JP2002524580A - Co-extrusion structure - Google Patents

Abstract

Summary [57] A stampable and matrix-peelable adhesive structure and associated manufacturing methods are disclosed. This adhesive structure finds utility as a label comprising a coextrudate of a polymer film (31) and an adhesive layer (30) that can be formed from a thermoplastic elastomer and a tackifier. In addition, additional and release layers (21) can be incorporated into the adhesive structure of the present invention.

Description

DETAILED DESCRIPTION OF THE INVENTION

CROSS-REFERENCE TO RELATED APPLICATIONS [0001] This application is related to co-pending US application Ser. No. 09 / 148,365 (September 4, 1998).
Which is a continuation-in-part application of the present invention, and the entire description and claims thereof are incorporated herein by reference.

FIELD OF THE INVENTION [0002] The present invention relates to thin co-extruded adhesive structures used to make tags, labels, labels, transfer papers, and the like, and more particularly to highly compliant, The present invention relates to a cost-effective coextruded pressure-sensitive adhesive structure.

BACKGROUND OF THE INVENTION [0003] Pressure sensitive adhesive (PSA) structures, such as labels, tapes, transfer papers, signs, etc., are known in the art. For example, PSA label structures are commonly used to apply specific facestocks having specific print properties to an object or article. A PSA label structure typically includes a release liner, a PSA layer disposed on the liner, and a facestock laminated on the PSA layer. The lamination may be by first coating or laminating the PSA to the liner and then laminating the facestock to the PSA coated liner; alternatively, the PSA may be coated or laminated to the facestock and then the PSA coated face It can be formed by laminating the stock on a liner. The facestock is manufactured from a web or sheet, paper, cardboard or plastic, as a feature, on which information or other indicia is placed, either before or after the facestock is laminated to the PSA and liner. Is printed. Facestock / PSA /
In a typical process of "converting" a liner laminate, the laminate is printed on an exposed facestock surface, the laminate is stamped to the liner surface, contouring the shape of the label, and Waste material (matrix) is cut off. The PSA label facestock and adhesive are then
The label is separated from the liner and adhered to the substrate surface by contacting the PSA layer of the label with the substrate surface. In the most prevalent labeling process, the label is separated from the liner by bending the liner back over the peel plate, where the label is sufficient to maintain a straight path to the desired substrate surface. Hard.

[0004] As used in this patent application, "separation" refers to removing the label from the liner, "apply" refers to adhering the label to the substrate surface, and "enforcement". Or "operability" refers to the combined steps of separation and application. "Peel plate enforcement" means the use of a peel plate or other similar device having a small radius of curvature in separating the liner from the label.

[0005] The term "faceless" pressure-sensitive adhesive structure is referred to herein as being very thin (
(E.g., less than 1 mil, preferably 0.1-0.5 or 0.6 mils), and that the manufacturing methods disclosed herein are in contrast to conventional PSA label structure manufacturing methods. Represents As described above, in conventional manufacturing of PSA label materials, a self-supporting preformed web or sheet is laminated to the PSA ("preforming" means that the facestock is self-contained in a previous manufacturing process). Formed on a supporting web or sheet, and, in the case of liquid or molten facestock material, means that the material has been dried or cured)
. The faceless structure of the present invention is a film-forming material (hereinafter referred to as “FFM”).
And sometimes by co-extruding an adhesive, whereby the facestock web or sheet and the adhesive are formed in situ.

[0006] In making and manufacturing PSA structures, a significant amount of the overall cost involved is the material cost for different material layers (eg, PSA and facestock (for paper, cardboard, or plastic)). caused by. Layer thickness and layer material may be, for such conventional PSA structures, convertible (eg, by conventional conversion techniques, such as punching and matrix release); workability (eg, conventional, such as peel plates, etc.). Providing the desired properties of compliance (e.g., by the enforcement equipment); and of being adaptable (e.g., allowing applied labels to adhere to irregular or deformable substrate surfaces without detachment or damage). And so on.

[0007] The stiffness of a PSA structure can have an impact on its convertibility and workability.
It is known. The stiffness of a label for a given material is such that the thinner the label is made,
Decrease. As a rule of thumb, the more stiff a structure is, the more transformable and enforceable it is. However, it is known that the compliance of PSA structures decreases as the stiffness of the structure increases. Thus, the objective stiffness of the PSA structure is a compromise between convertibility / enforceability and adaptability, and cost. If the stiffness of the label is too low, the label will go around the lined peel plate. It is an object of the present invention to provide a label structure with minimal material that is sufficiently rigid to be enforceable using a peel plate.

[0008] Prior art PSA structures having a Gurley stiffness of at least 10, more typically at least 20 or more, are known and are disclosed in US Pat. No. 5,186,186.
Nos. 782; 5,516,393; 4,713,273; and 5,451,283. Patents' 782, '393, and' 2
No. 83 teaches that heat-set films can be run at high speeds, with the appropriate difference between longitudinal and transverse stiffness (the latter of the two being lower) and still be flexible films. The concept that it could be suitable for end use was used. Such label films provide acceptable overall compliance to flexible substrates, even though the inherent flexibility of the film is lower than the then standard polymer labels based on polyvinyl chloride (PVC). Could be shown.

For certain end uses requiring a highly compliant PSA structure, the label may include:
Uses that are adhered to small diameter contoured or irregular surfaces. In such end use, unnecessary structural stiffness or stiffness may impede the ability of the label to conformally adhere to the underlying substrate surface. Further, these conventional PSA structures are not manufactured in the most economically efficient manner.

Furthermore, conventional PSA label structures are not well suited for certain uses (eg, the use of labels where the label and underlying substrate are exposed to certain process conditions). For example, conventional PSA label constructions having a paper facestock and / or lacking the required conformability properties can be used to clean / rinse, fill, and pasteurize when used on glass beverage bottles. During the process,
It is known to affect disadvantages. This is due not only to the decomposition of the paper facestock itself, but also to the inadequate maintenance of PSA adhesion to the substrate surface. Such label lifting can be due to the stiffness or stiffness of such conventional PSA labels, and this lifting, once the PSA is heated, causes the label and PSA to separate and cause the substrate to peel off. It is thought to float off the surface. In this example, the paper label is applied to the bottle after the bottle has been rinsed, filled, and pasteurized to avoid damage to the paper label. That is, the label is "post applied." Generally, printed paper labels are post-applied to filled bottles using water-based or hot melt adhesives.

