Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J153/00—Adhesives 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
  • C09J153/02—Vinyl aromatic monomers and conjugated dienes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
  • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
  • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J153/00—Adhesives 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
  • C09J153/02—Vinyl aromatic monomers and conjugated dienes
  • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
  • C09J193/04—Rosin
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/38—Pressure-sensitive adhesives [PSA]
  • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C09J7/387—Block-copolymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/24—All layers being polymeric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/412—Transparent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/75—Printability
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2405/00—Adhesive articles, e.g. adhesive tapes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2519/00—Labels, badges
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives
  • C08G2170/20—Compositions for hot melt adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives
  • C08G2170/40—Compositions for pressure-sensitive adhesives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition 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
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition 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
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
  • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2423/00—Presence of polyolefin
  • C09J2423/04—Presence of homo or copolymers of ethene
  • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2423/00—Presence of polyolefin
  • C09J2423/10—Presence of homo or copolymers of propene
  • C09J2423/106—Presence of homo or copolymers of propene in the substrate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2453/00—Presence of block copolymer
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J2493/00—Presence of natural resin
• • 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
  • Y10T428/14—Layer or component removable to expose adhesive
  • Y10T428/1452—Polymer derived only from ethylenically unsaturated monomer
• • 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.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• • 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
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions
• • 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
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions
  • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
• • 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
  • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
  • Y10T428/2852—Adhesive compositions
  • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
  • Y10T428/2883—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer of diene monomer [e.g., SBR, SIS, etc.]

Definitions

• the present invention relates to a hot-melt pressure-sensitive adhesive (HMPSA) composition suitable for bonding permanently adhesive self-adhesive labels to any type of smooth or rough surface support, an article comprising said adhesive composition, and that the method of preparation of said article.
• HMPSA hot-melt pressure-sensitive adhesive
• Hot melt adhesives are solid substances at room temperature that do not contain water or solvents. They are applied in the molten state and solidify during cooling, thus forming a seal which secures the substrates to be assembled. Some Hot MeIt are formulated to give the coated medium a relatively hard and tack free character. Other Hot MeIt provide the support with a relatively soft and tacky type: these are PSA that are widely used for the manufacture of self-adhesive labels; the corresponding adhesives are designated by the name of "hot melt pressure-sensitive adhesives" or, in English, by that of "Hot MeIt Pressure Sensitive Adhesive" (or HMPSA).
• Pressure-sensitive adhesives also known as pressure-sensitive adhesive adhesives or PSA are substances which give the support which is coated therein immediate tackiness at room temperature (often referred to as "tack"), which allows its instant adhesion to a substrate under the effect of a light and brief pressure.
• PSAs are widely used for the manufacture of self-adhesive labels which are affixed to articles for the purposes of presenting information (such as bar code, name, price) and / or for decorative purposes.
• PSAs are generally applied by continuous coating processes over the entire surface of a large printable support layer made of paper or film of a single or multi-layered polymeric material.
• the adhesive layer which covers the printable support layer is itself covered with a protective layer (often referred to as the "release liner"), for example consisting of a film or silicone paper.
• the multilayer system obtained is generally packaged in the form of large coils up to 2 m wide and 1 m in diameter, which can be stored and transported.
• This multilayer system can be subsequently converted into end-user-applicable self-adhesive labels, by means of transformation methods that include printing the desired informative and / or decorative elements on the printable side of the support layer, and then cutting to the shape and dimensions desired.
• the protective layer can be easily removed without modification of the adhesive layer which remains attached to the printable support layer. After separation of its protective layer, the label is applied at a temperature ranging from 0 ° C to 50 ° C on the article to be coated either manually or using labellers on automated packaging lines.
• the PSAs make it possible to quickly grip or hold the label on the article to be coated, which is suitable for obtaining high production rates.
