US20080027199A1 - Shape memory polymer articles with a microstructured surface - Google Patents

Shape memory polymer articles with a microstructured surface Download PDF

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US20080027199A1
US20080027199A1 US11/460,685 US46068506A US2008027199A1 US 20080027199 A1 US20080027199 A1 US 20080027199A1 US 46068506 A US46068506 A US 46068506A US 2008027199 A1 US2008027199 A1 US 2008027199A1
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Prior art keywords
article
siloxane
radically polymerizable
shape memory
meth
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US11/460,685
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Inventor
Mieczyslaw H. Mazurek
Robert K. Galkiewicz
Audrey A. Sherman
James R. Starkey
Wendi J. Winkler
Haiyan Zhang
Jeffrey M. Olofson
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3M Innovative Properties Co
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3M Innovative Properties Co
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Priority to US11/460,685 priority Critical patent/US20080027199A1/en
Assigned to 3M INNOVATIVE PROPERTIES COMPANY reassignment 3M INNOVATIVE PROPERTIES COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAZUREK, MIECZYSLAW H., OLOFSON, JEFFREY, SHERMAN, AUDREY A., STARKEY, JAMES R., WINKLER, WENDI J., ZHANG, HAIYAN, GALKIEWICZ, ROBERT K.
Priority to KR1020097001561A priority patent/KR20090036117A/ko
Priority to EP07799431A priority patent/EP2046408A4/en
Priority to PCT/US2007/073097 priority patent/WO2008014109A1/en
Publication of US20080027199A1 publication Critical patent/US20080027199A1/en
Priority to US13/296,362 priority patent/US10279069B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/046—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/068—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/148—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/16—Materials with shape-memory or superelastic properties
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

Definitions

  • the invention relates to shape memory polymers, and particularly, to shape memory polymers having microstructured surfaces.
  • Shape memory materials have the unique ability to “remember” a pre-set shape and, upon exposure to the appropriate stimuli, shift from a deformed or altered shape back to the pre-set shape.
  • shape memory materials For example, shape memory metal alloys are commonly used in various medical, dental, mechanical, and other technology areas for a wide variety of products.
  • Shape memory polymers and the uses of these materials have emerged more recently. However, the basic premise behind these materials is the same—that the material can be pre-set in a particular shape, deformed, and then revert back to the pre-set shape when exposed to the appropriate stimuli.
  • the present disclosure relates generally to shape memory polymer articles.
  • the shape memory polymer articles may include a microstructured surface.
  • an illustrative article that includes a polymeric member.
  • the polymeric member may include a surface having a microstructure and it may include a shape memory polymer.
  • the shape memory polymer may include a copolymer network.
  • the copolymer network may include the reaction product of a free radically polymerizable siloxane having greater than one functional free radically polymerizable group and at least one (meth)acrylate monomer.
  • the at least one (meth)acrylate monomer when homopolymerized, may form a homopolymer that has a glass transition temperature, a melting temperature, or both greater than about 40° C.
  • an illustrative article in another embodiment, includes a polymeric member having a microstructured surface.
  • the microstructured surface may include a surface feature that is not visible to an unaided eye.
  • the polymeric member may include a shape memory polymer.
  • an illustrative article in yet another embodiment, includes a polymeric member having a microstructured surface.
  • the microstructured surface may include a surface feature that is not visible to an unaided eye.
  • the polymeric member may include a shape memory polymer.
  • the shape memory polymer may include a copolymer network.
  • the copolymer network may include the reaction product of (meth)acryloxyurea siloxane and isobornyl acrylate.
  • FIG. 1 is a side view of an illustrative article having a surface with a microstructure
  • FIG. 2 is a side view of another illustrative article having a surface with a microstructure
  • FIG. 3 is an alternative side view of the illustrative article shown in FIG. 2 .
  • this disclosure is directed to shape memory polymer articles that have a microstructured surface. While the present invention is not so limited, an appreciation of various aspects of the invention will be gained through discussion of the various features and components provided below.
  • Weight percent, percent by weight, wt %, wt-%, % by weight, and the like are synonyms that refer to the concentration of a substance as the weight of that substance divided by the weight of the composition and multiplied by 100.
  • alkyl refers to a straight or branched chain monovalent hydrocarbon radical optionally containing one or more heteroatomic substitutions independently selected from S, O, Si, or N.
  • Alkyl groups generally include those with one to twenty atoms. Alkyl groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example.
