CA2159476A1 - Thermoplastic elastomers - Google Patents

Thermoplastic elastomers

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Publication number
CA2159476A1
CA2159476A1 CA002159476A CA2159476A CA2159476A1 CA 2159476 A1 CA2159476 A1 CA 2159476A1 CA 002159476 A CA002159476 A CA 002159476A CA 2159476 A CA2159476 A CA 2159476A CA 2159476 A1 CA2159476 A1 CA 2159476A1
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CA
Canada
Prior art keywords
tpe
blocks
psa
crystalline
scc
Prior art date
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Abandoned
Application number
CA002159476A
Other languages
French (fr)
Inventor
Steven P. Bitler
Raymond Clarke
David A. Kamp
Andrew Larson
Ray F. Stewart
Valentine Y. Yoon
Dale Meier
Robert G. Freelin
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Lifecore Biomedical Inc
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Individual
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Publication of CA2159476A1 publication Critical patent/CA2159476A1/en
Abandoned legal-status Critical Current

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    • C09J153/00Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
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    • C05G5/00Fertilisers characterised by their form
    • C05G5/30Layered or coated, e.g. dust-preventing coatings
    • C05G5/37Layered or coated, e.g. dust-preventing coatings layered or coated with a polymer
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    • C05FERTILISERS; MANUFACTURE THEREOF
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    • C05G5/00Fertilisers characterised by their form
    • C05G5/40Fertilisers incorporated into a matrix
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    • C06B45/04Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
    • C06B45/06Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
    • C06B45/10Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
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    • C06B45/18Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/006Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C09J171/00Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02Polyalkylene oxides
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    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38Pressure-sensitive adhesives [PSA]
    • C09J7/381Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/387Block-copolymers
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    • C08G2170/00Compositions for adhesives
    • C08G2170/40Compositions for pressure-sensitive adhesives
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2250/00Compositions for preparing crystalline polymers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2390/00Containers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852Adhesive compositions
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852Adhesive compositions
    • Y10T428/2878Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2883Adhesive compositions including addition polymer from unsaturated monomer including addition polymer of diene monomer [e.g., SBR, SIS, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852Adhesive compositions
    • Y10T428/2878Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2887Adhesive compositions including addition polymer from unsaturated monomer including nitrogen containing polymer [e.g., polyacrylonitrile, polymethacrylonitrile, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852Adhesive compositions
    • Y10T428/2878Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2891Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/28Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852Adhesive compositions
    • Y10T428/2896Adhesive compositions including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]

Abstract

Pressure-sensitive adhesives (PSA's) and hot melt adhesives having good shear strength contain a thermoplastic elastomer in which the hard (A) blocks, or the soft (B) blocks, or both, contain side chain crystallizable (SCC) moieties. PSA's of this type in which (a) the A blocks contain SCC moieties and (b) the B blocks are crystalline, are novel.

Description

WO 94/24219 215 9 ~ 7 ~ PCT/US94/04138 THERMOPLASTIC ELASTOMERS

BACKGROUND
This invention relates to therrnoplastic elastomers.
Thermoplastic elastomers, which are often referred to as TPE's, are well known.
The TPE's in general use contain (i) polymeric blocks (usually referred to as "hard" blocks 0 or A blocks) which (a) are amorphous and have a second order transition point~Tgh~ which is well above room le~ ldture, or (b) have a crystalline polymer backbone and have a crystalline melting point, Tmh, which is well above room temperature, and (ii) amorphous polymeric blocks (usually referred to as "soft" blocks or B blocks) which have a glass transition point, Tgs~ which is well below room ~e~ ture. Each soft block is linked to at least two hard blocks, so that at lelllpeldlur~;s between TgS and Tmh, or Tgs and Tgh, the amorphous B blocks are tied together, res--lting in ela~L~mc.ic behavior. Above Tmh or Tgh, melting or softening of the hard blocks permits viscous flow of the polymeric chains, resulting in thermoplastic behavior. Known TPE's are described for example in U.S.
Patent Nos. 4,260,659 (Gobran), 4,361,526 (Allen), 4,483,978 (Manser), 4,551,388(Schl~(lem~n), 4,554,324 (Husman), 4,656,213 (Schl~(lm~n), 4,764,586 (Manser), 4,778,852 (FUIdlllUl~), 4,806,613 (Wardle), 4,830,855 (Stewart), 4,919,737 (Biddle et al), 4,952,644 (Wardle et al), and 4,976,794 (Biddle et al) and in the articles in Polymer, 29 (7), 1233-1239 (1988) Kallitsis et al; J. Appl. Poly. Sci 37 (1), 267-281 (1989) Murphy et al; J. Poly. Sci, Part A, Poly Chem, ~ (9) 2393-2401 (1990) Talukder et al;
Makromol Chem, 190, 1069-1078 (1989) Khan et al, ~L. 603-614, 615-624, and 2341-2354 (1990) Fakirov et al, and 191 2355-2365 (1990) Gogeva; and Macromolecules ~8 (2), 123-127 (1985) Miyamoto et al, and ~, 333-337 (1990) Chow.

In our earlier International Patent Application No. PCT/US92/08508 (Docket 9213.1-PCT), ~lled October 8, 1992, published April 15, 1993, as Publication No.WO 93/07194 (Docket 9213.1-PCT), we described and claimed thermoplastic elastomers (TPE's) which contain hard (A) blocks comprising side chain cryst~lli7~hle (SCC) moieties which render the block cry-stalline, and which have a melting point Tq, and soft (B) blocks which are amorphous and have a Tgs which is less than (Tq-10)C. That earlier application WO 94/24219 215 9 ~ 6 PCT/US94/04138 ~

had not been published on the priority date of this application (April 14, 1993), and the TPE's described therein are not, therefore, regarded as known TPE's in this application.