• the present invention has the first object of providing an adhesive which makes it possible to stick a label permanently to an article, such as a packaging and / or a container (for example glass bottles or plastic bottles), and which also offers the possibility of improving the maintenance of labels, such as avoiding problems of curling edges or edge peeling (haloing) of the self-adhesive label before, during and after labeling, whatever the roughness of the labeled surface.
• the present invention also aims more specific to provide a self adhesive transparent label to obtain an article called "no label look" that is to say, an article on which the label is invisible and where only the prints are apparent.
• the transparent self-adhesive label at departure before application to the article becomes invisible on the surface of the article in a time compatible with the manufacturing process and delivery before placing on the market (called “wet out” time). ), while not having any separation of the edges (haloing) and this also whatever the surface roughness of the article on which the label is applied.
• the present invention also aims to obtain an article on which the self-adhesive label remains peelable on the surface of the article for at most 36h and preferably for 24 hours or for 12h. This implies being able to completely separate the label from the article to which it is attached, without leaving any adhesive residue on the surface of the latter, so as to facilitate a process for recycling of tagged items when they are non-compliant.
• the invention therefore firstly relates to a hot melt pressure sensitive adhesive composition
• a hot melt pressure sensitive adhesive composition comprising: - from 20 to 50% by weight of a polymer part A) comprising a mixture of styrenic block copolymers consisting of i) 10 to 100% by weight of one or more radial or linear triblock copolymers of Styrene-Butadiene-Styrene (SBS), Styrene-Isoprene-Styrene (SIS), Styrene-Ethylene / Butylene-Styrene (SEBS), Styrene-Isoprene / Butylene Styrene (SIBS) , Styrene-ethylene / propylene-styrene (SEPS) and ii) less than 90% by weight, preferably 0% to 80%, of one or more styrene-butadiene (SB) or styrene-isoprene di-block
• said liquid part comprising (B1) comprising one or more tackifying resins chosen from liquid polar compounds optionally mixed with (B2) comprising at least one polar oil, preferably a benzoate oil;
• the solid part C) represents 0 to 75% by weight of the mixture B + C and has a softening point measured according to ASTM E 28 greater than 70 0 C, preferably between 90 and 150 0 C, and is constituted one or more polar or apolar solid tackifying resins;
• said part B + C comprising from 0 to 40% by weight of apolar resin, preferably from 5 to 35% by weight, and from 60% to 100% by weight of polar resin, preferably from 65% to 95% by weight; weight.
• the liquid part B consists solely of the part B1 comprising one or more tackifying resins chosen from polar liquid compounds based on rosins or their ester derivatives of rosins.
• HMPSA hot melt adhesive composition pressure sensitive
• a polymer component A comprising a mixture of styrenic block copolymers consisting of i) 10 to 100 % by weight of one or more radial or linear triblock copolymers of Styrene-Butadiene-Styrene type
• SBS Styrene-Isoprene-Styrene
• SEBS Styrene-ethylene / butylene-styrene
• SEPS styrene-butadiene
• SI styrene-isoprene diblock copolymers
• said liquid portion comprising (B1) comprising one or more tackifying resins chosen from liquid polar compounds based on rosins or their rosin ester derivatives, optionally in admixture with (B2) comprising at least a benzoate oil, optionally supplemented with one or more naphthenic or paraffinic hydrocarbon-based apolar oils; advantageously only consists of the part (Bl);
• the solid part C) represents 0 to 75% by weight of the mixture B + C and has a softening point measured according to ASTM E 28 greater than 70 0 C, preferably between 90 and 150 ° C, and is constituted one or more apolar solid tackifying resins or terpenic resins resulting from the polymerization of terpene hydrocarbons in the presence of Friedel-Crafts catalysts, and modified by the action of phenols; said B + C portion comprising from 0 to 40% by weight of apolar resin, preferably from
• the solid tackifying resins of part C are chosen from apolar resins.
• part A represents from 25% to 45% by weight of the adhesive composition and portion B + C represents from 55% to 75% by weight of the adhesive composition.