  • alkyl as used herein include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isobutyl, and isopropyl, and the like.
  • aryl refers to monovalent unsaturated aromatic carbocyclic radicals having a single ring, such as phenyl, or multiple condensed rings, such as naphthyl or anthryl.
  • Aryl groups may be unsubstituted or substituted with those substituents that do not interfere with the specified function of the composition. Substituents include alkoxy, hydroxy, mercapto, amino, alkyl substituted amino, or halo, for example.
  • Such an aryl ring may be optionally fused to one or more of another heterocyclic ring(s), heteroaryl ring(s), aryl ring(s), cycloalkenyl ring(s), or cycloalkyl rings.
  • aryl as used herein include, but are not limited to, phenyl, 2-naphthyl, 1-naphthyl, biphenyl, 2-hydroxyphenyl, 2-aminophenyl, 2-methoxyphenyl and the like.
  • (meth)acrylate is used to define both acrylates and methacrylates.
  • telechelic siloxane refers to siloxanes with 2 reactive groups, one at either end of the siloxane chain.
  • shape memory polymer refers to polymeric materials that are stimuli-responsive. Upon application of an external stimuli they have the ability to change their shape. A change in shape initiated by a change in temperature can be referred to as a thermally induced shape memory effect. While not being bound by theory, the shape memory effect may result from the polymer's structure, that is, its morphology in combination with a certain processing and programming technology. Therefore, the shape-memory behavior can be observed for several polymers that may differ significantly in their chemical composition.
  • the present disclosure is directed to articles.
  • the articles may include a polymeric member that has a surface with a microstructure and that includes a shape memory polymer.
  • the articles contemplated span a vast array of technical fields and include essentially any structure that may find utility or otherwise benefit from having a shape memory polymer incorporated into their construction. This may include a variety of different devices, apparatuses, components or portions of devices, layers or surfaces on devices, and the like, or any other suitable structure.
  • the articles of this disclosure may include an adhesive, a tape or substrate including an adhesive, a heat-activated tape, a microstructured tape, a backing member, a foam tape, a device having a fluid disposed or encapsulated therein, a microfluidic device, a circuit or circuit board, a printed circuit, a film (including multilayer optical films), a micromachined article, an embossed article, a printing plate or film used to create 3 D prints, a substrate for pattern coating and/or pattern printing, an electrode, a device having cube corners with retroreflective characteristics, a secure identification article, a secure license or license plate, a directional organic light emitting diode, a sensor, an indicator, a switch, and the like, or any other suitable device.
  • this list of articles is not intended to be limiting as the articles contemplated can take the form of any suitable structure, apparatus, or device.
  • an exemplary article may include a shape memory polymer.
  • shape memory polymers suitable for the articles are described in more detail below.
  • the entire article is made from the shape memory polymer.
  • only a portion of the article is made from a shape memory polymer. This may include a shape memory polymer layer, a shape memory polymer surface, a shape memory polymer portion, or any other suitable configuration.
  • the remaining materials making up the article may include metals, metal alloys, polymers, ceramics, and the like, or any other suitable material. Regardless of whether the article is completely or partially made from a shape memory polymer, the articles described herein can be described as “shape memory polymer articles”.
  • Shape memory polymers are known to have the unique ability to be set in a pre-set shape, deformed to an altered shape, and then revert back to the pre-set shape when exposed to the appropriate stimuli (e.g., changes in temperature, application of solvent, etc.). Because the articles disclosed herein include a shape memory polymer, the portion of the article (or all of the article if made completely from a shape memory polymer) having the shape memory polymer can be configured to utilize this property.
  • the article may include a shape memory polymer surface that has been cast or otherwise shaped to have a pre-set shape or configuration. This surface can be deformed to an altered or deformed shape and then be shifted back to the pre-set shape when appropriately cued. Triggering the shift from the deformed shape to the pre-set shape can vary depending on the particular polymer used or other parameters. However, at least some of the shape memory polymers disclosed herein can be shifted by exposure to elevated temperatures and/or to an appropriate solvent.
  • the articles include a surface having a microstructure.
  • a surface with a microstructure is different than a “flat” or unstructured surface.
  • the term “microstructure” means the configuration of features wherein at least 2 dimensions of the features are microscopic. The topical and/or cross-sectional view of the features, therefore, are microscopic.
  • the term “microscopic” refers to features of small enough dimension so as to require an optic aid to the naked eye when viewed from any plane of view to determine its shape.