SU~ARY OFTHEn~VENl~ON ~'~
This invention relates to TPE's compri~ing A blocks, or B blocks, or both A blocks and B blocks, which are crystalline and in which at least a part of the crystallinity results from the presence of cryst~lli7~hle side chains. Such crystalline blocks are referred to herein as SCC blocks. TPE's containing SCC A blocks and arnorphous B blocks are 0 described and cl~imed in our earlier application referred to above. TPE's contSlining SCC
A blocks and crystalline B blocks (which may also be SCC blocks) are novel and as such form part of the present invention; they are referred to herein as "the novel TPE's". The invention also includes a wide range of novel processes, compositions, shaped articles and assemblies which make use of (l) the novel TPE's, (2) the TPE's described in the earlier 5 application, and (3) TPE's described in the prior art.
We have discovered that the novel TPE's have the same advantages as the TPE's described in the earlier application. Like the TPEs of the earlier applir~tion, they can exhibit a much more rapid change in viscosity in the region of the crystalline melting point 20 of the side chains in the TPE (l~r~llc;l to herein as Tq) than is exhibited by known TPE's in the region of Tmh or Tgh. This results in a number of illlpO~ t advantages. One is that the novel TPE's can be melt processed at temperatures not far above Tq, e.g. below about (Tq + 10)C, typically below 100C, for example below 75C and even below 50C, whereas known TPE'S are typically melt processed at Le~ c,~tures at least 40C above Tmh 25 or Tgh, usually above 100C. This is particularly useful when the TPEis preferably or n~cess~rily m~int~ined at a temperature below a critical limit (referred to herein as TCnt)~ for example when the TPEis associated with a the~m~lly responsive substance which may undergo, at a temperature above TCnt~ an undesirable change. The substance may be for example in the form of (i) solid particles dis~ ed within the TPE, e.g. particles of an 30 explosive solid, or a pharm~eutic~l or agricultural chemical, or (ii) a substrate which is contacted by the TPE, e.g. a vessel in a living animal into which the TPE has been injected or otherwise placed, or (iii) a solid or a liquid which is encapsulated by the TPE. Another advantage is that the novel TPE's can be used as carriers (including encapsulants) for substances which are at least partially protected against physical and/or chemi~l damage by 35 the TPE at tel,lpel~tures subst~nti~lly below and approaching Tq. The hard blocks in the ~ WO94/~219 321 5 9 ~ 7 6 PCT~S94/04138 TPE will begin to melt at a ~ CldtUlC To which is sc,lllGwl,at below Tq, e.g. 3-12C below Tq. As the temperature is increased from To to Tq, there is a rapid change in the protection provided by the TPE, and above Tq the subst~n~e may be released entirely from the TPE.
For example, an agricultural chemical surrounded by the TPE can be applied while the s r---b cnt ~c~ ature is below Tq and will be released when the ~mhient k;lll~ld~UlC çx~eeflc Tq. Similarly a seed coated with the TPE will not g.. i,~t~. until the ambient lell-~cl~lu c approaches or exceeds Tq.

Another illlpOl ~nt advantage shown by the novel TPE's (and also by the TPE's in the 10 earlier application) is that Tq can be closely controlled through selection of the cryst~lli7~hle moieties in the side chains. For a given cryst~lli7~hle moiety, Tq is mainly dependent on the length of the cryst~lli7~hle moiety, and changes by at most a few C, e.g. less than 5C, with changes in the molecular weight of the A block. In the known TPE's, by CO~ dsl, Tmh or Tgh changes ~,ub~ t~ 11y with changes in the mo1çc~ r weight of the A block. In the novel 15 TPE's, therefore, it is possible to change the physical pr~l ~llies of the TPE (e.g. the elongation, modulus and tensile shrength) without subst~nti~11y ch~nging Tq, by changing the total molecular weight of the TPE and/or the molecular weight of the A blocks and/or the relative amounts of the A and B blocks.

The novel TPE's also show a relatively small difference between Tq and the cryst~11i7~hon peak on a DSC curve as the TPE is cooled.
Another very important advantage of the novel TPE's is that the presence of the SCC A blocks results in improved shear shrengt'n. Furthermore, we have discovered that 2s this advantage is also shown by the TPE's described in the earlier application. In addition, we have discovered that for both the novel TPE's of this application and the TPE's of the earlier application, shear shength can be yet further improved by mixing the TPE with a relatively low mo1ec~ r weight and low melting crystalline additive, particularly an SCC
polymer. The crystalline additive must be intim~tely mixed with the TPE, preferably by mixing the TPE and the additive in the melt or in a common solvent. Particularly good results are obtained when the SCC blocks in the TPE and in the additive are ~,lluclul~lly similar, and we believe that the improved shear strength results from co-cryst~11i7~tion of the additive and the SCC blocks. Thus a preferred combin~tion is a TPEco~ .i.-gSCC
blocks comp~i~ing polymethylene or poly (substituted methylene) groups and an SCC
35 additive compri~ing polymethylene or poly (substituted methylene) groups. The additive Wo 94/24219 PCT/US94/04138 ~
215 9 ~7 6 4 ;

and the amount thereof are preferably such that the composition has a shear strength which is at least 1.3 times, particularly at least 2 times, especially at least 3 times, the shear strength of the composition which is i~lentir~l exce~pt that it does not contain the additive.
The crystalline additive preferably has a numb~r àverage molecular weight of less than s 25,000, or a weight average molecular wei`ght-`of less than 25,000, or both.

The advantages noted above make the TPEs with SCC hard blocks (and either crystalline or amorphous soft blocks), and lllixLules thereof with crystalline additives, particularly suitable for use as plGs~,ule-sensitive adhesives (PSA's) and as hot melt lo adhesives. The TPE, or mixture thereof with a crystalline additive, can be the sole polymeric ingredient(s) of the adhesive, or can be mixed with other polymeric ingredients.
For example, a conventional PSA can be mo lifie~l by addition of the TPE or mixture of TPE
and additive. The adhesive preferably contains 25 to 100%, particularly 75 to 100%, of the TPE, and 0 to 50%, preferably 1 to 40%, of the additive. PSA's for use in the me~ l field 1S for attachment to human skin preferably contain 20 to 35% of the additive. PSA's for use in other fields preferably contain less than 15%, e.g. 1 to 5%, of the additive. The adhesive can also contain additives such as tackifiers, pl~tici7ers, fillers, stabilizers and pigments.
PSA's which contain the crystalline additive have the valuable pi~,~ly that they have reduced adhesive strength when heated to le~ dLulGs approaching or above the crystalline melting point of the additive, as ~ cl-c~e~l in Schmitt et al US Application Nos. 07/829494 and 07/928,800 and the corresponding PCT Application No. US92/01153, publication No.
WO 92/13901, the disclosures of which are incol~old~Gd herein for all llul~oses and to which reference should be made in particular for disclosure of crystalline additives, suitable substrates for PSA composites and uses of PSA composites.
The soft blocks in the novel TPE's can also be SCC blocks, and TPE's containing both SCC soft blocks and SCC hard blocks are particularly useful in the form of films and other shaped articles which are heat-sealed to other polymeric articles. The TPE undergoes a rapid change in its physical properties, including its permeabilit~y to at least some gases and vapors, e.g. 2, C2 and water vapor, in the region of TmS~ but will retain substantial strength until heated to a tell,pe,d~u,G in the region of Tq, when it will again undergo a rapid change in its physical properties, including its heat sealability. The repeating units of the dirr.,lGI~t SCC blocks can be selected to provide a change in permeability (or other ~ )Gl~y) over a desired temperature range, and to provide a hard block which, above Tmh, will be WO 94/24219 ~! 1 S 9 4 7 6 PCT/US94/04138 co~ ible with the other polymeric m~t~ri~l to which the TPE is to be heat sealed. In this way, it is possible to make a TPE which is sufficiently flexible at 0C, which undergoes a marked change in perm~hility in the range of 0C to 40C, which retains adequate physical strength at te~ ;ldtures up to Tq (or close to it) and which can be melt extruded and heat 5 sealed at temperatures not far above Tq, e.g. 60 to 100C. If desired, the physical strength of the TPE can be improved by cro~linking, but this is not generally nçces~ry Such a TPE can be particularly useful as a p~ ging m~teri~l, e.g. for actively respiring biological material, as disclosed in our earlier International Application No. PCT/US9 1/09218 (docket 9209 PCT) filed Decembçr 6, 1991, the disclosure of which is incorporated herein for all O purposes and to which reference should be made for details of this aspect of the invention.