• the invention has for object a second multilayer system comprising: an adhesive layer consisting of the preferred HMPSA as defined above a printable support layer adjacent to said adhesive layer, consisting of a non-porous material, transparent or not ;
• the second subject of the invention is a multilayer system comprising: an adhesive layer, consisting of HMPSA as defined above, a printable support layer adjacent to said adhesive layer, consisting of a transparent non-porous material; a protective layer adjacent to said adhesive layer.
• the support layer consists of a transparent polymer film with one or more layers, preferably a single-layer OPP or PE polymer film.
• the printed face of the monolayer film is in contact with the adhesive layer.
• the third object of the invention is a self-adhesive label that can be obtained by cutting the multilayer system as defined above, in which the amount of adhesive on the support surface is from 10 to 70 g / m 2, preferably from 15 to 25 g / m2.
• the invention has for its fourth object an article whose external surface roughness Ra, measured with an interferometric microscope, is greater than or equal to 0.1 ⁇ m, preferably greater than or equal to 1 ⁇ m, coated with a self-adhesive label as defined. upper.
• the article is selected from the objects made of glass or plastics, such as packaging, containers or tires.
• the article says "no label look” consists of plastic coated with a self-adhesive label in which the backing layer consists of a polymer film is transparent and self-adhesive label is invisible.
• the fifth invention is a method of preparing an article coated with a self-adhesive label comprising: a) applying at a temperature between 0 ° C and 50 ° C of a self-adhesive label as defined in the claim 8 of a rough surface of which preferably the outer Ra surface roughness is greater than 0.1 microns, preferably between 2 and 5 microns, b) optionally, in the event of non-compliance of the positioning of the label to the surface of the article in the previous step, the manual take-off of this label within a period not exceeding 24 hours, then recycling said item not comprising traces of adhesives on its surface by return to the step a).
• the method allows the preparation of an article called "no label look" in which the self-adhesive label is transparent and becomes invisible in less than 10 days, preferably between 1 and 7 days.
• the sixth invention relates to the use of a self-adhesive label as defined above for coating the surface of an article, preferably a packaging plastic or tire.
• the label used does not curling the edges (curling) or haloing phenomenon of the edges, within a period of at least 72 hours.
• the adhesive composition comprises from 20 to 50%, preferably from 25% to 45% by weight of a polymeric portion (A) comprising a blend of styrenic block copolymers.
• the block copolymers that can be used in the HMPSA according to the invention have a weight average molecular weight Mw generally of between 60 kDa and 400 kDa and consist of blocks of different polymerized monomers. They have a tri-block configuration of general formula: A-B-A (I) in which: A represents a styrene non-elastomeric block (or polystyrene), and
• B represents an elastomeric block which may be:
• polyisoprene the block copolymer then has the structure: polystyrene-polyisoprene-polystyrene, and for denomination: SIS;
• the block copolymer then has the structure: polystyrene-poly (ethylenepropylene) -polystyrene and for denomination: SEPS; polybutadiene: the block copolymer then has the structure: polystyrene-polybutadiene-polystyrene, and for denomination: SBS
• the block copolymer then has the structure: polystyrene-poly (ethylenebutylene) -polystyrene and for denomination: SEBS.
• SEBS polystyrene-poly (ethylenebutylene) -polystyrene and for denomination: SEBS.
• This SEBS copolymer may optionally have been chemically modified with maleic anhydride.
• triblock styrenic copolymers can be obtained according to methods known per se and are commercially available. The processes for obtaining these Commercial products also generally lead to the formation of varying amounts of di-block compounds of formula AB.
• the terms SIS, SIBS, SEBS, SEPS and SBS refer to mixtures of triblocks and diblocks.
• the amount of diblock can vary without disadvantage from 0 to 80% based on the total weight of styrenic copolymers.
• the tri-block styrene copolymers which can be used in I 1 HMPSA according to the invention may also have a radial structure.