If the post-applied paper label does not adhere completely to the bottle, is not aligned with the bottle, or is otherwise incorrectly applied to the filled bottle, The entire bottle and contents are unusable and must be disposed of. Thus, a glass bottle is desired that is labeled and inspected before filling and pasteurizing, thereby eliminating defective bottles and labels.

Following bottle formation in a bottle manufacturing plant, certain high performance acrylic PS
It is known in the art to use A to pre-apply flexible labels to glass bottles. Examples include Optiflex labels available from Flexcon and Primeli available from Polykote Corporation.
Ne label film. These labels are generally able to withstand bottle washing / rinsing, filling, and pasteurization operations in bottle filling plants, but they use special adhesives (eg, solvent or emulsion acrylics) Adhesives are not economically desirable from a manufacturing perspective and make these labels an unattractive option when compared to conventional gum type labels.

Accordingly, it is desirable to provide a thin PSA structure for use on labels, tags, transfer paper, signs, and the like. In one embodiment, any messages or indicia printed on such structures are protected from damage that may be caused by contact with adjacent physical objects or by exposure to moisture, water, etc. Is desirable. It is also desirable that the PSA label structure be converted at high speed and have high performance by stamping and matrix stripping methods. Such a PSA structure, when applied to a glass beverage bottle, can withstand rinsing, filling, and pasteurization operations, whereby the PSA structure can be used as a pre-applied label. It is even more desirable. Such PSA constructs are also useful in fruit labeling, and in this application these labels may be labeled during the various transport methods used (sorting, washing, etc.). (Including floating the fruit in various solutions) should be resistant to moisture. It is also desirable that the PSA label structure be manufactured in an economically efficient manner as compared to conventional PSA structures.

SUMMARY OF THE INVENTION A stampable and matrix-separable adhesive structure is described, which comprises the following: A continuous polymer film having an upper surface and a lower surface,
B. a polymer film having a thickness from about 0.1 mil to about 1 mil; An adhesive layer having an upper surface and a lower surface, wherein the upper surface of the adhesive layer is adhesively bonded to the lower surface of the polymer film, provided that the adhesive layer has If the adhesive contains a thermoplastic component and a solid tackifying resin component, the thickness of the polymer film (A) can be up to 1.5-2 mils.

The present invention also relates to a stampable and matrix-peelable pressure-sensitive adhesive label structure, which comprises: A coextrudate comprising: A-1. A continuous polymer film having an upper surface and a lower surface, wherein the film thickness is from about 0.1 mil to about 1 mil; and A-2. A. A pressure-sensitive adhesive layer having an upper surface and a lower surface, wherein the upper surface of the adhesive layer adheres and bonds to the lower surface of the polymer film; A substrate having a release surface, wherein the release surface contacts the lower surface of the adhesive layer of the co-extrudate, provided that the adhesive of the adhesive layer comprises a thermoplastic elastomer component and a solid When a tackifier component is contained, the thickness of the polymer film (A) is 2
Can be a mill. In some applications, particularly where the thickness of the continuous polymer film is at the lower end of the stated range, the stiffness and other properties of the structure may result in another polymer film being laminated on top of the continuous polymer film. Can be improved. Alternatively, if the structure does not have the stiffness required for peel plate application, U.S. Patent Nos. 4,217,164 and 4,303,
The structure may be applied to a given substrate using manual and other application techniques described in U.S. Pat. No. 461, and U.S. Pat. No. 4,896,793.

The invention also includes a punched label, especially a coextrudate, which can be prepared by punching the punchable and matrix-peelable adhesive structure of the present invention, in combination with a substrate having a release surface, wherein: An adhesive structure as described above wherein the release surface is in contact with the lower surface of the coextrudate adhesive layer is described. In general,
The substrate having a release surface is a release coated liner or carrier. The adhesive structure and the method for preparing the stamped label are also
be written.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a thin, printable, replaceable, dispersible, and conformable co-extruded adhesive structure, the adhesive structure generally comprising: A) a thin continuous layer of polymer film from about 0.1 mil to about 1 or 2 mils, and (B) an adhesive layer adhesively bonded to the lower surface of the polymer film. A significant advantage of such a coextrudate is the low caliper (c) laminated to the hot melt PSA.
aliper A technique is provided for forming a very thin label structure of a printable film. Such a thin film PSA label structure,
Due to the difficulties in handling such thin polymer films, which can be as thin as 0.2 to about 0.5 or 0.6 mils, they are commonly obtained using conventional manufacturing processes. Absent. In one embodiment, the thin continuous layer (A) of the polymer film may include one or more film layers. Thus, film (A) can be a multi-layer polymer film containing as few as 9 or 10 thin polymer layers or even 500 or 1000 polymer film layers.

In a first embodiment, the coextruded polymer film may be any polymer material that can be coextruded with various adhesives and, more particularly, as described below, with a pressure sensitive adhesive. Can be obtained from For example, it is desirable that the polymer film material have a solubility parameter that is inconsistent or incompatible with the solubility parameter of the adhesive to prevent migration between the two layers when co-extruded. obtain. The polymer film material also self-supports sufficiently to facilitate label dispersion (label separation and application) when combined with the adhesive layer (
A self-supporting structure should be provided. Alternatively, if the polymer film combined with the adhesive is not sufficiently self-supporting, a top laminate layer is applied to the exposed surface of the polymer film to provide additional rigidity and dispersibility and more details below. Other properties may be provided as described in. Preferably, the polymer film material is selected to provide desired properties to the structure, such as printability, punchability, matrix strippability, dispersibility, and the like.

Polymer film materials useful in the coextrudates of the present invention include polystyrene, polyolefins, polyamides, polyesters, polycarbonates, polyvinyl alcohols, polyethylene vinyl alcohols, polyurethanes, polyacrylates, poly (vinyl esters), ionomers and the like. And mixtures thereof. In one preferred embodiment, the polymer film material is a polyolefin. The polyolefin film materials are generally characterized as having a melt index or melt flow rate of less than 30, more often less than 20, and most often less than 10, which are referred to as ASTM Test M
determined by method 1238.