  • One criterion is found in Modern Optic Engineering by W. J. Smith, McGraw-Hill, 1966, pages 104-105 whereby visual acuity,“ . . .
  • microstructures may be formed along portions or all of any number of surfaces of the article.
  • some surfaces of the articles may include sections that have microstructures and sections that are free from microstructures.
  • substantially all of one or more surfaces of the articles may include microstructures.
  • shape and/or configuration of the microstructures can also vary.
  • microstructures can include one or more projections, one or more depressions, a combination of projections and depressions, ridges, posts, pyramids, hemispheres, cones, protrusion, or any other suitable feature.
  • the shapes of the various projections and/or depressions can also vary.
  • some embodiments of projections and/or depressions can be rounded in shape (e.g., circular, semicircular, spherical, hemispherical, oval, pill-shaped, partially pill-shaped, etc.) or include a rounded portion, polygonal in shape or include a polygonal portion (e.g., triangular, squared, cubed including cube corners, tetrahedrical, rectangular, paralleopiped, pentagonal, hexagonal, etc.), an irregular shape, a regular shape, a pointed shape, a truncated shape, combinations thereof, or any other suitable shape.
  • the projections and/or depressions may include or define one or more channels, valleys, wells, ridges, and the like, combinations thereof, or any other configuration.
  • Microstructures may be formed in a surface of an article through the use of a microstructured molding tool.
  • a microstructured molding tool is an implement for imparting a structure or finish to at least a portion of an article and that may be continuously reused in the process.
  • Microstructured molding tools can be in the form of a planar stamping press, a flexible or inflexible belt, a roller, or the like.
  • microstructured molding tools are generally considered to be tools from which the microstructured surface feature is generated by embossing, coating, casting, or platen pressing and do not become part of the finished microstructured article. Instead, a surface on the article corresponding to where the article came into contact with the microstructured surface of the molding tool defines the microstructure or microstructured surface feature of the article.
  • microstructured molding tools can also be prepared by replicating various microstructured surfaces, including irregular shapes and patterns, with a moldable material such as those selected from the group consisting of crosslinkable liquid silicone rubber, radiation curable urethanes, etc. or replicating various microstructures by electroforming to generate a negative or positive replica intermediate or final embossing tool mold.
  • microstructured molds having random and irregular shapes and patterns can be generated by chemical etching, sandblasting, shot peening or sinking discrete structured particles in a moldable material.
  • any of the microstructured molding tools can be altered or modified according to the procedure taught in U.S. Pat. No. 5,122,902, the entire disclosure of which is herein incorporated by reference.
  • FIG. 1 is provided to depict a portion of an example article 10 .
  • Article 10 includes a shape memory polymer such as, for example, any of the shape memory polymers described herein.
  • Article 10 may comprise a polymeric member that includes a surface 12 having a plurality of surface features or microstructures 14 formed therein.
  • microstructures 14 are depicted as projections extending outward from surface 12 .
  • this arrangement is not intended to be limiting as a wide variety of differing arrangements are contemplated including those described above.
  • article 10 may be in the “pre-set” shape or may be in the “deformed” shape. If article 10 , as shown in FIG. 1 , is in the pre-set shape, surface 12 can be deformed. This may be accomplished, for example, by changing the configuration of microstructures 14 . For example, microstructures 14 may be flattened. The deformed article 10 can be shifted back to the pre-set configuration (i.e., the configuration depicted in FIG. 1 for this example) upon exposure to, for example, increased temperature, solvent, or any other suitable stimuli. Alternatively, if article 10 is in the deformed shape or configuration when arranged as shown in FIG. 1 , exposure to the appropriate stimuli may shift article 10 back to the pre-set shape. In this later embodiment, the pre-set shape may include a generally flat or planar arrangement for surface 12 or any other suitable shape.
  • FIGS. 2-3 depict another example article 1010 .
  • Article 1010 may comprise, a sensor.
  • article 1010 may include a surface 1012 having a microstructure defined therein.
  • the microstructure may include, for example, a plurality of rows or wells 1014 .
  • This configuration may be the pre-set shape of surface 1012 .
  • Surface 1012 can be deformed into a deformed shape that is, for example, substantially flat.
  • a secondary surface 1012 ′ for example on the opposite side of article 1010 (which is indicated in FIG. 3 as article 1010 ′) may have a generally flat pre-set shape that can be deformed to have a microstructure that includes or defines a hexagonal pattern therein. Mobilizing may restore both surfaces 1012 / 1012 ′.