• styrenic block copolymer (s) included in the MPSA according to the invention which are selected from the group comprising SIS, SBS, SIBS, SEBS, SEPS may belong to one or more of these 5 families of copolymers.
• the amount of styrenic block can vary within wide limits, such as from 10% to 50% (based on the total weight of block copolymers).
• Examples of commercial products include:
• Kraton Gl 726 ® (70% diblock and 30% styrene).
• Kraton ® G 1924 (30% diblock and 13% styrene) is a SEBS grafted with 1% maleic anhydride.
• the adhesive composition comprises 50 to 80% preferably 55 to 75% by weight of a resin consisting part of a liquid portion B and "a solid portion C.
• the liquid part B) is 25 to 100% by weight, preferably 50 to 80% by weight of the B + C mixture and has a minimum softening point in the range of -10 ° C to 50 ° C, preferably in the range of 5 to 50 ° C. ° C and 20 ° C, softening point measured according to ASTM E 28 for the range 20 ° C to 50 ° C, or by the method DSC (Differential scanning calorimetry) for the range -10 ° C to
• This liquid part comprises a part (B1) comprising one or more tackifying resins chosen from liquid polar compounds, optionally mixed with (B2) comprising at least one polar oil, preferably a benzoate oil;
• Part B1 comprises tackifying resins which have weight average molar masses M n generally between 200 and 5000 and are chosen specifically from solid or liquid polar compounds.
• polar products include rosins of natural origin or modified, such as for example rosin extracted from pine gum, wood rosin extracted from the roots of the tree and their hydrogenated, dehydrogenated, dimerized derivatives. , polymerized or esterified with monoalcohols or polyols such as glycerol.
• Part B2 comprises at least one polar oil, preferably an oil of
• Benzoate such as benzoflex 2088 from the company Velsicol or a phthalate-based oil such as Diisol Nylon phthalate.
• This part B2 may be supplemented with one or more naphthenic or paraffinic hydrocarbon-based apolar oils, such as a paraffinic and naphthenic oil such as Primol 352 from the company ESSO.
• tackifying resins B 1 or are selected from resins whose softening temperature is high it may be useful to mix them with a polar oil comprising for example at least one benzoate oil in order to obtain a liquid mixture whose temperature softening is between -10 ° C and
• the tackifying resins or resins of the portion B1 are chosen from polar liquid resins, for example resins based on rosin whose softening temperature is between 0 ° C. and 50 ° C.
• the liquid part comprising (B1) comprising one or more tackifying resins chosen from liquid polar compounds based on rosins or on their rosin ester derivatives, optionally mixed with (B2) comprising at least one benzoate oil, will be preferred.
• the liquid portion B consists solely of the portion B1 comprising one or more tackifying resins selected from polar liquid compounds based on rosins or their ester derivatives of rosins.
• the solid part C) represents from 0 to 75%, preferably from 20 to 50% by weight of the B + C mixture and has a softening point measured according to ASTM E 28 greater than 70 ° C. preferably between 90 and 150 ° C, and consists of one or more polar or apolar solid tackifying resins;
• Part B + C generally comprises from 0 to 40%, preferably from 5 to 35% by weight of apolar resin, and from 60% to 100%, preferably from 65% to 95% by weight, of polar resin.
• the polar or apolar selected solid tackifying resins or resins have weight average molar masses M n generally between 300 and 5000 and are chosen in particular from:
• Rosin of natural origin or modified such as for example rosin extracted from pine gum, wood rosin extracted from tree roots and their hydrogenated, dehydrogenated, dimerized, polymerized or esterified derivatives by monoalcohols or polyols such as glycol, glycerol, pentaerythritol.