Polyolefins that can be utilized as the polymer film material include blends of polymers and copolymers such as ethylene, propylene, 1-butene, or mixtures of such polymers and copolymers. Preferably, these polyolefins include ethylene and propylene polymers and copolymers. In another preferred embodiment, these polyolefins include propylene homopolymers and copolymers such as propylene-ethylene and propylene-1-butene copolymers. Also useful are blends of polypropylene and polyethylene with each other, or one or both of them with a polypropylene-polyethylene copolymer. In another embodiment, these polyolefin film materials have a very high propylene content (
Either a polypropylene homopolymer or a polypropylene-ethylene copolymer), or a blend of polypropylene and polyethylene having a low ethylene content, or a blend of propylene-1-butene copolymer or polypropylene and poly-1-butene having a low butene content.

[0021] Various polyethylenes can be used as the polymer film material, including low density, medium density, and high density polyethylene. Useful low density polyethylene (
An example of (LDPE) is Rexene 1017 available from Huntsman.

[0022] Propylene homopolymers that can be utilized as the polymer film material in the structures of the present invention, either in combination with the propylene copolymers described herein or alone, include from about 0.5 to about 20 melt flow rate (MF
R) (ASTM Test D 1238, determined by condition L). In one embodiment, 1
Propylene homopolymers having an MRF of less than 0, and more often from about 4 to about 10, are particularly useful and provide a facestock with improved punchability. Useful propylene homopolymers also may be characterized as having a density in the range of about 0.88～ about 0.92 g / cm ^3. Many useful propylene homopolymers are commercially available from various sources, and some useful polymers include: 5A97 (Uni)
commercially available from Carbide on Carbide, with a melt flow of 12.0 g / 10 min.
DX5E66 (which also has a density of 90 g / cm ³ );
commercially available from ide, having an MFI of 8.8 g / 10 min and a density of 0.90 g / cm ³ ); and WRD5-1057 (commercially available from Union Carbide, 3.9 g / 10 min MFI and 0.90 g / cm ^3). Having a density of. Useful commercial propylene homopolymers are also available from Fina and Montel.

Particularly useful polyamide resins include EMS American Grilon
Inc. Sumter, SC. From General Trademarks (CF6S, C
R-9, SE3303 and G-21). Gri
Vory G-21 has a glass transition temperature of 125 ° C., a melt flow index of 90 ml / 10 min (DIN 53735) and an elongation at break of 15 (AST).
MD638). Grivor
y CF65 is a nylon 6/12 film grade resin with a melting point of 135 ° C., a melt flow index of 50 ml / 10 min, and an elongation at break of over 350%. Grilon CR9 has a melting point of 200 ° C., 200 ml / 1.
Another nylon 6/12 film grade resin having a melt flow index of 0 minutes and an elongation at break of 250%. Grilon XE 3303
Has a melting point of 200 ° C., a melt flow index of 60 ml / 10 min, and 1
Nylon 6.6 / 6.10 film grade resin with an elongation at break of 00%. Other useful polyamide resins include, for example, Wayne, New Jers
marketed in the Uni-Rez product line from Union Camp of ey,
And Bostik, Emery, Fuller, Henkel (Versam
(product line). Other suitable polyamides include those produced by condensing a dimerized vegetable acid with hexamethylene diamine. Examples of polyamides available from Union Camp include Uni-Rez 2665; Uni-Rez.
2620; Uni-Rez 2623; and Uni-Rez 2695. Some of the physical properties of polymer films formed from Uni-Rez polyamides are summarized in Table 1 below.

[0024]

[Table 1] Polystyrene can also be utilized as the polymer film material in the coextruded bonded structures of the present invention, and styrene and substituted styrene (eg, α
-Methylstyrene). Examples of styrene copolymers and styrene terpolymers include: acrylonitrile-butene-styrene (ABS); styrene-acrylonitrile copolymer (SAN); styrene butadiene (SB); styrene-maleic anhydride (SM
A); and styrene-methyl methacrylate (SMMA). Examples of useful styrene copolymers are KR-10 (Phillips Petroleum C
o. From). KR-10 is believed to be a copolymer of styrene with 1,3-butadiene.

[0025] Polyurethanes can also be used as the polymer film material in the coextruded adhesive structures of the present invention, and these polyurethanes can include aliphatic and aromatic polyurethanes.

[0026] Polyesters prepared from various glycols or polyols and one or more aliphatic or aromatic carboxylic acids are also useful film materials. Polyethylene terephthalate (PET) and PETG (PET modified with cyclohexane dimethanol) are useful film-forming materials, these being Eastm
available from a variety of commercial sources, including an. For example, Kodar 676
3 is PETG available from Eastman Chemical. du
Another useful polyester from Pont is Selar PT-8307, which is a polyethylene terephthalate.

Acrylate polymers and copolymers and alkylene vinyl acetate resins (eg, EVA polymers) are also useful as film-forming materials in preparing the coextruded adhesive structures of the present invention. Commercial examples of available polymers include E
screenene UL-7520 (Exxon) (copolymer of ethylene with 19.3% vinyl acetate); Nucrell 699 (du Pont)
) (Ethylene copolymer containing 11% methacrylic acid).

Also useful are ionomers (polyolefins containing molecular chain ionic bonds).
Examples of ionomers include ionomeric ethylene copolymers such as Surlyn 1706 (du Pont), which is believed to contain interchain ionic bonds based on the zinc salt of the ethylene methacrylic acid copolymer. Surlyn
1702 (du Pont) is also a useful ionomer.

[0029] Polycarbonates are also useful, and these are Dow Chemical
al Co. (Calibre) E. FIG. Available from Plastics (Lexan) and Bayer (Makrolon). Most commercially available polycarbonates are obtained by the reaction of bisphenol A with carbonyl chloride in an interfacial process. Typical commercial polycarbonates have a molecular weight of about 22,000.
0 to about 35,000, and the melt flow rate is typically 4
２２22 g / 10 min.

The polymer film material may include inorganic fillers and other organic or inorganic additives to provide desired properties, such as appearance properties (opaque or colored films), durability and processing properties. Nucleating agents can be added to increase crystallinity and thereby increase stiffness. Examples of useful materials include calcium carbonate, titanium dioxide, metal particles, fibers, flame retardants, antioxidants, heat stabilizers, light stabilizers, UV stabilizers, antiblocking agents.
nt), processing aids, acid acceptors, and the like.