We have also discovered that TPE's cor t~ining SCC soft (B) blocks have important and previously unrealized properties which make it possible to use such TPE's in ways which are novel and surprisingly valuable, even when the A blocks are not SCC blocks and 5 the TPE is in itself known for use in other ways. For example, such TPE's can be used to provide pressure-sensitive adhesives (PSA's) with very valuable properties, to provide films and other shaped articles which can be heat-sealed to other articles, and to provide hot melt adhesives.

In a first aspect, this invention provides novel TPE's cont~ining SCC hard (A) blocks and crystalline soft (A) blocks. These novel TPE's preferably comprise polymeric molecules which comprise (i) polymeric A blocks which 2s (a) are crystalline and have a melting point Tq, and (b) wherein at least one of the A blocks comprises a side chain comprising cryst~lli7~hle moieties which render the block crystalline;
and (ii) at least one polymeric B block which is linked to at least two A blocks andwhich is crystalline and has a melting point TmS which is less than (Tq-10)C.
Any process can be employed to make the novel TPE's of the present invention.
However, particularly useful processes, which provide the second aspect of the present 3s invention, are the processes I to IV disclosed in our earlier International Patent Application WO 94/24219 PCT/US94/04138 ~
2,~5~ 6 -No. PCT/US92/08508 (Publication No. WO 93/07194), to which reference should be made for details, bearing in mind that the B blocks must be crys~alline and can also be SCC blocks.
In a third aspect, this invention provides a composition, shaped article or assembly s which comprises a novel TPE as defined abovè a`nd a second cc ~ ollent which is acsoci~t~d with te.g. is mixed with, is surrounded (e.g. encapsulated) by, surrounds or provides a substrate for) the TPE. In one ~l~rt;ll~d embodiment, the second cc,lll~onent is a thermally responsive substance which undergoes a the~n~lly inrlllced change at a ~mp~,ldlulc TCnt which is above the l~lU~Gldlulc at which the TPE can conveniently be melt lo processed. Because the novel TPE's can be melt-processed at teml)eldtul~s close to Tq, generally below (Tq + 60)C, often below (Tq + 40)C, and even lower, they are superior to known TPE's, which are usually melt processed at temperatures well above Tgh or Tmh-TCnt is preferably above (Tq + 10)C, e.g. (Tq + 10)C to (Tq + 40)C or (Tq + 60)C.
In a fourth aspect, this invention provides a process for making a shaped article, which process comprises (A) melting a novel TPE as defined above, (B) dispersing an additive in the molten TPE, (C) shaping the dispersion from step B, and (D) cooling the shaped article from step C to a l~;lllpeldture below Tq.
In a fifth aspect, this invention provides a process for releasing the second component from a composition, shaped article or assembly of the third aspect of the invention, which process comprises heating the composition, article or assembly by means of heat which is (i) generated by a ~ n body or (ii) generated artifically, e.g. by an electric~l or other heater or by an engine or electrical motor, and/or (iii) conveyed artifically to the TPE. The heat may be conveyed to the TPE by convection, conduction or radiation, but is preferably conveyed by means of a stream of heated fluid, e.g. heated air or a body fluid, which also assists in removal of the second colnpollent from the TPE.
The sixth, seventh, and eighth aspects of the invention are based upon our discovery that TPE's containing SCC blocks (which may be hard blocks or soft blocks or both) have valuable properties which are not disclosed in the prior art or in the earlier International Application No. PCT/US92/08508.

WO 94/24219 215 9 ~ 7 ~ PCT/US94/04138 In a sixth aspect, this invention provides a composition which is suitable for use as (or in the production of) a ~cs~ulc-sensitive adhesive (PSA) and which comprises a TPE
in which the A blocks, or the B blocks, or both, are SCC blocks. Particularly useful PSA
compositions comprise a llli~Lule of the'rPE with (a) a crystalline polymer additive, 5 preferably a side chain cryst~lli7~hle (SCC) polymer, and/or (b) with an amorphous polymer (which may be an el~ctomer), e.g. a known PSA. In this aspect, the invention includes also PSA composites comrricing a backing having a coating thereon of such a cclllposiLion, particularly PSA-coated articles for use in the m~oAit~l field, for example an assembly which comprises (1) a flexible backing, (2) a solvent-free layer of a pressure-sensitive adhesive (PSA) which is securedto the backing, and which comprises a TPE or is at least partially covered by a layer comprising a TPE, said TPE comprising polymeric molecules which comprise (i) polymeric A blocks which (a) are crystalline and have a melting point Tq, or (b) are amorphous and have a glass transition point Tgh;
(ii) at least one polymeric B block which is linked to at least two A
blocks and which (a) is crystalline and has a melting point TmS which is less than (Tq-10)C or less than (Tgh-10)C or (b) is amorphous and has a glass transition point Tgs which is less than (T¢10)C or less than (Tgh-10)C.
wherein at least one block selected from the A and B blocks comprises a side chain comprising cryst~lli7~ble moieties which render the block crystalline. . This aspect of the invention also includes processes for preparing assemblies by joining articles together using such a composition; and processes for rlic~csemhling such assemblies which include heating the PSA
to weaken it. These PSA's, PSA composites, assemblies, and processes preferably have the - functional characteristics set out in the earlier Tnt~rn~tion~l Patent Application No.
PCT/US92/01153, Publication No. WO 92/13901 referred to above to which reference should be made for details of this aspect of the invention. Reference should also be made to that publication for amorphous base resins, crystalline polymer additives, methods of fonnnl~ting Wo 94t24219 PCT/US94/04138 2159476 ` 8 PSA's, methods of applying PSA's to backings, backings, and methods of using PSAcomposites, which are generally suitable for use in this aspect of the invention.

In a seventh aspect, this invention pl~ov~ldes a film or other article which comprises a 5 TPE in which the A blocks, or the B blocks, or both, are SCC blocks, particularly an article which is suitable for use as a componellt of a food package and/or in a method which requires heat-sealing the film These films preferably have the functional characteristics set out in our earlier International Application No. PCT US91/09218 filed December 6, 1991, which also discloses food packages, and methods of p~r~ing and storing foodstuffs, suitable for use in 0 this aspect of the invention, and to which reference should be made for further details of this aspect of the invention. One ~embly according to this aspect of the invention comprises (1) a first film which comprises a TPE as defined in paragraph (2) above of the sixth aspect of the invention, and (2) a second film which is heat-sealed to the first film and which is composed of a polymeric composition which is co np~tible with the A block, or the B
block, or both, of the TPE.
In an eighth aspect, this invention provides a hot melt adhesive co~ ising a TPE in which the A blocks, or the B blocks, or both, are SCC blocks and processes for joining two articles together which comprise forming a layer of a molten polymeric composition cont~ining such a TPE beLween the articles, pushing the articles together, and allowing the composition to cool. Preferably the composition comprises a TPE as defined in p~ra r~ph (2) of the sixth aspect of the invention.
In a ninth aspect, this invention provides a composition which co---plises (1) a TPE as defined in paragraph (2) of the sixth aspect of the invention, and (2) intim~tely mixed with the TPE, a crystalline polymeric additive which (a) has a first order transition point Ta in the composition of 23 to 120C, and (b) has a heat of fusion of at least 5 Joules/g.