• terpene resins generally resulting from the polymerization of terpene hydrocarbons in the presence of Friedel-Crafts catalysts as for example mono-terpene (or pinene), alpha-methyl styrene, and modified by the action of phenols; the latter are preferred and represent polar resins in the context of the preferred HMPSA;
• Apolar resins such as; (iii) resins obtained by hydrogenation, polymerization or copolymerization (with an aromatic hydrocarbon) of unsaturated aliphatic hydrocarbon mixtures having about 5, 9 or 10 carbon atoms derived from petroleum cuts;
• terpene resins generally resulting from the polymerization of terpenic hydrocarbons in the presence of Friedel-Crafts catalysts, for example mono-terpene (or pinene), copolymers based on natural terpenes, for example styrene / terpene, alpha-methyl styrene / terpene and vinyl toluene / terpene.
• Friedel-Crafts catalysts for example mono-terpene (or pinene)
• copolymers based on natural terpenes for example styrene / terpene, alpha-methyl styrene / terpene and vinyl toluene / terpene.
• Escorez 5600 (resp. 5615) available from Exxon Chemicals which is a hydrogenated dicyclopentadiene resin modified with an aromatic compound having a softening temperature of 100 ° C (resp. 12O 0 C) and an M w of about 980 Da; Escorez 5400 also from the company Exxon Chemicals with a softening temperature of 100 0 C; Wingtack Extra from Cray Valley Company
• Sylvarez ZT 105 LT from the company Arizona Chemical which is a styrene / terpene copolymer with a softening point of 105 ° C., Norsolène W100 from the company Cray Valley having a softening point of 100 ° C.
• the tackifying resins used in the adhesive composition are said to be compatible, that is to say a tackifying resin which when mixed into the 50% / 50% proportions with a selected styrene block copolymer (SIS or SBS) gives a substantially homogeneous mixture.
• Tackifying resins having a softening temperature of 95 to 130 ° C are preferred, such as Escorez 5600 or 5615. 1.3. Other additives.
• the composition used in the invention may also include a wax of a polyethylene homopolymer (such as Honeywell's AC 8), or a wax of a polyethylene / vinyl acetate copolymer, preferably in an amount ranging from 0 to 5% by weight of the adhesive composition.
• a wax of a polyethylene homopolymer such as Honeywell's AC 8
• a wax of a polyethylene / vinyl acetate copolymer preferably in an amount ranging from 0 to 5% by weight of the adhesive composition.
• An amount of 0.1 to 3% of one or more stabilizers (or antioxidant) is further preferably included in the composition of the invention. These compounds are introduced to protect the composition from degradation resulting from a reaction with oxygen which is likely to be formed by the action of heat, light or residual catalysts on certain raw materials such as tackifying resins .
• These compounds may include primary antioxidants that scavenge free radicals and are generally substituted phenols like Irganox ® 1010 from CIBA or Sumilizer ® GS.
• the primary antioxidants can be used alone or in combination with other antioxidants such as sulphites such as Irganox ® PS800 also from CIBA, or with UV stabilizers such as amines such as Tinuvin ® 770 (family HALS) or UV filters such as Tinuvin ® 328.
• the hot-melt self-adhesive composition according to the invention is prepared by simply mixing its components at a temperature of between 130 and 200 ° C., until a homogeneous mixture is obtained.
• the mixing techniques required are well known to those skilled in the art.
• the hot melt adhesive composition according to the invention belongs to the category of permanent adhesives having a coefficient of adhesion such that they possess the characteristic of defibrating a vellum 70g on which the label (once coated with the adhesive) defigures this paper after a 20 minute deposit.
• the adhesive composition has an initial adhesive strength measured according to FINAT No. 1 by peeling on glass greater than or equal to 2.5N / cm. This power adhesive may increase over time to become greater than or equal to 3N / cm beyond 24h or 36h. Thus, in the period of less than 36 hours, a label stuck on a support via the adhesive composition according to the invention remains peelable from the support manually without any trace of adhesive remaining on the support. 4. Multilayer system.