  • mobilizing may include the application of heat and/or the exposure to solvent or solvent vapors to one or both of surface 1012 and/or surface 1012 ′.
  • surfaces 1012 / 1012 ′ may be exposed to heat and restored.
  • surfaces 1012 / 1012 ′ may be exposed to solvent or solvent vapors.
  • This later embodiment may allow article 1010 to be used as a sensor that can “smell” a solvent. For example, a user may visually observe the changes in the shape of article 1010 (on one or both sides) in order to observe that the sensor has smelled a particular solvent.
  • FIGS. 2-3 in addition to illustrating that article 1010 can be used as a sensor, also indicate that a surface having a pre-set shape may be formed on multiple sides of an article.
  • FIGS. 2-3 illustrate article 1010 having surface 1012 with a pre-set shape that includes a microstructure whereas surface 1012 ′ has a pre-set shape that is generally planar.
  • one or both of the surfaces 1012 / 1012 ′ can be deformed.
  • surface 1012 can be flattened whereas surface 1012 ′ can be deformed to have a microstructure.
  • article 1010 can be seen as having a secondary surface 1012 ′ with a microstructure.
  • secondary surface 1012 ′ may, alternatively, have a pre-set shape that includes the microstructure shown in FIG. 3 and it can be deformed to have another shape.
  • the secondary surface 1012 ′ (or other surfaces having a pre-set shape) may be defined along any area of the article 1010 and need not be limited to just a surface that is opposite of surface 1012 . Regardless of the configuration of surfaces 1012 / 1012 ′, mobilization shifts surfaces 1012 / 1012 ′ back to their pre-set shape.
  • other articles are contemplated that have multiple surfaces with pre-set shapes including multiple planar surfaces and/or multiple surfaces with microstructures.
  • other embodiments are contemplated where one or more surfaces have a microstructure formed therein and one or more of these surfaces can be deformed to have a different microstructure.
  • Shape memory polymers can be classified as elastomers. On the molecular level they represent polymer networks that include segment chains that are connected by netpoints. The netpoints can be formed by entanglements of the polymer chains or intermolecular interaction of certain polymer blocks. These cross-links are called physical netpoints. Cross-links in the form of covalent bonds form chemical netpoints.
  • An elastomer exhibits a shape-memory functionality if the material can be stabilized in the deformed state in a temperature range that is relevant for the particular application. This can be achieved by using the network chains as a kind of molecular switch.
  • the copolymer network includes an elastomeric phase or component and a “glassy” or high glass transition temperature phase or component.
  • the glassy phase holds or constrains the elastomeric component so that the substrate can be deformed into and stays in the deformed shape. Shifting from a deformed shape to the pre-set shape generally includes mobilizing the glassy phase of the shape memory polymer in order to allow the elastomeric component to “spring back” or otherwise shift to the original pre-set shape.
  • mobilizing is understood to be the mobilization of the glassy phase through the application of the appropriate external stimuli.
  • the elastomeric phase comprises a free radically polymerizable siloxane having greater than one functional free radically polymerizable group.
  • the glassy phase may comprise at least one (meth)acrylate monomer that, when homopolymerized, forms a homopolymer having a glass transition temperature, a melting temperature, or both greater than about 40° C.
  • exposure of the shape memory polymer to temperatures greater than 40° C. can mobilize the glassy phase and cause the deformed surface of the substrate from the deformed shape to the pre-set shape.
  • a solvent such as alkyl alcohol, acetone, etc. can partially dissolve or plasticize the glassy phase and effectuate the same change.
  • the (meth)acrylate monomer may crystallize when reacted with the free radically polymerizable siloxane having greater than one functional free radically polymerizable group.
  • exposing the copolymer network to temperatures above the melting point of the (meth)acrylate monomer may mobilize the glassy phase.
  • the relative proportions of the various components of the copolymer network can vary.
  • the copolymer network may include about 10-70 weight-percent of the free radically polymerizable siloxane.
  • the copolymer network may include about 10-60 weight-percent of the free radically polymerizable siloxane.
  • the copolymer network may include about 20-60 weight-percent of the free radically polymerizable siloxane.