WO 94/24219 215 94 7 6 PCTtUS94tO4138 DF.T~lT F.n DESCRI~I'ION OF THE INVENl~ON
For clarity and conv~ni~nce, the following ~ltot~ description of the invention is divided into various headings and sub-headings, e.g. by reference to the various different aspects of the invention. It is to be understood, however, that where a particular feature is discussed only under one he~rlin~, e.g. in relation to one aspect of the invention, that feature is applicable to the invention generally, and can for example be used in other aspects of the invention.

0 Definitions. Abbreviations and Mea~u,~",~nls In this specification, parts, amounts and percent~ges are by weight. Temperatures are in C. Molecular weights are in Daltons and are deterrnined by gel perme~tion chromatography (GPC) in THF (tetrahy~ ful~l) against a polystyrene standard, the Mn values being number average molecular weights and the Mw values being weight average molecular weights. In some places, Mw values are given in thousands, abbreviated as "k";
thus an Mw given as 65k means that the weight average molecular weight is 65,000Daltons. First order transition points (often referred to as melting points), glass transition points, and heats of fusion (~F) are determined by a differential sc~nning calolilllele, (DSC), using the second heat cycle and a heating rate of 10C/minute. The peak of the DSC curve is Tq when the measurement is carried out on the TPE, and Tm when the measurement is carried out on the hard block pl'~;UlSOl before it is incorporated into the TPE. Glass transition points are taken at the mid-point (first derivative) of the secondary transition. Elongation (El) and tensile strength (TS) values are measured at 25C using a 2s tensile test instrument, for example an Instron tensile tester, at a crosshead speed of 0.5 inch/minute (1.27 cm/minute). Modulus values are Young's Modulus (YM) values measured in the same way as the elongation values. Viscosity values are measured at 25C
and a solids content of 30% (we used a Brookfield Viscomelel Model LVT) and expressed in centipoise.
The term Cn is used herein to denote a linear compound or group con~ining n c carbon atoms, and the abbreviations CnA, CnMA and CnIEMA are used to denote linear alkyl acrylates, linear alkyl meth~crylates, and linear alkyl oxycarbonylamido-J ethylmethacrylates in which the alkyl group contain n carbon atoms. For example, C4A is butyl acrylate, C16A is hexadecyl acrylate, and C22MA is docosanyl (also known as Wo 94/24219 PCT/US94/04138 2,S9476 behenyl) methacrylate. The abbreviations EHA, HEA, MBA and AA are used for 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 3-methoxybutyl acrylate, and acrylic acid, respectively. The abbreviation AIBN is used for azo bis-isobu~yl~ niL,ile. The abbreviation IEMA is used for isocy~n~t~ ethylmethacrylate~
S
Shear and Tack Values are measurèd by Test Procedures PSTC-7 and PSTC-6, respectively, of the Pressure-Sensitive Tape Council. In the Shear Test, a sample of the PSA composite 0.5 inch (1.25 cm) square is pressed against a vertical steel plate, and after 5 ...i-~ s, a lO00 g weight is secured to the backing; the shearvalue is the time in seconds 0 before the backing falls off the plate. In the Tack Test7 a ball bearing 7/16 inch (1.1 cm) in m~tt~r is allowed to roll down a standard incline onto the PSA surface of the composite;
the tack value is the distance in cms that the ball runs over the PSA.

Peel Strengths for PSA composites applied to human skin are measured as follows.ls After removing the release sheet (if any), two irlent~ samples are placed on the underside of the ro,~ of an adult, with the length of the strips parallel to the atm bone. Light hand plt;s~,ule is applied to the entire surface of the strips. After about 0.5 hour, 1 hour, 24 hours, or 48 hours, one end of one strip is detached from the skin and attached to a clip which is attached by a wire to the load cell of an Instron M~t~qri~lc Testing Instrument (IMTI) or an equivalent insL~.~ment. The sample is then removed by peeling it off at a rate of 10 inch (25.4 cm) per minute, the sample being bent back over itself at an angle of about 180. The other strip is removed in the same way, except that a hair dryer is used to warm the entire strip to a temperature of about 40C before it is peeled off. The average peel strength for each strip is recorded at room temperature (LT) and at the higher lem~ ture (~).
Moisture Vapor Tr~ncmicsion Rates (MVTR) are measured by ASTM E96-60, using the ~ cicc~nt method, at 37C and a hllmitlity ~lirrer~,lce of about 70%, and are ~y~issed in glmillm2/24 hr.

SCC Blocks The earlier International Application PCT/US9V08508 (Publication No. 93/07194) contains a full disclosure of SCC blocks which may be present as hard blocks in the TPE's of that application. That disclosure is generally applicable to the SCC blocks which may be used as hard or soft blocks in the various aspects of this invention, subject of course to the l~uirGIllent that an SCC block which is a soft block must have a mPlting point less than the Tg or Tm of the hard block. The following description can therefore be supplemPnt~l by l~ire~Gnce to the disclosure in that earlier application. When the SCC block melts, the difference between the onset of melting (To) and the peak (Tq or TmS) on a DSC curve is s preferably less than 10C, more preferably less than 8C, particularly less than 6C, especially less than 4C. The melting point of the SCC block on its own, Tm, is closely related to Tq (in a hard block) or TmS (in a soft block). Tq or TmS will generally be between (Tm - 10)C and (Tm + 5)C, usually between (Tm - 5)C and Tm. Tq and/or TmS aregenerally 0 to 200C, preferably less than 150C, particularly less than 85C. In the SCC
blocks, preferably 50 to 100%, particularly 70 to 100%, especially 90 to 100%, of the repeating units contain crystallizable side chains. The ~F of the SCC block on its own is generally at least 5 or at least 10, preferably at least 20, particularly at least 40, for example 60 to 120, Joules/g.

The SCC blocks can be broadly defined as polymer blocks which comprise y repeating units of the general formula I where Y is an organic radical forming part of the Cy polymer backbone and Cy comprises a cryst~lli7~ble moiety. The radical Cy may bealiphatic or aromatic, for example alkyl of at least 10 carbons, fluoralkyl of at least 6 carbons or p-alkyl styrene wherein the alkyl contains 6 to 24 carbons. P~erGlled SCC
20 blocks comprise side chains cont~ining in total at least 5 times as many carbon atoms as the backbone of the block, particularly side chains comprising linear polymethylene moieties containing 12 to 50, especially 14 to 22, carbon atoms, or linear perfluorin~ted or subst~nti~lly perrluorinated polymethylene moieties containing 6 to 50 carbon atoms. The blocks can optionally also contain units derived from one or more other comonomers 25 generally in total amount less than 50%, particularly less than 35%, especially less than 25%, e.g. 0 to 15%.