• the present invention also relates to a multilayer system comprising:
• an adhesive layer consisting of the hot-melt pressure-sensitive adhesive composition according to the invention, in particular the preferred HMPSA; a printable support layer adjacent to said adhesive layer, consisting of a non-porous material, transparent or not, preferably a single or multi-layered polymeric film;
• the adhesive layer which covers the printable support layer is itself covered with a protective layer (often called the "release liner"), for example consisting of a film or silicone paper.
• a protective layer for example consisting of a film or silicone paper.
• the multilayer system obtained is generally packaged in the form of large coils up to 2 m wide and 1 m in diameter, which can be stored and transported.
• the support layer may comprise a coated layer called "barrier" on the face to be adhesive.
• This coating such as, for example, acrylic polymers, is generally intended to prevent the migration of components of the adhesive into the film and to avoid curling phenomena. But this additional treatment has a significant cost on the film.
• it is preferred to use as a printable support layer a "monolayer" film of the OPP or PE type having no barrier layer on the face to be coated. This reduces the total cost of the label.
• the HMPSA according to the invention is applied in the molten state at a temperature above 120 ° C. on the release liner and transferred in line to the printable support at a quantity of between 10 and 70 g. / m 2 to form the adhesive layer.
• the amount of adhesive is defined according to the desired thickness when applied to the final support and in relation to the surface condition of the targeted support.
• the application is carried out by known coating techniques such as, for example, the coating technique of the nozzle type (at a temperature of about 160 to 180.degree. C.) or of the curtain type (at a temperature of about 120.degree. at 180 ° C).
• HMPSA by lip nozzle is generally performed on the protective layer, the assembly then being laminated to the support layer (transfer coating).
• transfer coating The application of HMPSA by curtain type coating can be directly carried out on the support layer, depending on the coating temperature.
• printing can be done on the face where the adhesive will be deposited. This technique allows the printing of the label to better guard against scratching.
• the invention also relates to a self-adhesive label that can be obtained by transformation of the multilayer system described above.
• the transformation method implemented generally comprises at least one cutting step with a printing step on the printable support layer beforehand if the printing has not already been done on the support layer at the time of the preparation of the system. multilayered. The cut is then followed by a roll for storing the labels.
• the self-adhesive label according to the invention comprises an amount of adhesive on the surface of the support which ranges from 10 to 70 g / m 2 , preferably from 15 to 25 g / m 2 .
• the invention also relates to an article coated with said label.
• the article labeled according to the invention is preferably an object (packaging or container) made of glass or a usual plastic material selected from polyethylene terephthalate (PET), polyvinyl chloride (PVC), polyethylene (PE) or PolyPropylene (PP), polycarbonates, acrylonitriles butadiene styrene (ABS), polymethyl methacrylates (PMMA).
• PET polyethylene terephthalate
• PVC polyvinyl chloride
• PE polyethylene
• PP PolyPropylene
• ABS acrylonitriles butadiene styrene
• PMMA polymethyl methacrylates
• the coated article may be a tire for any type of vehicle. 6.1. Measurement of the surface condition of an article:
• the external surface state of an article is defined by its roughness Ra measured by interferometric microscopy in 3D according to the method described in the examples.
• the objects concerned, according to their surface treatment or composition may have very varied surface roughness.
• plastic containers whose composition comprises more or less pigment may have surface roughness ranging from a so-called smooth surface to a surface described as rough.
• a smooth surface material is represented by Ra less than or equal to 1 ⁇ m, preferably from 0.1 ⁇ m to 1 ⁇ m.
• the final materials of smooth surface include PET bottles containing no pigment and obtained by a blowing process.
• a rough surface material is represented by Ra strictly greater than 1 ⁇ m, preferably between 1.5 ⁇ m and 5 ⁇ m.
• the rough surface materials include non-transparent bottles in pigmented PP.