  • the free radically polymerizable siloxanes for use in the copolymer networks may be represented by the following formula:
  • X is a group having ethylenic unsaturation
  • Y is a divalent linking group
  • n is an integer of 0 to 1;
  • D is selected from the group consisting of hydrogen, an alkyl group of 1 to about 10 carbon atoms, aryl, and substituted aryl;
  • R is a divalent hydrocarbon group
  • R 1 are monovalent moieties which can be the same or different selected from the group consisting of alkyl, substituted alkyl, aryl, and substituted aryl;
  • R 2 are monovalent moieties which can be the same or different selected from the group consisting of alkyl, substituted alkyl, aryl, and substituted aryl;
  • R 3 are monovalent moieties which can be the same or different selected from the group consisting of alkyl, substituted alkyl, vinyl, aryl, and substituted aryl;
  • R 4 are monovalent moieties which can be the same or different selected from the group consisting of alkyl, substituted alkyl, vinyl, aryl, and substituted aryl;
  • n is an integer of about 10 to about 2000.
  • Suitable free radically polymerizable siloxanes for use in the articles described herein may include those described in U.S. Pat. No. 5,091,483, the entire disclosure of which is herein incorporated by reference.
  • the free radically polymerizable siloxanes comprise telechelic siloxanes.
  • the telechelic siloxanes may include, for example, (meth)acryloxyurea siloxane (MAUS), acrylamidoamido siloxane (ACMAS), methacrylamidoamido siloxane (MACMAS), and methylstyrylurea siloxane (MeStUS).
  • these telechelic siloxanes are formed by reacting silicone diamines with capping reagents such as isocyanatoethylmethacrylate (IEM), vinyldimethylazlactone (VDM), isopropenyl dimethyl azlactone (IDM), and m-isopropenyl alpha, alpha-dimethyl benzyl isocyanate (m-TMI), respectively.
  • IEM isocyanatoethylmethacrylate
  • VDM vinyldimethylazlactone
  • IDM isopropenyl dimethyl azlactone
  • m-TMI m-isopropenyl alpha, alpha-dimethyl benzyl isocyanate
  • telechelic siloxanes may have a number average molecular weights in the range of about 1,000 to 200,000.
  • the telechelic siloxanes have free radically polymerizable end groups. Due to the polar nature of the hydrogen bonding end groups and the nonpolar nature of the polydimethylsiloxane chain, a transient network is formed wherein the polar end groups tend to associate with each other. The relative strength of the end group association for the various telechelic siloxanes is reflected in their viscosities, with higher viscosities seen in the case of the more strongly associating end groups (e.g., ACMAS and MeStUS).
  • the telechelic siloxanes are obtained from amine-functional siloxane intermediates.
  • Suitable polydiorganosiloxane diamines and methods of making the polydiorganosiloxane diamines are described, for example, in U.S. Pat. No. 3,890,269 (Martin), U.S. Pat. No. 4,661,577 (Jo Lane et al.), U.S. Pat. No. 5,026,890 (Webb et al.), U.S. Pat. No. 5,276,122 (Aoki et al.), U.S. Pat. No. 5,214,119 (Leir et al.), U.S. Pat. No.
  • polydiorganosiloxane diamines are commercially available, for example, from Shin Etsu Silicones of America, Inc., Torrance, Calif. and from Gelest Inc., Morrisville, Pa. Particularly useful polydiorganosiloxane diamines include bis(3-aminopropyl)polydimethylsiloxanes.
  • Polydimethylsiloxanes having acrylamidoamido end groups can be prepared by the reaction of a polydimethylsiloxane diamine with 2 equivalents of vinyl dimethyl azlactone (VDM).
  • polydimethylsiloxanes having methacrylamidoamido end groups can be prepared in the same manner by the reaction of a polydimethylsiloxane diamine with 2 equivalents of isopropenyl dimethyl azlactone (IDM).
  • Polydimethylsiloxanes having methacryloxyurea end groups can be prepared using the same procedure, by the reaction of a polydimethylsiloxane with 2 equivalents of isocyanatoethyl methacrylate (IEM).
  • Polydimethylsiloxanes having alpha-methylstyrylurea end groups can be made by the reaction of a polydimethylsiloxane with 2 equivalents of m-isopropenyl-alpha,alpha-dimethyl benzyl isocyanate (m-TMI).
  • the free radically polymerizable siloxanes comprise non-techelic siloxanes.
  • These siloxanes are ones according to the above formula where at least some of the groups R 3 and/or R 4 comprise vinyl groups.