Other precursors of SCC blocks, and SCC blocks which can be formed by a living polymerization on another plGr~,l,lled block, include atactic and isotactic polymers of n-30 alkyl (x-olefins, n-alkylglycidyl ethers, n-alkyl vinyl ethers, n-alkyl-oc-epoxides, n-alkyl oxycalbonylamido-ethylmethacrylates, n-fluoro alkyl acrylates, n-alkyloxazolines, and polymers obtained by reacting an hydroxyalkyl acrylate or methacrylate with an alkyl WO 94/24219 215 9 ~7 ~ ; 12 PCT/US94/04138 ~

isocyanate, or by reacting a difunctional isocyanate, a hydroxyalkyl acrylate orm~th~rrylate, and a primary fatty alcohol.

~,rc;lled SCC blocks comprise 60 to 100% of units derived from at least one 5 monomer select~d from the group consisting~Qf alkyl acrylates, alkyl m.oth~c rylates, N-alkyl acryl~mides, N-alkyl methacryl~mides,~ky~ oxazolines, alkyl vinyl ethers, aLkyl vinyl esters, a-olefins, alkyl 1,2-epoxides and alkyl glycidyl ethers in which the alkyl groups are n-alkyl groups containing 14 to 50 carbon atoms, and the co .,i,~onding fluoroalkyl monomers in which the alkyl groups are n-alkyl groups containing 6 to 50 carbon atoms; 0 0 to 20% of units derived from at least one monomer selecte~l from the group conci~ting of alkyl acrylates, alkyl methacrylates, N-alkyl acryl~mi-les, alkyl vinyl ethers, and alkyl vinyl esters in which the alkyl groups are n-alkyl groups containing 4 to 12 carbon atoms; and 0 to 15% of units derived from at least one polar monomer selected from the group consisting of acrylic acid, meth~rylic acid, itaconic acid, acrylamide, methacrylamide, acrylonitrile, 15 ethacrylonitrile, vinyl acetate and N vinyl pyrrolidone. Such SCC block polymers may also contain units derived from other lllollomGl~ to change compatibility with other blocks, or to raise the mo~lulll~ of the TPE; such monomers include styrene, vinyl acetate, monoacrylic functional polystyrene and the like.

The number average molecular weight of the SCC block is preferably less than 200,000, more preferably less than 100,000, particularly less than 50,000, more particularly 2,000 to 20,000, especially 3,000 to 20,000.

When a TPE used in this invention includes hard SCC blocks, preferably all the hard blocks in the TPE are SCC blocks. The hard SCC blocks are preferably all of the same type, with each block being derived from the same monomer or mixture of monomers. When two different SCC hard blocks are present, the TPE may have two or more distinct Tq~s~ corresponding to the different SCC blocks. When conventional hard blocks are also present, they preferably do not amount to more than 10%, particularly not more than 5%, of the TPE. Such other hard blocks, if present, can be of any kind, including those disclosed in the documents incorporated by reference herein.

When the TPE's include non-SCC soft (B) blocks, the soft blocks can be of any kind, including those disclosed in the documents incorporated by reference herein. The -~ WO 94/24219 13 21 S 9 ~ 7 6 PCT/US94/04138 TPE can contain one or more different types of non-SCC B blocks. The glass transition point (Tgs) or melting point (TmS) of the B blocks should be below (Tq - 10)C, preferably less than (Tq - 20)C, particularly less than (Tq - 40)C. Tgs or TmS should also be below the temperature at which the TPE should exhibit elastomeric properties in use, for example s less than 20C, preferably less than 0C, particularly less than -20C, e.g. less than -40C.

When the TPE cont~in~ more than one non-SCC B block, the B blocks will usually be the same; however, the TPE can contain two or more different B blocks. A B block can contain a single repeating unit (which may be derived from a single monomer or a pair of lo monomers) or two or more dirrGlt"~ repeating units. When there are two or more different repeating units in a B block, they can be distributed randomly or in blocks.

Examples of suitable amorphous B blocks are polyethers, polyacrylates, polyesters, polyamides, polyurethanes, and polysiloxanes.
The linkages between repeating units in a B block can be the same as, or dirrelGIll from, the linkages be~weGIl lGpea~ g units in the SCC A blocks. The linkages ~weell the B block(s) and the A blocks can be the same as, or dirrel~ t from, the link~ges between repeating units in the B block(s). They can for example be the residue of a linking compound which contains at least two reactive groups which will react with groups on the A and B blocks, for example a diisocyanate such as methylene diphenylene diisocyanate, tolylene diisocyanate, or hexamethylene diisocyanate.
The number average molecular weight of the B blocks is generally more than 5,000and less than 900,000, preferably less than 500,000, particularly less than 200,000, especially less than 100,000, e.g. 10,000 to 80,000.

When the TPE includes soft SCC blocks, preferably all the soft blocks in the TPEare SCC blocks. The soft SCC blocks are preferably all of the same type, with each block being derived from the same monomer or ",i~lu.~ of monomers. When t-wo different SCC
soft blocks are present, the TPE may have two or more distinct TmSls~ corresponding to the dirrel.,.~t SCC blocks. When conventional soft blocks are also present, they preferably do not amount to more than 10%, particularly not more than 5%, of the TPE. Such other soft blocks, if present, can be of any kind, including those disclosed in the do~ume incc.l~ulalt;d by reference herein.

WO 94/242192 1 5 9 4 ~ ~ PCT/US94/04138 As in~lic~ted above, TmS will be selected according to the int~-nded use of the TPE.
Thus TmS can be select~l so that the TPE changes, over a predetçrmin.-A and relatively narrow temperature range including TmS~ belweell a-~Qlatively hard and inflexible m~t~ri~l s and an el~tQmeri~ m~tçri~l For most uses, TmS is preferably less than 60C, particularly less than 45C, especially less than 30C. Tm~ jl~ also preferably more than 0C, particularly more than 5C. For example, l~ffiS may be 3 to 40C, preferably 5 to 20C. In one preferred embo~lim~nt, the B block is a polyacrylate, preferably a polyacrylate which contains 50 to 100%, preferably 80 to 100%, of units derived from at least one n-alkyl acrylate or methacrylate in which the alkyl group contains 4 to 16, particularly 12 to 14, carbon atoms or from an equivalent monomer, e.g. an acrylamide or m~th~rrylamide.
Such B blocks may for example include units derived from one or more other ethylenically unsaturated comonomers including AA, EHA, HEA, MBA and methacrylic acid.

When the TPE includes non-SCC hard (A) blocks, the det~ l description given above for non-SCC soft (B) blocks is generally applicable, subject only to the limit~tion that the melting point (Tmh) or glass transition point (Tgh) of the block must be higher, rather than lower, than the melting point of the SCC block (TmS). Thus TmS should be below (Tmh-10)C or (Tgh-10)C, preferably below (Tmh-20)C or (Tgh-20)C, particularly 20 below (Tmh-40)C or (Tgh-40)C.