• the adhesive When the label is deposited on the article, the adhesive is spread without constraints or pressure and impregnate this surface so as to remove air bubbles or voids which may remain on the surface of the article. These defects must absolutely be eliminated in a time compatible with the manufacturing and delivery process to finally obtain an article on which the transparent label is invisible. This time impregnating called time to "wet out” depends on the physical parameters of the adhesive composition used as its viscosity, its surface energy, its cohesion and its rheology, or its polarity.
• this "wet out” time is less than 10 days, preferably between 3 and 5 days, regardless of the roughness level of the support.
• the support layer of the label is a transparent polymer film
• the self-adhesive label becomes invisible once applied to the surface of an article, preferably plastic, regardless of its level of roughness and gets an article called "no label look" in less than 10 days.
• the self-adhesive label becomes invisible between 1 and 7 days even when applied on the surface of a rough plastic article, i.e. the surface has a roughness greater than 1 micron and preferably between 1, 5 and 5 microns.
• the adhesive according to the invention it is possible to preserve the label-holding and invisibility properties described above with reduced amounts of adhesive and between 15 and 30. g / m 2 or preferably 15 to 25 g / m 2 and this in particular when the label is applied to a rough surface.
• the self-adhesive label is applied to the surface of a section preferably filled with the product to market.
• the method of preparing an article coated with a self-adhesive label comprises: a) applying at a temperature between 0 ° C and 50 0 C of a self-adhesive label as defined above preferably on a rough surface, in particular whose external Ra surface roughness is between 2 and 5 microns, b) optionally, in the event of non-compliance of the positioning of the label on the surface of the item in the previous step, the manual takeoff this label within a period not exceeding 24 hours, then recycling said item comprising no traces of adhesives on its surface by returning to step a).
• the method allows the preparation of a so-called "no label look" article in which the self-adhesive label is transparent and becomes invisible in less than 10 days, preferably between 1 and 7 days.
• the invention also relates to the use of a self-adhesive label as defined above for coating the surface of an article, preferably a plastic package or a tire.
• the label used does not curling the edges (curling) or haloing phenomenon of the edges, within a period of at least 72 hours.
• Viscosities are measured using a Brookfield RVT viscometer according to ASTM D 3236.
• the softening points of the solid resins which are greater than 20 ° C are measured by the ball and ring method according to ASTM E 28.
• the principle is as follows. A brass ring about 2 cm in diameter is filled with the resin to be tested in the molten state. After cooling to room temperature, the ring and the solid resin are placed horizontally in a thermostated bath of glycerine whose temperature can vary from 5 ° C per minute. A steel ball with a diameter of about 9.5 mm is centered on the solid resin disc. The softening temperature is, during the temperature rise phase of the bath at a rate of 5 ° C per minute, the temperature at which the resin disc flows 25.4 mm under the weight of the ball.
• the softening points of the resins which are between -10 ° C. and 20 ° C. are measured by the DSC (differential scanning calorimetry) method.
• the principle is the following. The measurement is made on a rise in temperature at a rate of 10 ° C / min of the sample after erasing the thermal memory of the product. We get an endotherm curve (head down) and the melting temperature is the extremum of this curve. 8.3. Measure of "curling"
• Curling is measured visually with the placement of a 10cm x 10cm size label on a 5mm diameter glass or metal mandrel.
• the label without its protective support is glued to bare in its center and tangentially on this mandrel.
• the mandrel is fixed on a support so that the label is positioned without stress in a vertical plane.
• the Haloing is measured visually with the placement of a rectangular shaped label 7cm x 10cm with round angles (lcm diameter) on bottles with a radius of curvature of 10cm.
• the label is cut automatically under industrial conditions and stuck manually those bottles.