  • (meth)acrylate monomers are monomers that are the (meth)acrylate esters of non-tertiary alkyl alcohols, the alkyl groups of which comprise from about 1 to about 20, or about 1 to about 18 carbon atoms.
  • Suitable (meth)acrylate monomers include, for example, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, ethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, methyl methacrylate, 1-methylcyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, 3-methylcyclohexyl methacrylate, 4-methylcyclohexyl methacrylate, and 2-phenoxy ethyl methacrylate.
  • Particularly suitable (meth)acrylate monomers are those that, when homopolymerized, form a homopolymer having a glass transition temperature, a melting temperature, or both greater than about 40° C. These monomers are suitable in forming a copolymer network with a free radically polymerizable siloxane.
  • preferred (meth)acrylate monomers include isobornyl acrylate, cyclohexyl acrylate, trimethyl cyclohexyl acrylate, methyl methacrylate, methacrylic acid, t-butyl acrylate.
  • a single (meth)acrylate monomer or a combination of (meth)acrylate monomers may be used.
  • the glass transition temperature (and/or the melting temperature) may be measured by conventional techniques such as Differential Scanning Calorimetry (DSC) or Dynamic Mechanical Analysis (DMA). Some additional details regarding these components of the copolymer network are described in more detail below.
  • DSC Differential Scanning Calorimetry
  • DMA Dynamic Mechanical Analysis
  • the shape memory polymer may be a copolymer network including the reaction product of a free radically polymerizable siloxane having greater than one functional free radically polymerizable group and at least one (meth)acrylate monomer.
  • the reaction may include, for example, polymerization via curing. Curing may be carried out in an oxygen-free, e.g., in an inert atmosphere such as nitrogen gas or by utilizing a barrier of radiation-transparent material having low oxygen permeability. Curing can also be carried out under an inerting fluid such as water. When visible or ultraviolet radiation is used for curing, the reaction may also contain a photoinitiator.
  • Suitable photoinitiators include benzoin ethers, benzophenone and derivatives thereof, acetophenone derivatives, camphorquinone, and the like.
  • Some examples of commercially available photoinititaors include DARACUR 1173, DAROCUR 4265, IRGACURE 651, IRGACURE 1800, IRGACURE 369, IRGACURE 1700, and IRGACURE 907, commercially from Ciba Geigy.
  • the photoinitiator may be used at a concentration of from about 0.1% to about 5% by weight of the total polymerizable composition, and, if curing is carried out under an inerting fluid, the fluid is preferably saturated with the photoinitiator or photoinitiators being utilized in order to avoid the leaching of initiator from the reaction.
  • the rapid cure observed for these materials allows for the use of relatively low levels of photoinitiator, hence uniform cure of thick sections can be achieved due to deeper penetration of radiation.
  • curing can also be achieved thermally, which may include the use of thermal initiator such as peroxides, azo compounds, or persulfates generally at a concentration of from about 1% to about 5% by weight of the total polymerizable composition.
  • any initiator (thermal or photo-) utilized may be soluble in the reaction components themselves, thereby avoiding the need for a separate solvent. Liquid initiators may be preferred.
  • Polymerization mixtures can be prepared by dissolving telechelic siloxanes in the (meth)acrylate monomers and adding a photoinitiator Such polymerization mixtures typically have viscosities that permit the preparation of samples in film form by direct coating and radiation curing by standard procedures.
  • the shape memory polymer article may be formed by coating and curing the polymerizable mixture in a structured configuration, by curing the polymerization mixture in an unstructured configuration and then applying a structure through the imposition of heat and pressure, or by a combination of the these processes.
  • the polymerization mixture can be coated onto a carrier layer such as a liner (either structured or unstructured), onto a substrate (such as a metal sheet or foil, a film, a ceramic or piece of glass, etc) or onto a tool or mold.
  • a covering layer which may be another liner, substrate, tool or mold and may be the same or different from the carrier layer.
  • the resulting construction is then cured, preferably with UV radiation.
  • one or both of the carrier layer and or the covering layer are removed and the shape memory polymer article may then be subjected to additional processing (to create or remove structuring, to form in articles of a desired shape, etc).
  • 5K MeStUS Alpha-methyl styrylurea siloxane a difunctional silicone alpha-methyl styrene prepared from PDMS diamine 5K as described in U.S. Pat. No. 5,514,730 column 14 for 35K MeStUS, using 5,000 g/mole PDMS diamine instead of 35,000 g/mole PDMS diamine.