When a TPE used in the invention contains SCC hard (A) blocks, each soft (B) block must be linked to at least two SCC A blocks having a Tq higher than the Tgs or TmS
of the B block. The A blocks are insoluble in the B block(s) when the TPE is solid, and 25 therefore anchor the B block(s) at le~ dtures below Tq, thus providing elastomeric properties below Tq and above Tgs or TmS. However the cryst~lli7~ble side chains in the novel A blocks apparently plasticize the TPE at ~ pGldtures above Tq and thus assist in the very rapid reduction in viscosity at le---~tldtures just above Tq. The greater the compatibility of the A and B blocks above Tq, the larger the reduction in viscosity. The 30 complex viscosity of the TPE preferably decreases from a first value Ql dynes/cm2 to a second value Q2 dynes/cm2, where Q2 is less than Ql x 10-3, preferably less than Ql x 10-5, as the temperature increases from Tl to T2, where Tl is less than Tq, e.g. (Tq - 3)C, (Tq - 5)C or (Tq - 10)C and T2 is at most (Tq + 10)C, e.g. (Tq + 7)C or (Tq + 4)C. The TPE eYhibit~ a co.,e~.l,ollding decrease in complex modlllus over the same temperature range.
~ .
When the soft block is cryst~lline, preferably Tq is 40 to 125C and TmS is 3 to40C. In one p,efcl,~d TPE, the B block comprises 50 to 100%, preferably 75 to 100%, by weight of units derivable from at least one n-alkyl acrylate or meth~rylate in which the n-alkyl group contains 4 to 16 carbon atoms, preferably C12A or C14A or both, and the A
block comprises 50 to 100%, preferably 75 to 100%, by weight of units derivable from at least one n-alkyl acrylate or m~th~r~rylate in which the n-alkyl group contains at least 18 lo carbon atoms, preferably 18-30 carbon atoms, particularly from C22A.

The TPE's generally have an ABA (triblock), (AB)n, or AnB structure where n is at least 2, though ll~ ;s of such structures can be used. The AnB structure includes the various different types of graft copolymer which can be prepared. The TPE's willgenerally contain 2 to 90% of the SCC blocks. TPE's to be used in PSA's preferably contain 2 to 15%, particularly 3 to 10%, of the SCC hard blocks. TPE's for other uses can contain for example 10 to 90%, preferably 10 to 70%, particularly 25 to 60%, of the SCC
hard blocks. The cryst~ hle moieties in the SCC hard blocks may provide less than 65%, particularly less than 60%, of the TPE.
The TPE's used in this invention generally exhibit elongations of 5 to 500%, e.g.
50 to 500%. Their modulus is generally 10 to lO0,000 psi (0.7 to 7,000 kg/cm2), e.g.10 to 50,000 psi (0.7 to 3500 kg/cm2). The higher the proportion of hard blocks, the higher the modulus. The TPE's generally contain less than 90%, preferably less than 70%, and more than 2% of the hard blocks.

The number average molecular weight (Mn) of the TPE's used in this invention is generally 5,000 to 800,000, preferably 10,000 to 800,000, for example 5,000 to 400,000, particularly 10,000 to 200,000. The ratio MW/Mn is generally from 1 to 15, e.g.2 to 4.
The TPE's used in this invention can be prepared by the methods which are described in detail in the earlier International Application No. PCT/US92/08508,Publication No. WO 93/07194 (Docket No.9213.1 PCT), to which reference should bemade for details of this aspect of the invention.

Wo 94/24219 21~ 9 4 7 6 PCT/US94/04138 Co,l,yo~ilions. Sha~ed Articles and Assemblies In the colllpo~iLions, shaped articles, and a~ssemblies of the invention, a TPE
s cont~ining SCC hard blocks and crystalline soft b~?cks is associated with a second component which contacts the TPE. The~e~ampositions, shaped articles and assemblies (including their preparation, their use, an~ their advantages) can be subst~nti~lly the same as the corresponding compositions, shaped arfticles and assemblies which contain SCC
hard blocks and amorphous soft blocks, and which are described in detail in the earlier 0 International Application No. PCT/US9V08508, Publication No. WO93/07194 (Docket No. 9213.1 PCT), to which reference should be made for details of this aspect of the invention.
The invention is illustrated in the following Examples.
F.XAMPLES
In Examples 1 to 14, the first step was to make a hard block SCC acrylate and/ormethacrylate polymer, using the ingredients and amounts thereof (in grams) shown in Table 1 to make one of the SCC polymers Hl to H4 having the pl~,lies shown in Table 1. The SCC
polymer was then filnction~li7~i by reaction with isocyanatoethylmeth~rrylate (IEMA).
Preparation of Hard Block SCC Polvmers Hl to H4 SCC polymer Hl was prepared by adding the C16A (400 g), C18A (100 g~, mercaptoethanol (5.2 g) as capping agent, and AIBN (1 g) as initi~tl~r, to toluene (1000 mL), and heating the reaction mixture with reflux and stirring under nitrogen first at 60C for 16 hours and then at 80C for 6 hours. The SCC polymer was then functionalized by heating with EMA (10 g) and dibutyl tin dilaurate (7 drops) at 60C for 16 hours. SCC polymers H2 to H4 were made simil~rly Pre~aration of the TPE's In Examples 1-8, the Hl functionalized SCC polymer, EHA and HEA, in the amounts shown in Table 4, were added to a reaction vessel, together with ethyl acetate (100 g), heptane (100 g) and AIBN (0.15 g), and heated at 60C for 16 hours under nitrogen. The reaction ; was cooled and poured into ethanol to recover the TPE as a l~r~i~ilate, and the WO 94/24219 17 21 S 9g 7 6 PCT/US94/04138 prer~ipit~te was dried at elevated le,l,~cl~ture under reduced pressure. In Examples 9-14, the TPE was made similarly, using the ingredients and amounts thereof shown in Table 4. In FY~mrle 11, the TPE, which contained 20% of H2, had a crystalline soft block with a TmS of about 6C (and onset of melting at 2C) resulting from the C12A and C14A units and a 5 crystalline hard block with a Tq of about 61C (and onset of melting at about 54C) reslllting from the H2 (C22A) macromer.
Prep~ration of Copolymers C1-C13 0 Copolymers C1-C13 are random high molecular weight acrylate polymers. Typically they were prepared by adding the monomers and amounts thereof in Table 3 to a reaction vessel, together with ethyl acetate (100 g), heptane (100 g) and AIBN (0.15 g) and heating the reaction mixture at 60C for 16 hours under nitrogen. The copolymer was recovered by pouring the cooled reaction mixture into ethanol and drying the precipitate at elevated temperature under reduced pressure.

Preparation of Copolvmers WOC1, WOC2 and WOC3 Copolymers WOC1, WOC2 and WOC are low moleclll~r weight random SCC
polymers which can be added to PSA's to reduce peel strength on warming. They were prepared in the same general way as C1-C13, using the monomers and amounts thereof shown in Table 4, but taking steps to control the molecular weight.