Various nucleating agents and pigments can be incorporated into the films of the present invention. The amount of nucleating agent added should be sufficient to provide the desired modification of the crystal structure, but not to have a deleterious effect on the desired properties of the film. The use of nucleating agents to modify the crystal structure, provide large amounts of fairly small crystals or spherulites, and improve the clarity (clarity), and stiffness, and punchability of the film is generally Is desired. Obviously, the amount of nucleating agent added to the film formulation should not have a deleterious effect on the clarity of the film. Nucleating agents previously used for polymer films include mineral nucleating agents and organic nucleating agents. Examples of mineral nucleating agents include carbon black, silica, kaolin and talc. Organic nucleating agents suggested as useful in polyolefin films include salts of aliphatic mono- or di-basic acids or arylalkyl acids (e.g., sodium succinate, sodium glutarate, Sodium caproate, sodium 4-methylvalerate, aluminum phenylacetate, and sodium cinnamate). Alkali metal and aluminum salts of aromatic and cycloaliphatic carboxylic acids, such as aluminum benzoate, sodium or potassium benzoate, sodium beta naphtholate, lithium benzoate and ter
Aluminum t-butyl benzoate) is also a useful organic nucleating agent. Substituted sorbitol derivatives such as bis (benzylidene) sorbitol and bis (alkyl benzylidine) sorbitol (where the alkyl group contains from about 2 to about 18 carbon atoms) are useful nucleating agents. More specifically, 1,3,2,4
Sorbitol derivatives such as dibenzylidene sorbitol, 1,3,2,4-di-para-methylbenzylidene sorbitol, and 1,3,2,4-di-para-methylbenzylidene sorbitol are effective nucleation for polypropylene Agent. Useful nucleating agents are commercially available from many sources. Millad 8C
-41-10 (a concentrate of 10% Millad 3988 and 90% polypropylene), Millad 3988 and Millad 3905 are Mill
iken Chemical Co. Is a sorbitol nucleating agent available from the US

[0032] The amount of nucleating agent incorporated into the film formulations of the present invention generally ranges from about 100 to about 6000 ppm of the film. In another embodiment, the amount of nucleating agent is from about 1000 to about 6000 ppm, more preferably from about 1500 to about 350 ppm.
0 ppm, more preferably in the range of about 2000-2500 ppm.

The polymer film material co-extrudes desired properties such as improved printability, weatherability, strength, water resistance, abrasion resistance, gloss, punchability, matrix strippability and other properties. Selected to provide a continuous polymer film in the article. That the surface of the film can be printed or adapted to be printed with ink using printing techniques (eg, flexographic printing, screen printing, offset lithography, letterpress printing, thermal transfer, etc.), and coating It is particularly desirable that the inks provided have acceptable adhesion to the surface of the film of the adhesive structure. The choice of polymer film forming material also
It is determined by its physical properties, such as melt viscosity, high-speed tensile strength, percent elongation. As discussed in more detail below, the co-extrusion of the polymer film material and the adhesive forming the co-extrudate depends on the melt viscosity of these two materials (ie, the first layer polymer film material and the adhesive material). Is promoted if are similar. Thus, the choice of the polymeric material used in forming the coextruded adhesive structure of the present invention can depend on the melt viscosity of the adhesive coextruded with the polymeric film forming material. In one embodiment, the first layer of polymer film material has a hot melt viscosity of about 0.5 at the applied shear rate during the coextrusion process.
07 to about 15 times, more often greater than 1 to about 15 times, and preferably 1 to about 1
It has a hot melt viscosity that is up to 0 times. Generally, this shear rate is about 100 / sec.
It is in the range of about 10.000 / sec.

[0034] The thickness of the polymeric film material is from about 0.1 to about 1.5 or even 2.0 mils. More often, the thickness of the film is from about 0.2 to about 1.0 mil. A thickness of about 0.5 mil is particularly useful. The continuous polymer film may include a single layer, or the film may be a multilayer film of two or more adjacent coextruded layers. For example, the film may comprise one layer of polyolefin and one layer of polyolefin and a copolymer of ethylene and vinyl acetate (
EVA). In another embodiment, the film comprises 3
Layers, such as a polyolefin base or core layer, and skin layers on either side of the base or core layer, which may be composed of the same or different polymer blends.

Here, considering the adhesive, the co-extruded structure of the present invention also includes an adhesive layer having an upper surface and a lower surface (hereinafter sometimes referred to as “substrate adhesive”).
including. Here, the upper surface of the adhesive layer is adhesively bonded to the lower surface of the polymer film. The adhesive can be a heat-activated adhesive, a hot melt adhesive, or a pressure sensitive adhesive (PSA). About 160 ° C
Adhesives that are tacky at any temperature up to (about 320 ° F.) are particularly useful.
PSAs that are tacky at ambient temperature are particularly useful in the coextruded bonded structures of the present invention. A variety of conventional PSAs can be used, provided that the viscosity has been modified or modified to be similar to the viscosity of the polymer film material coextruded with the adhesive. Useful PSA compositions are fluid or pumpable at the temperatures used in melt processing. Further, the adhesive composition,
It should not decompose significantly or gel at the temperatures used and over the time required for melt processing and extrusion. Typically, the adhesive composition has a viscosity at the processing temperature of 1000 poise to 1,000,000 poise.

The adhesives can be generally classified into the following categories: Random copolymer adhesives (eg, those based on acrylate and / or methacrylate copolymers, α-olefin copolymers, silicone copolymers, chloroprene / acrylonitrile copolymers, etc.) ), Block copolymer adhesives (including those based on linear block copolymers (ie, AB and ABA types), branched block copolymers, star block polymers, grafted or radial block copolymers, etc.). And natural and synthetic rubber adhesives.

A description of useful pressure sensitive adhesives is found in Encyclopedia of Polym
er Science and Engineering, Volume 13, Wile
y-Interscience Publishers (New York, 1
998). A further description of useful pressure sensitive adhesives can be found in Encyclopedia
pedia of Polymer Science and Technology
ogy, Volume 1, Interscience Publishers (New
York, 1964).

[0038] Commercially available pressure sensitive adhesives are useful in the present invention. Examples of these adhesives include HM-1597, HL-2207-X, HL-2115-X, HL-2193.
H. such as -X. B. Fuller Company, St. Paul, Mi
nn available hot melt pressure sensitive adhesives. Other useful commercially available pressure sensitive adhesives include Century Adhesives Corporation
on, Columnus, Ohio.