  • 50K MAUS Methacryloxyurea siloxane a difunctional silicone acrylate prepared from PDMS diamine 50K as described in U.S. Pat. No. 5,514,730 column 14 for 35K MAUS, using 50,000 g/mole PDMS diamine instead of 35,000 g/mole PDMS diamine.
  • 50K MeStUS Alpha-methyl styrylurea siloxane a difunctional silicone alpha-methyl styrene prepared from PDMS diamine 50K as described in U.S. Pat. No. 5,514,730 column 14 for 35K MeStUS, using 50,000 g/mole PDMS diamine instead of 35,000 g/mole PDMS diamine.
  • a curable precursor solution of 40 parts of 5K MAUS dissolved in 60 parts of IBA, containing 0.5 wt % DAROCUR 1173 was poured on the first tool, which was an unstructured PET film laid down on the surface of a glass plate.
  • the first tool was bordered by a compliant adhesive film of 3 millimeters thickness to serve as a dam for the curable adhesive precursor as well as a spacer to control the thickness of the cured film.
  • the liquid layer of curable precursor was covered with a cover sheet (an unstructured UV transparent film) and the excess fluid was squeezed out by placing a rigid glass plate over the cover sheet and pressing the thus formed sandwich construction until the glass plate rested against the spacer.
  • the sandwich construction was exposed to low intensity UV lights through the cover sheet for 10-15 minutes.
  • the resulting cured film (slab) had two surfaces replicated from the first tool and from the cover sheet (second tool) and was removed from both the first tool and from the cover sheet. The edges of the substrate were trimmed.
  • Example 1 The slab prepared in Example 1 was deformed by pressing against the structured surface of the metal tool and a polished steel plate with heat/pressure (110° C. for 10 minutes, pre-press 4.1 MegaPascals (600 lbs/in 2 ) for 10 minutes, 30 MegaPascals (2 ton/in 2 ) high pressure for 10 minutes) and quenched (25 minutes until temperature reached 60° C.).
  • the structure of the tool an array of tilted triangular prisms with millimeter-size dimensions, was partially replicated—approximately 60-70% of the height of the pyramid.
  • Example 2 A part of the film made in Example 2 was heated to approximately 110° C. on a heating plate. The area exposed to heat became essentially flat, with some traces of the embossed microstructure still visible.
  • a shape-memory substrate was prepared as described in Example 2.
  • One part of the sample was submitted to a secondary process of shaving off the temporary surface features.
  • the portion of the sample with shaved-off material showed rounded cavities with topologies corresponding to the shaved-off elements.
  • a shape-memory substrate was prepared as described in Example 1 except that the first tool was a microstructured film having linear array of rectangular channels (200 micrometers at the bottom, 100 micrometers at the top, 200 micrometer high) and a 1 millimeter spacer was used.
  • the sample was flattened between the two polished steel plates under the conditions as described in Example 2 except flat tools were used.
  • One part of the film was sprayed with metallic silver paint to form a thin layer of metallic silver.
  • the electrical conductivity of the sample was checked using a Fluke 87 III RMS Multimeter, which was independent of the position of the electrodes (x and y conductive). A portion of the sample was heated to 120° C. on a heating plate to restore the original shape of the surface. Electrical conductivity of the sample was again checked. While the sample maintained the electrical conductivity along the channels the conductivity in the cross-direction was primarily destroyed and/or disrupted.
  • a shape-memory substrate was made as described in Example 1 except that the first tool was a metal tool with structured surfaces as described in Example 2.
  • the substrate having sharp macroscopic features was subsequently submitted to heat and pressure between two polished steel plates under the conditions described in Example 2 except flat tools were used.
  • the substrate became essentially flat with the pyramids being partially flattened and partially bent. Part of the original structure was restored by selectively focusing sunlight through a lens onto several of the pyramids.
  • a shape-memory substrate was tested through the stages of making, distorting and restoring.
  • the sample was made as described in Example 1 except that the first tool was a metal tool having an array of cube corners as described in U.S. Pat. No. 5,706,132.
  • the pyramids had a height of 87 micrometers (3.5 mil).
  • the spacer used was 125 micrometers.
  • the sample was removed from the first tool while maintained on the flat PET cover.
  • the sample showed retroreflectivity when analyzed using a retroviewer (the sample “made” stage).
  • a part of the sample was flattened between the two polished steel plates under the conditions described in Example 2 except that the tools were flat.