Preparation and Testin~ of PSA's A number of PSA composites were made and tested, as ~ ed in Table 5 below.
Table 5 shows the results for PSA composites in which the PSA comprises a TPE cont~ining SCC hard blocks. A number of the PSA's also contained one of the crystalline SCC additives ("cryst. SCC") WOC1, WOC2 or WOC3. Table 6, which is included for co-llpalison, shows results for comparable PSA's which do not include such SCC hard blocks. Table 7 shows the results of testing on human skin.

'' Except for PSA composite No. QA141, the PSA composites were made and tested as follows. The specified polymer(s) was dissolved in a suitable solvent, e.g. toluene or heptane, 3s to give a homogeneous, bubble-free composition with a solids content of about 45%. The composition was applied to a polyester TPE ("Hytrel 4056") ~llm 1.75 mil (0.0045 cm) thick, WO 94/2421g 21~ 9 ~ 7 6 18 PCT/US94/04138 ~

in the following way. The film was secured to a flat glass plate 18 x 12 inch (46 x 30.5 cm) and smoothed to remove air bubbles between the film and the plate. A wire-wound applicator rod (No. 70 Gardco Wet Film Applicator Rod) ~was then used to apply a coating of the composition to the film. The coating was dri~ed~in an oven at 90C for 30 Il~inul~S or more.
s The dried coating thickness was about 1.6;~D~.8 mil (0.0040 to 0.0046 cm). The coating was r covered with a siliconized polyethylene-~npregnated paper. The resl-lting l~min~te was removed from the glass plate and samples about 4.0 x 0.5 inch (10 x 1.25 cm) were cut from the l~min~te 0 PSA composite QA141 was made by coating PSA QAl 12 by the method described above to give a coating 1 rnil thick. This coating was then covered by a coating about 3 microns thick of PSA QAl 11, by transfer coating from a siliconized Mylar film.
The PSA composites were tested as previously described.
Preparation and Heat Sealin~ of Films of TPE's The TPE of Example 11 was formed into a film as follows. The polymer (10 g) was dissolved in a Illi~CI.ulG of toluene (12.5 mL) and heptane (12.5 mL), coated onto a siliconized polyester b~ing and dried at 90C. The dried film was transferred to a mich,~~ s support (Cellgard K878). The random copolymer C13 was formed into a film in the same way. The Example 11 film could readily be heat-sealed to a co~ rl .;ially available film of a blend of polyethylene (PE~ and ethylene/vinyl acetate copolymer (EVA). The copolymer C13 film gave a markedly inferior heat seal. The oxygen perm~bilities of the Example 11 film and the 2s PE/EVA film were measured and are shown below (in cc-ml/lOOin2-atm-24 hrs).

at 45F at 72F
Example 11 1800 5150 Wo 94/24219 ~ 21 5 9 4 7 G PCT/US94/04138 HARD BLOCK TYPE
Hl H2 ¦ H3 ¦ H4 HL~RD BLOCK D~GREDr~rrS

TI~RD BLCPCK PRO~K lW
Mw 13,100 6700 11,700 9000 MW~ln 1.661.2 1.561.27 DSC onset C 35 DSC peak C (Tm) 38 63 Hard Block Soft Block Mw Mw Viscosity Ex ~o. Type ATrt EHA A~ HEA
~ ~4 - 488k ~.6 231 - ~ ~3 - 700k l .r 587 ~ - 5 557 c - 3 ~ 5 - 11 ~ . 1313 9r~ . l 2600 6 ~ 5 1 - .2S c 6 7 ~ 5 7 - ~54c 19.~ -8 H 5 7 - >1000c 14.: 25.~- k 9 5 ~ + > ~ k n -- 5 ~' - + 72.c 9.4 5~ 0 ~) ++ - - 2r- c ~ - , - 8 9 c 2.85 1960 _ ' _=~'- J 7 - 8 4 H~ 6 08 6 -272k 3.8 + In Examples 9 and 10, the soft block monomers also included 5 g MPEG
(Example 9) or 25 g MBA (Example 10) ++ In Example 11, the soft block was formed from C12A, C14A and AA
(50/47/3) WO 94/24219 215 9 ~ ~ 6 20 PCT/US94/04138 TABT F. 3 Copolymer Ingredient~ Mw Mw/Mn EHA EE~A ~18A AA f Cl 92 8 - - 1200k 2.38 C2 96 4 - - 318k 7.7 C3 92 8 - - 401k 3.2 C4 95 - - 5 1002k 1.76 C5 92 8 - - 504k 4.3 C6 92 8 - - 1750k 1.7 C7 92 8 - - >lOOOk C8 92 8 - - 882k 4.9 C9 87 5 8(C18A) - 984k 5.9 C10 90 - 5(C18A) 5 Cll 47 - 47(C4A) 6 >lOOOk C12 97 - - 3 629k 6.21 C13 47 3(C14A) -C9 had a viscosity of 3000cps. C10 had a viscosity of 400 cps.
s Copolyrner Ingredier ts Mw Mw/Mn WOCl 54.140.9 5.0 2.5k 1.48 WOC2 54.140.9 5.0 3.7k 1.5 WOC3 95 - 5 2k 1.57 9 ~ 7 6 TART .F.5 PSA~ . POLY~IERS PROPERTIES
No. BaseRe--in Cryst. SCC Shear Tack Type Amt Type Amt Al. Base Resin is EHA/AA/H I 6,(95-x)/5/x x= 1 QAllEx 1 100 - - 180 16 x = 2 QA12Ex 2 100 - - 916 14 x = 3 QA13Ex 4 100 - - 1637 11 x = s QA14Ex 5 100 - - >lOk >30 A2. Base Resin is EHA/AA/E 16, 94/5/1 QA21 Ex 1 100 - - 180 16 QA22 Ex 1 90WOCl 10 329 QA23 Ex 1 80WOCl 20 694 QA24 Ex 1 70WOCl 30 611 A3. Base Resin is EHA/AA/~ 16, 93/5/2 QA31Ex 2 100 - O 916 14 QA32Ex 2 90 WOCl 10 2060 QA33Ex 2 80 WOCl 20 2719 QA34Ex2 70 WOCl 30 2774 A4. Base Resin is EHA/HEA/H16,92/5/3 QA41 Ex 3100 - O 470 12 QA42Ex 3 90 WOCl 10 1143 QA43Ex 3 80 WOCl 20 1575 QA44Ex 3 70 WOCl 30 2770 AS. Base Resin is EHA/AA/~ 16, 90/5/5 QA51 _x 5 100 - O >lOk >30 QA52 x 5 90WOCl O 20,000 QA53 _x 5 80WOCl 'O
QA54 Ex 5 70WOCl :,0 27,000 2~S9~6 22 TAB~ F.5. con1in~