Conventional PSAs, including silicone-based PSAs, rubber-based PSAs, and acrylic-based PSAs are useful. Another commercially available example of a hot melt adhesive is Ato
Findley, Inc. (Wauwusa, Wisconsin) available from H2187-01. Further, U.S. Pat. No. 3,239,478
-Based block copolymer PSA described in Harlan
May also be utilized in the co-extruded adhesive structures of the present invention, which patent is incorporated herein by reference for its disclosure of such hot melt adhesives.

In one preferred embodiment, the pressure-sensitive adhesive utilized in the present invention includes a rubber-based elastomeric material such as a linear, branched, grafted or radial block copolymer, which comprises Represented by diblock structures AB, triblock structures ABA, radial or coupled structures (AB) _n and combinations thereof, wherein A is a hard thermoplastic phase or block Which is non-rubber or glassy or crystalline at room temperature, but fluid at high temperatures, and B represents a soft block, At room temperature or rubbery or elastomeric. These thermoplastic elastomers can have from about 75% by weight to
It contains about 95% by weight of rubber segments and may contain about 5% to 25% by weight of non-rubber segments.

The non-rubbery segments or hard blocks are composed of mono- or polycyclic aromatic hydrocarbons, more particularly vinyl-substituted aromatic hydrocarbons (which may in fact be mono- or bicyclic). Including polymers. Preferred rubbery blocks or segments are
A polymer block of a homopolymer or copolymer of an aliphatic conjugated diene.
Rubber materials such as polyisoprene, polybutadiene, and styrene butadiene rubber can be used to form rubber blocks or segments. Particularly preferred rubbery segments include polydienes and saturated olefin rubbers of ethylene / butylene or ethylene / propylene copolymers. The latter rubbers can be obtained from the corresponding unsaturated polyalkylene moieties such as polybutadiene and polyisoprene by hydrogenating them.

Block copolymers of vinyl aromatic hydrocarbons and conjugated dienes that can be utilized include any that exhibit elastomeric properties. The block copolymer may be a diblock, triblock, multiblock, star block, polyblock, or graft block copolymer. Throughout the specification and claims of the present invention, with respect to the structural features of block copolymers, the terms diblock, triblock, multiblock, polyblock, and graft or graft block refer to Encyclopedia of Polymer Sci.
once and Engineering, Vol. 2, (1985) John
Wiley & Sons, Inc. , New York, 325-326,
And J. E. FIG. Block Copolymers by McGrath, Sc
ence Technology, Dale J. et al. Meier, Harwo
od Academic Publishers, 1979, pp. 1-5.

Such block copolymers may include various ratios of conjugated dienes to vinyl aromatic hydrocarbons, including those containing up to about 40% by weight of vinyl aromatic hydrocarbon. Thus, linear or radial symmetry or asymmetry and of the formula A-
B, ABA, ABAB, BAB, (AB) ₀ , ₁ , ₂ . . . A multi-block copolymer having a structure represented by BA or the like may be utilized, where A is a polymer block of vinyl aromatic hydrocarbon or a conjugated diene / vinyl aromatic hydrocarbon tapered copolymer block; Is a rubbery polymer block of a conjugated diene.

Block copolymers can be prepared by any of the well known block or copolymerization procedures, including the sequential addition of monomers, increased addition of monomers, or coupling techniques (eg, US Pat. No. 3,251,905; No. 3
No. 3,598,887; and No. 4,219,62.
No. 7). As is well known, tapered copolymer blocks can be incorporated into multi-block copolymers by taking advantage of differences in copolymerization reaction rates to copolymerize mixtures of conjugated diene monomers and vinyl aromatic hydrocarbon monomers. Various patents describe the preparation of multi-block copolymers containing tapered copolymer blocks, including US Pat. No. 3,251,905;
Nos. 3,639,521; and 4,208,356, the disclosures of which are incorporated herein by reference.

Conjugated dienes that can be used to prepare polymers and copolymers include 4-
Those containing about 10 carbon atoms, more usually 4 to 6 carbon atoms.
Examples include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene, chloroprene, 1,3-pentadiene, 1,3-hexadiene, and the like. No. Mixtures of these conjugated dienes can also be used. Preferred conjugated dienes are isoprene and 1,3-butadiene.

Examples of vinyl aromatic hydrocarbons that can be used to prepare the copolymer include styrene and various substituted styrenes (eg, o-methylstyrene, p-methylstyrene, p-tert-butylstyrene, 1,1 3-dimethylstyrene, α-methylstyrene, β-methylstyrene, p-isopropylstyrene, 2,3-dimethylstyrene, o-chlorostyrene, p-chlorostyrene, o-bromostyrene,
2-chloro-4-methylstyrene). The preferred vinyl aromatic hydrocarbon is styrene.

Many of the above copolymers of conjugated dienes and vinyl aromatic compounds are commercially available. Prior to hydrogenation, the number average molecular weight of the block copolymer is about 20,000
To about 500,000, preferably from about 40,000 to about 300,000.

[0048] The average molecular weight of the individual blocks in the copolymer can vary within certain limitations. In many cases, the vinyl aromatic block has a number average molecular weight on the order of about 2000 to about 125,000, preferably between about 4000 and 60,000. The conjugated diene block, before or after hydrogenation, is on the order of about 10,000 to about 450,000, and more preferably about 35,5
It has a number average molecular weight of 000 to 150,000.

Also, prior to hydrogenation, the vinyl content of the conjugated diene moiety is typically about 10%
And about 80%, and the vinyl content is preferably about 25% to about 65%, especially 35% to 55% (if it is desired that the modified block copolymer exhibit rubbery elasticity). The vinyl content of the block copolymer can be measured by a nuclear magnetic resonance method.

Particular examples of diblock copolymers include styrene-butadiene (SB), styrene-isoprene (SI), and hydrogenated derivatives thereof. Examples of triblock polymers include styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (SIS), α-methylstyrene-butadiene-α-
Methylstyrene and α-methylstyrene-isoprene-α-methylstyrene. Examples of commercially available block copolymers useful as the adhesives of the present invention include those available from Shell Chemical Company and those listed in Table II below.

[0051]

[Table 2] Vector 4111 is a SIS block copolymer commercially available from Dexco (Houston Texas).

Hydrogenation of an SBS copolymer containing a rubbery segment of a mixture of 1,4 and 1,2 isomers gives a styrene-ethylene-butylenestyrene (SEBS) block copolymer. Similarly, hydrogenation of a SIS polymer results in a styrene-ethylene propylene-styrene (SEPS) block copolymer.