  • Example 7 A series of samples were made, distorted and restored as in Example 7 except that different compositions of the curable precursors were used (containing Monomer 1, IBA and DAROCUR 1173) as shown in Table 1. Results of the testing are shown in Table 2.
  • a shape-memory substrate was made as described in Example 1 except that a 125 micrometers spacer was used.
  • One of the surfaces of the substrate was deformed by pressing the sample between the metal tool, having regularly arranged square posts (150 micrometers at the bottom, 150 micrometers at the top, 50 micrometers high), to create a corresponding array of microcavities.
  • the substrate was coated with a Water-borne PSA. Upon drying the water at 25° C. for 24 hours, the film contained PSA distributed within the pockets of microstructure substrate and showed no/little tack.
  • a portion of the sample was heated to 120° C. on a heating plate causing the restoration of the original flatness of the substrate and making the sample tacky by exposing the PSA layer on the surface.
  • a shape-memory substrate was made as described in Example 1 except that a 1 millimeter spacer was used.
  • One of the surfaces of the substrate was deformed by pressing the sample between the metal tool, having an array of triangular posts (420 micrometers depth), to create an array of visible cavities.
  • the substrate was flooded with colored aqueous fluid to fill the cavities.
  • Silicone pressure sensitive adhesive tape (as described in U.S. Pat. No. 6,569,521, Example 28) was laminated to the substrate to seal off the cavities filled with the fluid. When heated to 120° C. the substrate returned to its original shape exerting pressure on the laminated tape causing the tape to also distort, and causing the adhesive border seals to rupture.
  • a shape-memory substrate was made as described in Example 1, except that the first tool was a metal tool, a replica of the tool used to deform the substrate in Example 14, having regularly arranged square cavities (150 micron at the bottom, 150 micron at the top, 45 micrometer high) and a 1 millimeter spacer to create a corresponding array of micro-posts.
  • the sample was flattened between two polished steel plates under the conditions as described in Example 2. The sample was heated to 120° C. on a heating plate to restore the original structure (posts) of the surface. The posts were able to pick up water-based ink for transfer to paper.
  • a shape-memory substrate was made as described in Example 1 except that a 125 micrometers spacer was used.
  • One of the surfaces of the substrate was deformed by pressing the sample between the metal tool having regularly arranged square posts, as described in Example 14, to create a corresponding array of micro-cavities.
  • a droplet of the solution of dye (bromothymol blue, sodium salt) in ethylene glycol was deposited on the surface of the film, clear-cut borders along the line of the pattern were naturally established, and the solvent essentially restored the “printed” area to flatness with the clearly visible high concentration of the dye in the spots corresponding to the arrangement of cavities in which it was originally deposited.
  • a shape-memory substrate was made as described in Example 1 except that a 125 micrometers spacer was used and the first tool was a metal tool with an array of square posts, as described in Example 14.
  • the cured sample was pressed between 2 flat surfaces using the technique described in Example 2.
  • a droplet of the solution of dye (bromothymol blue, sodium salt) in ethylene glycol was deposited on the surface of the film, clear-cut borders along the line of the pattern were naturally established, and the solvent essentially restored the “printed” area to its micro-cavitated form dragging the ink into the cavities.
  • a shape-memory substrate was made as described in Example 1 except that a 125 micrometers spacer was used. One of the surfaces of the cured substrate was deformed by pressing the sample between the metal tool, used in Example 16. A droplet of the aqueous solution of dye (bromophenol blue indicator solution) was deposited and pressed on the microstructured surface of the shape-memory substrate. The solution was primarily distributed in the channels between the posts, and on the top of the posts having some small micro-channels. When exposed to heat (120° C.), the solvent (water) evaporated and the flatness of the first surface of the substrate was essentially restored leaving a regular pattern of the dye on the surface.
  • dye bromophenol blue indicator solution
  • a shape-memory substrate was made as described in Example 1 except that a 125 micrometers spacer was used. One of the surfaces of the substrate was deformed by pressing the sample between the metal tool (an array of cube corners as described in U.S. Pat. No. 5,706,132, pyramidal height of 87 micrometers), as described in Example 2.
  • a border of adhesive was made on a plastic substrate and the microstructured surface was placed within and on the border. The retroreflectivity of the microstructured surface disappeared where in contact with the adhesive border, but remained retroreflective within the border.

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EP2046408A4 (en) 2009-08-19

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