PSA POLY~IERS PROPE~TIES
No. BaseRe in Cryst. SCC Shear Tack Type Amt Type Amt t A6. Base Resin is EHA/HEA/H16, 87/8/5 QA61 Ex 7 100 - O 595 1.6 QA~2 Ex 7 90 WOC (~ 7.~7 QAfi3 Ex 7 0 WOC ' 1 ~ 7 QAl~4 Fx~ 7 O WOC ~ 2 QA~5 ~x 100 WOC . ' 0~
QAn6 Ex 75 WOC '5 >8 ~c QArl7 kx 75 WOC _5 13S c A7. Basc Resin is EHA/HEA/H16,MPEG, 82/5/-/5 QA71 Ex 9 100 - - 1900 9.76 QA72 Ex9 75 WOC2 25 2820 A8. Base Resin is EHAIHEA/H16, 3MBA, 62/8/5/25 QA81 Ex 10 100 - - 5055 16.3 QA82 Ex 10 75 WOC2 25 >86k A9. Base Resin is EH/VHEA/Hl9, 87/8/5 QA9 Ex ~ ~0 - - 1722 3.4 QA~ Ex ~ WOC2 25 >86k QA~ Ex ~ .,5 C6 12.5 C7 12.5 C8 12.5WOC2 25 717 A10. Base Resin is EHA/AAIH19,90/5/5 QA101 Ex 14 100 - - 1655 10 QA102 Ex 14 80 WOCl 20 3844 wO 94/24219 21 5 9 4 7 6 PCT/US94/04L38 TAB~ F.6 PSAPOLY~IERS PROPERTIES
No. BaseResinCryst. SCC Shear Tack Type Amt Type Amt B l; Base Resin is EHA/HEAQB 11 C2 100 -B2; Base Resin is EHA/HEAQB21 C3 100 - ~ 1.9 B3; Base Resin is EHA/HEAQB31 C4 100 - O 701 2.8 QB32 C480 WOCl 20 524 QB33 C470 WOCl 30 495 QB34 C460 WOCl 40 399 B4. Base Resin is EHA/HEAQB41 C5 100 - O O
QB42 C590 WOCl 10 0 QB43 C580 WOCl 20 0 QB44 C570 WOCl 30 0 BS. BaseResin is QB51 C9100 - 12.6 1.1 EHA/HEA/C18A, 87/8/5 B6.BaseResinis QB61 C10 100 - O 148 14.1 B7; Base Resin is EHA/HEA,QB71 Cl 75 WOC3 25 17 B8. Base Resin is EHA/AA,QB81 C4 63 B9; Base Resin is EHA/HEA, QBgl C6 25 2159~7~ 24 TAP~T -F 6 (eo~ ued) PSA POLY~ERS PROPE~TIES
No. Base ~esin T 'E Shear Tack Type Amt Type Amt B10. BaseResinisEHA/H '~QB101 C2 99WOC2 1 4.5 QB102 C2 97 WOC2 3 6.0 QB 103 C2 95 WOC2 5 11 .0 QB104 C2 90 WOC2 10 25.3 QB 105 C2 75 WOC2 25 >30 B 11. Bæe Resin is EHA/HE 4~B 111 C3 99 WOC2 1 2.8 QB 112 C3 97 WOC2 3 12.9 QB113 C3 95 WOC2 5 18.7 QB114 C3 90 WOC2 10 20.4 QB115 C3 75 WOC2 25 30.0 EHA/C4A/AA, 47/47/6 QB121 Cl l 100 ~ ~ 600 10 WO 94/24219 25 9 ~ 7 6 PCT/US94/04138 TABT .F.7 Peel Strengths of PSA's on Human Skin PSA Adhesive QA67 Qs7l Qs8l QA92 QA93 QBgl QA101 Qsl2l QAl41 After 0.5 hr, at LT - 60 at HT - 6 - - - - - - -% reduction - 90% - - - - - - -After 1 hr, at LT 29 - 23.8 14 40 55 43 44 26 at HT 3 - 3.4 2 5.5 2.5 - - 2.1 % reduction 89% - 86% 85% 26% 95% - - 92%
After 24 hr, at LT 80 211 89 - 95 - 79.5 78 at HT 9.5 21 29 - 9 % reduction 88% 90% 67% - 91%
After 48 hr, at LT 90 - 89 at HT 12 - 38 % reduction 87% - 57 Sheer Strength 139k 17 312 >86k 717 77 1655 600 1906 s

Claims (10)

1. A pressure-sensitive adhesive (PSA) composite which comprises (i) a flexible backing, (ii) a solvent-free layer of a pressure-sensitive adhesive (PSA) which is secured to the backing, and which comprises a thermoplastic elastomer (TPE) or is at least partially covered by a layer comprising a TPE, said TPE comprising A blocks, or B blocks, or both A blocks and B blocks, which are crystalline and in which at least part of the crystallinity results from crystallizable sidechains.
2. A PSA composite according to claim 1 wherein the PSA is a composition which comprises, intimately mixed with the TPE, a crystalline polymeric additive which(a) has a first order transition point Ta in the composition of 23° to 120°C, and (b) has a heat of fusion of at least 5 Joules/g.
3 . A PSA composite according to claim 2 wherein the composition has a shear value which is at least 1.3 times the shear value of a composition which is identical except that it does not contain the crystalline additive.
4. A PSA composite according to claim 2 wherein each of the A blocks is a polyacrylate or polymethacrylate, the B block is a polyacrylate or polymethacrylate, and the crystalline additive is a polyacrylate or polymethacrylate.
5. A PSA composite according to claim 2, 3 or 4 wherein each of the A blocks contains 50 to 100% of units containing linear unsubstituted alkyl groups containing 12 to 50 carbon atoms or linear substituted alkyl groups containing 6 to 50 carbon atoms, and the crystalline additive comprises repeating units of the general formula where Y is an organic radical forming part of the polymer backbone and Cy comprises a crystallizable moiety containing 12 to 20 carbon atoms.
6. A thermoplastic elastomer (TPE) comprising polymeric molecules which comprise (i) polymeric A blocks which (a) are crystalline and have a melting point Tq, and (b) wherein at least one of the A blocks comprises a side chain comprising crystallizable moieties which render the block crystalline;
and (ii) at least one polymeric B block which is linked to at least two A blocks andwhich is crystalline and has a melting point Tms which is less than (Tq-10)°C.
7. A TPE according to claim 6 wherein Tq is 40 to 125°C and Tms is less than (Tq-20)°C, preferably less than (Tq-40)°C, preferably 3 to 40°C.
8. A TPE according to claim 6 wherein the B block comprises 50 to 100% by weight of units derivable from at least one n-alkyl acrylate or methacrylate in which the n-alkyl group contains 4 to 16 carbon atoms, and the A block comprises 50 to 100% by weight of units derivable from at least one n-alkyl acrylate or methacrylate in which the n-alkyl group contains at least 16 carbon atoms.
9. A composition, shaped article or assembly which comprises (1) a TPE as defined in claim 6, 7 or 8, and (2) a second component which is (i) mixed with the TPE, or (ii) is surrounded by the TPE or (iii) supports the TPE
10. A process for releasing a second component from a composition, shaped article or assembly as defined in claim 9, which process comprises heating the composition, article or assembly to a temperature at least equal to Tq by means of heat which (i) is generated artificially or (ii) is generated by a mammalian body and/or (iii) is conveyed artificially to the composition, article or assembly.
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