• the vials are stored 24h at 23 ° C / 50% relative humidity, then stored in an oven for 48 hours at 40 ° C. At the end of the test, we note if there is delamination of the edges or not. 8.5. Measuring the "wet out" time
• the time to "wet out” is measured using bottles to known and measured roughness. A 10cm x 5cm surface label is glued manually or automatically to this bottle. A slight pressure is exerted so as to chase any air bubbles. The labeled bottle is thus stored in an air conditioned room at 23 ° C / 50% humidity. Every 24 hours a visual verification of the transparency is carried out. Once the transparency is complete, we stop the test and we note the wetting time or "wet out” time. 8.6. Adhesion measurement Peel test. The adhesive power of the HMPSA according to the invention is evaluated by the 180 ° C peel test on a glass plate or on HDPE as described in the FINAT test method No. 1, published in the Manual. Technique FINAT 6 th edition, 2001.
• FINAT is the international federation of manufacturers and converters of self-adhesive labels.
• the principle of this test is as follows. HMPSA is pre-coated at a rate of 20 g / m 2 on the OPP side of a support layer consisting of a 19 ⁇ m thick PET film which is laminated onto a 50 ⁇ m thick OPP film using a two-component polyurethane adhesive. A specimen in the form of a rectangular strip (25 mm x 175 mm) is cut from the support self-adhesive thus obtained. This test piece is fixed on a substrate consisting of a glass plate. The assembly obtained is left for 20 minutes at room temperature.
• the 180 ° peel on a glass plate of glues intended for the manufacture of self-adhesive labels is generally greater than 2 N / cm, preferably 4 N / cm.
• the immediate sticking power or tack of the HMPSA according to the invention is evaluated by the instantaneous adhesion test called the loop, described in the FINAT test method No. 9.
• the HMPSA is pre-coated at a rate of 20 g. / m 2 on an OPP film 50 ⁇ m thick, so as to obtain a rectangular band of 25 mm by 175 mm.
• the two ends of this band are joined so as to form a loop whose adhesive layer is oriented outwards.
• the two joined ends are placed in the movable jaw of a traction device capable of imposing a movement speed of 300 mm / minute along a vertical axis with the possibility of going back and forth.
• the lower part of the loop placed in the vertical position is first brought into contact with a 25 mm by 30 mm horizontal glass plate over a square zone of about 25 mm side. As soon as this contact is made, the direction of movement of the jaw is reversed.
• the immediate tackiness is the maximum value of the force required for the loop to come off the plate completely.
• the tackiness of a PSA is generally greater than or equal to 1 N / cm 2 . 8.7. roughness measurements. The roughness is observable qualitatively visually in the form of small dips and bumps by reflection of light on the support.
• the roughness is measured quantitatively automatically using an interferometric microscope such as Zygo New View according to the method described in the publication by De Groot, P., Colonna de Lega XC, Kramer, J. and Turzhitsky, M (2002) '. Order determination in white-light microscopy interference, Appl. OpL, Vol. 41, pp. 4571-4578.
• This device and its associated software reconstruct the entire topography of the surface and determines the value of the parameter Ra in 3D as described in the Zygo New View 200 manual Metropro 1 Reference OMP 0514A revision 06/2005.
• Example 1 Preparation of the adhesive compositions.
• compositions appearing in the following Table 1 are prepared by simple hot mixing at 180 ° C. of the ingredients until a homogeneous mixture is obtained.
• the mixing techniques required are well known to those skilled in the art.
• Formulations C1 to C3 which represent comparison compositions are described in Table 1. These compositions contain in the liquid part B only an apolar oil which does not allow them to achieve the desired non-curling property and obtained with the compositions according to the invention. Indeed, formulas C1, C2 give cohesive fractures on glass after 20 minutes according to FINAT test l.
• compositions F4 to Fl3 of compositions according to the invention are described in Table 1.
• the formulas according to the invention give adhesive breaks after 20 minutes and 1 hour which leaves time to recover the vials on the labeling line and remove the labels to recycle the vial to the labeling.
• the formulas F6, F7, F8, F8, Fl1 and Fl2 make it possible to obtain adhesive fractures after 24 h with only a slight increase in peel over time (approximately 20%).

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