The selective hydrogenation of block copolymers can be carried out by a variety of well-known processes, including precious metals such as Raney nickel, platinum, palladium, and catalytic hydrogenation such as soluble transition metal catalysts. Is mentioned. A suitable hydrogenation process that can be used is that the diene-containing polymer or copolymer is dissolved in an inert hydrocarbon diluent such as cyclohexane and hydrogenated by reaction with hydrogen in the presence of a soluble hydrogenation catalyst Things. Such a procedure is described in U.S. Pat.
Nos. 986 and 4,226,952, the disclosures of which are incorporated herein by reference. Such hydrogenation of the block copolymer is selectively hydrogenated with a residual unsaturation content in the polydiene block of about 0.5% to about 20% of the original unsaturation content prior to hydrogenation. It is carried out in a manner and to a degree to produce a polymerized copolymer.

In one embodiment, the conjugated diene portion of the block copolymer is at least 90% unsaturated, more often at least 95% unsaturated, while the vinyl aromatic portion is significantly hydrogenated. Not done. Particularly useful hydrogenated block copolymers are the hydrogenated products of styrene-isoprene-styrene block copolymers, such as styrene- (ethylene / propylene) -styrene block polymers. When the polystyrene-polybutadiene-polystyrene block copolymer is hydrogenated, it is preferred that the ratio of 1,2-polybutadiene to 1,4-polybutadiene in the polymer is from about 30:70 to about 70:30. When such a block copolymer is hydrogenated, the product obtained is ethylene and 1-
It resembles the regular copolymer block of butene (EB). As shown above,
When a conjugated diene is used as the isoprene, the resulting hydrogenated product resembles a regular copolymer block of ethylene and propylene (EP).

Many selectively hydrogenated block copolymers have the commercial name “Krato”
"nG" is commercially available from Shell Chemical Company. One example is Kraton G1652, a hydrogenated SBS triblock containing about 30% by weight of a styrene endblock and a mid-block that is a copolymer of ethylene and 1-butene (EB). A low molecular weight version of G1652 is available from Shell under the name Kraton G1650. Kraton G1651 is another SEBS block copolymer, which contains about 33% by weight styrene. Kraton G1657
Is a SEBS diblock copolymer, which contains about 13% by weight styrene. The styrene content is determined by Kraton G1650 and Kraton G
Less than the styrene content in 1652.

In another embodiment, the selective hydrogenated block copolymer is of the formula: B _n (AB) _{o Ap} where n = 0 or 1; o is 1-100 P is 0 or 1; before hydrogenation, each B is predominantly from about 20,000 to about 450,00
A polymerized conjugated diene hydrocarbon block having a number average molecular weight of 0; each A is primarily a polymerized vinyl aromatic hydrocarbon block having a number average molecular weight of about 2000 to about 115,000. Yes; Block A comprises about 5% to about 95% by weight of the copolymer; and the unsaturation of Block B is less than about 10% of the original unsaturation. In another embodiment, the unsaturation of block B is reduced by hydrogenation from its original value to less than 5% and the average unsaturation of the hydrogenated block copolymer is reduced to less than 20% of its original value. Is done.

The block copolymer also comprises reacting an α, β-olefinic unsaturated monocarboxylic or dicarboxylic acid on the selectively hydrogenated block copolymer of a vinyl aromatic hydrocarbon and a conjugated diene as described above. Functional polymers such as may be obtained. The reaction between the carboxylic reagents of the graft block copolymer can be performed in solution in the presence of a free radical initiator or by a melting process.

The preparation of block copolymers of conjugated dienes and vinyl aromatic hydrocarbons grafted with various selectively hydrogenated carboxylic reagents is disclosed in US Pat.
No. 4,657,970; and No. 4,795,78.
No. 2, including the disclosure of these patents,
In the context of selectively hydrogenated block copolymers of conjugated dienes and vinyl aromatic compounds, the preparation of such compounds is incorporated herein by reference. U.S. Pat. No. 4,795,782 discloses a solution process and a melt process.
An example of the preparation of a grafted block copolymer is described and given. U.S. Pat. No. 4,578,429 discloses Kraton G1652 (SEBS) polymer using 2,5-dimethyl-2,5-di (t-butylperoxy) hexane by a melting process in a twin screw extruder. Includes examples of grafting with maleic anhydride (see column 8, lines 40-61).

Examples of commercially available maleated selective hydrogenated copolymers of styrene and butadiene include Kraton FG1901X, FG1921X, and FG1
924X (Shell), often referred to as a maleated, selectively hydrogenated SEBS copolymer. FG1901X is about 1.7% by weight.
Containing bound functional groups, such as succinic anhydride, and about 28% by weight of styrene. FG1921X contains about 1% by weight of bound functional groups such as succinic anhydride and 29% by weight of styrene. FG1924X contains bound functional groups such as about 13% styrene and about 1% succinic anhydride.

[0060] Useful block copolymers are also available from Nippon Zeon Co. , 2-1
, Marunouchi, Chiyoda-ku, Tokyo, Japan. For example, Quintac 3530 is available from Nippon Zeo
n and is considered to be a linear styrene-isoprene-styrene block copolymer.

[0061] The polymer film materials and adhesive compositions used to form the structures of the present invention can be neat, or they can be emulsion or solvent based. Emulsion and solvent-based acrylic-based PS
A is known and is described, for example, in US Pat. Nos. 5,638,811 and 5,538,811.
No. 164,444, and these patents are incorporated herein by reference for such disclosure. If emulsions of film materials and / or adhesive compositions are used, US Pat. No. 5,716,669 (
Water can be removed in an extruder using the process described and claimed in LaRose et al.). However, the co-extruded film material and PSA are compositions that are substantially free of water and / or solvent (eg, less than 1% by weight). The presence of water or solvent during the coextrusion process can and generally results in pinholes or bubbles in the coextruded film. The presence of voids in the film due to steam is known in the art as "moist slits.
ure slit) ".

