight of a thermoplastic urethane resin, (C) 2 to 15 parts by weight of an ethylene/vinyl ester copolymer, and (D) 10 to 150 parts by weight of a pigment.
2. The film of claim 1 wherein the resin composition contains at least one additive selected from the group consist-ing of up to about 10 parts by weight of a lubricant, up to about 10 parts by weight of a stabilizer, and up to about 15 parts by weight of a liquid plasticizer.
3. The film of claim 1 wherein the comonomer unit of the resin (A) is selected from ethylene, propylene, butene, vinyl acetate, alkyl acrylates, vinylidene chloride, vinyl esters and vinyl ethers.
4. The film of claim 1 wherein the thermoplastic urethane resin (B) is a thermoplastic urethane resin derived from an aliphatic or aromatic diisocyanate and a difunctional active hydrogen-containing compound.
5. The film of claim 1 wherein the copolymer (C) is a copolymer of ethylene and a vinyl ester of an aliphatic carboxylic acid containing 2 to 17 carbon atoms.
6. The film of claim 1 wherein the ethylene/vinyl acetate copolymer has an ethylene content of from 30 to 70% by weight.
7. The film of claim 1 wherein the vinyl ester in the copolymer (C) is at least one member selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, and mixtures of at least one of the foregoing vinyl esters with alkyl acrylate or alkyl methacrylate.
8. A process for preparing a destructible marking film having a thickness of from 30 to 100 microns and a destructibility of not more than 150 kg.cm/mm, which comprises molding a resin composition by calendering or melt-extrusion, said composition consisting essentially of (A) 100 parts by weight of a vinyl chloride resin having a degree of polymerization of from 600 to 1,600 and containing from 0 to 15% by weight of a comonomer unit, (B) 10 to 100 parts by weight of a thermoplastic urethane resin, (C) 2 to 15 parts by weight of an ethylene/vinyl ester copolymer, and (D) 10 to 150 parts by weight of a pigment.
9. A method for marking, which comprises applying to the surface of a substrate a destructible film having a thickness of from 30 to 100 microns and a destructibility of not more than 150 kg.cm/mm, said resin composition comprising (A) 100 parts by weight of a vinyl chloride resin having a degree of polymerization of from 600 to 1,600 and containing from 0 to 15% by weight of a comonomer unit, (B) 10 to 100 parts by weight of a thermoplastic urethane resin, (C) 2 to 15 parts by weight of an ethylene/vinyl ester copolymer, and (D) 10 to 150 parts by weight of a pigment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA305,527A CA1110792A (en) | 1978-06-15 | 1978-06-15 | Destructible films for marking, process for their production, and their utilization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA305,527A CA1110792A (en) | 1978-06-15 | 1978-06-15 | Destructible films for marking, process for their production, and their utilization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1110792A true CA1110792A (en) | 1981-10-13 |
Family
ID=4111695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA305,527A Expired CA1110792A (en) | 1978-06-15 | 1978-06-15 | Destructible films for marking, process for their production, and their utilization |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1110792A (en) |
-
1978
- 1978-06-15 CA CA305,527A patent/CA1110792A/en not_active Expired
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