The adhesive structure of the present invention is formed by co-extrusion of a film of the polymer film material described above and an adhesive layer as described more fully below, so that the hot melt of the polymer film material and the adhesive is performed. Viscosity is a viscosity that can provide a co-extrudate of a window or a continuous, uniform layer of polymer film material and adhesive to prevent defects in the film and mixing of the polymer film material and adhesive during the co-extrusion process. Should be within range. Mixing of the film material with the adhesive is not desired because it causes a loss of clarity in the extruded film and a tendency to cause blocking. Generally, polymer film materials are:
At the shear rate experienced during the co-extrusion process, the hot melt viscosity of the adhesive is about 0.0
It has a hot melt viscosity in the range of a factor of 7 to about 15 times. Generally, the shear rate varies between about 100 s ^-1 and about 10,000 s ^-1 . More often, this factor is from about 1 to about 15. Preferred factors are 1 to about 10. It is also desirable that the polymer film materials and adhesives have relatively similar melt viscosities at the extrusion temperature. For example, if the PSA is a conventional hot melt adhesive, the extrusion temperature of the PSA is in the range of about 150C to 200C, and preferably is about 175C.
~ 200 ° C. Accordingly, it is desirable that the polymeric film material selected for use with the PSA have an extrusion temperature of less than about 200C, and preferably in the range of about 150C to about 180C.

The continuous polymer film in the adhesive structure of the present invention has a high speed tensile strength of at least 1 lb / inch width and more often a high speed tensile strength in the range of about 2 lb / inch width to about 10 lb / inch width. It is desirable to have a tensile strength. Fast tensile strength is determined according to a modified TAPPI 494 test by moving the sample at a speed of 100 feet / minute. This high-speed tensile strength of the polymer film should be sufficient at a given thickness to allow matrix release after punching without excessive tearing of the film. The polymer film material in the coextruded adhesive structure of the present invention has less than about 200% at break, more preferably less than about 1%.
It is also desirable to have an elongation in the range of 25% to about 175%. At break,
A polymeric film material having a% ultimate elongation of greater than about 200% can produce an adhesive structure that is difficult to convert by stamping and matrix peeling, which depends on the type of adhesive and polymer film material, and their Depends on each coating weight.

In one embodiment, important features of the coextruded adhesive structure of the present invention include: (1) a thin polymer film and (2) an adhesive layer having a relatively low coat weight. . Thus, the adhesive structure of the present invention can be used in a range from about 0.1 mil to about 1 mil.
. It is characterized as having a polymer film thickness of 5 or 2 mils and an adhesive coating weight of less than 40 g / m ² , preferably less than 20 g / m ² . In one embodiment, the adhesive layer has a coating weight ranging from about ^{0.5g / m 2 ~20g / m 2} . Alternatively, the thickness of the adhesive layer is from about 0.02 mil to about 2 mil,
More preferably, it can range between about 0.02 mil and about 0.8 mil. It should be understood that the thickness and coat weight of both the polymer film and the adhesive layer can vary depending on the different types of polymer film materials and adhesives selected and the properties desired in the adhesive structure. is there. For example, different polymers and different film thicknesses result in structures with different conformability and different stiffness. In one embodiment, this structure of the invention should have sufficient Gurley stiffness to allow for rapid preparation, eg, by peel-plate, but is compatible with most surfaces Should be flexible enough to be possible. In applications where a high degree of conformability is required, the adhesive structure may be less than about 10, even about 5 in the machine direction.
It can be designed to have a Gurley stiffness of less than. Gurley stiffness is T
Determined according to APPI test 543 pm. Typically, the adhesive structures of the present invention have a Gurley stiffness of less than 40 mg, and even less than 25 mg, in the machine direction.

The features of the co-extruded adhesive structure of the present invention also indicate that such thin polymer films require the structural properties (eg, strength and stiffness) necessary to facilitate conversion.
Can be provided. The coextruded adhesive structure of the present invention having a predetermined thickness of the polymer film, in combination with an adhesive layer, provides a sufficiently self-supporting adhesive to facilitate conversion (ie, printing, punching and matrix release). Provide a structure. As described herein, if the longitudinal stiffness of the co-extruded adhesive structure is too low (eg, less than 10 Gurley) to be used satisfactorily in high speed peel-plate preparation techniques. The body can be prepared using other techniques, or this stiffness is increased by top laminating the polymer film to a thin polymer film of a co-extruded adhesive structure as described herein. Can be done. Useful preparation techniques and preparation equipment for low-rigid adhesive structures are described in U.S. Patent Nos. 4,217,164, 4,303,461 and 4,896,793, and , These patents are hereby incorporated by reference.
Incorporated for such an explanation.

As mentioned above, in one embodiment, the adhesive composition comprises a thermoplastic elastomer comprising at least one thermoplastic elastomeric block copolymer, including linear, branched, grafted or radial block copolymers. including. further,
The coextruded adhesive composition also includes at least one solid tackifying resin component. Solid tackifiers are defined herein as having a softening point above 80 ° C. When a solid tackifying resin component is present, the coextrudable pressure-sensitive adhesive composition generally comprises from about 40 to about 80% by weight of a thermoplastic elastomer component and from about 20 to about 60% by weight (preferably, about 55-65% by weight) of a solid tackifying resin component. This solid tackifier is build tack (build
reduce the module of the mixture sufficient for tack or adhesion. Also, solid tackifiers (particularly, higher molecular weight solid tackifiers (for example, 2000
Solid tackifiers with higher Mw) and lower dispersibility (Mw / Mn = less than about 3) have little sensitivity to migration to the polymer film layer, and this is desirable. This is because transfer of the tackifier to the polymer film layer causes dimensional instability and the structure can swell and / or wrinkle and become too soft.
In addition, the structure may lose adhesive properties or cause blocking, and the ability of the satisfactorily printed polymer film to be reduced by migration of the tackifier. For example, attempts to print the polymer film layer after migration of the tackifier or other components from the adhesive layer can cause poor fixation and / or blurring of the ink in the print. Migration of tackifiers or other components present in the adhesive layer is particularly problematic when the polymer film contains a polyolefin such as polyethylene.

Conventional solid tackifier resins include hydrocarbon resins, rosins, hydrogenated rosins, rosin esters, polyterpene resins, and other resins that exhibit the proper balance of properties. A variety of useful solid tackifier resins are commercially available (eg, A
Trade Name Zonata by rizona Chemical Company
terpene resin sold under the trade name Exxon Chemical Co.
petroleum hydrocarbon resins, such as the resins sold by E. mpany under the trade name Escorez). One particular example of a useful solid tackifier is Escorez 25
Is 96, which is a C ₅ -C ₉ (aliphatic is aromatic modified) Synthesis tackifier having a 2100 Mw and 2.69 dispersibility (Mw / Mn). Another useful solid tackifier is Escorez 1310LC, which is identified as an aliphatic hydrocarbon resin having a Mw of 1350 and a dispersibility of 1.8. Wi
ngtack 95 is a synthetic tackifier resin available from Goodyear, Akron, Ohio, which consists primarily of a polymerized structure derived from piperylene and isoprene.

The module of the adhesive mixture to be coextruded can also be reduced by the incorporation of a liquid rubber (ie, liquid at room temperature). Liquid rubbers generally have a Mw of at least 5,000 (often at least above 20,000).
Incorporation of the liquid rubber in an amount of less than 10% by weight, and even less than 5% by weight, based on the total weight of the adhesive formulation, results in an adhesive that can be co-extruded with the polymeric film material. The incorporation of liquid rubber also produces an adhesive with increased tack and adhesion. Liquid block copolymers (eg, liquid styrene-isoprene block copolymers) are particularly useful. For example, Kraton
LVSI-101 (available from Shell Chemical Company) is effective in lowering the module of the adhesive, and surprisingly it has been found that this liquid styrene-isoprene block copolymer functions as a processing aid. Issued, which improves the smoothness of the flow of the adhesive from the mold. Kraton LVSI-101 has a weight average molecular weight of about 40,000. Another example of a useful liquid rubber is liquid polyisoprene obtained by selectively or partially decomposing high molecular weight polyisoprene. An example of a commercially available partially degraded high molecular weight polyisoprene is Elementis Pe
rformance Polymers, Bellville, N.W. J. D-400, and the liquid rubber is about 20,000
Mw. Other liquid rubbers that can be incorporated into the adhesive mixture include liquid styrene-butadiene rubber, liquid butadiene rubber, ethylene-propylene rubber, and the like.

The adhesive composition may also include other materials (eg, antioxidants, heat and light stabilizers, UV absorbers, viscosity modifiers, fillers, colorants, antiblocking agents, reinforcing agents, processing acids (
processing acid)). Hindered
rd) Phenol and amine antioxidant compounds can be included in the adhesive composition, and a wide variety of such antioxidant compounds are known in the art. Various antioxidants are available from Ciba-Geigy under the generic trade names "Irganox" and "I.
rgafos ". For example, n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenol) -proprionate, a hindered phenol antioxidant, has a general trade name of Irgan.
ox 1076 ". Irganox 1010 is identified as tetrakis (methylene 3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenol) propionate) methane. Irgafos 168 is another useful antioxidant from Ciba-Geigy.

[0070] Hydroquinone-based antioxidants may also be utilized, and one example of such an antioxidant is 2,5-di-tert-amyl-hydroquinone.

Light stabilizers, heat stabilizers, and UV absorbers can also be included in the adhesive composition. Examples of the ultraviolet absorber include a benzotriazole derivative, hydroxybenzylphenone, an ester of benzoic acid, oxalic acid, and a diamine. Light stabilizers include hindered amine light stabilizers, and heat stabilizers include dithiocarbamate compositions (eg, zinc dibutyldithiocarbamate).

Adhesive compositions, such as polymer films, can contain inorganic fillers and other organic and inorganic additives to provide desired properties. Examples of useful fillers include calcium carbamate, titanium dioxide, metal powder, fiber, and the like. Examples of useful endblock enhancers are Neville Resins
From Cumar LX509.

The following example illustrates a specific pressure sensitive adhesive formulation, which can be coextruded with a polymeric film material as described above. All parts and percentages are by weight and temperatures are in degrees Celsius unless otherwise indicated in the examples, claims, and elsewhere in the description.

[0074]

[Table 3] As described above, the adhesive structure of the present invention includes a coextrudate of a polymer film and an adhesive layer. The polymer film may include one or more layers.

A co-extrusion technique useful for preparing one embodiment of the adhesive structure of the present invention is shown schematically in FIG. The apparatus shown in FIG. 1 utilizes three extruders 10, 11, and 12, which may provide three molten streams of material to a co-extrusion mold 17 (sometimes hereinafter referred to as , Referred to as streams A, B and C, respectively). Extruder 10 provides melt stream 13 of the adhesive composition to mold 17. The extruder 11 provides a melt stream 14 of the polymer film material to a mold 17. Extruder 12 is optional and, when present, provides a melt stream 15 of polymer film material, which may be the same as the polymer film material of melt stream 14 from extruder 11. May be different. It can of course be understood that if a third melt stream is not desired, it is not necessary to utilize an extruder 12. An extruder 12 is utilized, and the melt stream 15 is a polymer film material (which
(Same as the polymer film material of the melt stream 14), the resulting coextrudate is a two-layer structure, one layer is the polymer film and the other is the adhesive. The polymer film material of melt stream 15 is melt stream 1
4, the polymer film of coextrudate 23 comprises two layers (31 and 31A in FIG. 1B), and the coextrudate comprises three layers (two polymer film layers (31 And 31A) and adhesive layer 3
0). An additional extruder can be used if it is desired to have an additional stream of molten material fed to the mold 17. Two or more extruders containing the same polymer film material are used to provide a coextrudate with a thicker polymer film.

In one preferred embodiment, the polymer film material is extruded on extruder 1
2 or the polymer charged to the extruder 12 is the same as the polymer charged to the extruder 11, and the resulting coextrudate comprises a single layer of polymer film, and a layer of adhesive. including.

Extruders 10, 11 and 12 are utilized to blend and melt the composition and as a pump to deliver the melt stream to the feedblock and extruder. Alternatively, the composition can be pre-blended before being introduced into the extruder. The exact extruder used is not critical to this process. A number of useful extruders are known and include single and twin screw extruders, batch-off extruders, and the like. Such extruders are available from various commercial sources (
Killion Extruders, Inc. , C.I. W. Brabender
Inc. , American Leistritz Extruder Co
, and Davis Standard Corp.).

[0078] A variety of useful coextrusion systems are known. Examples of extrusion molds useful in the present invention are Cloeren "vane" molds and Cloe of Orange, Texas.
It is a multi-manifold type commercially available from ren Company.

The choice of the extrusion die utilized in the process of the present invention is not critical, but certain factors affect the performance of the extrusion process. For example, if a single manifold is utilized, the relative viscosities of the materials and their ability to be processed at a single manifold temperature must be considered. If the relative viscosity of the material exceeds acceptable limits, or if the material cannot withstand a single manifold temperature, a multi-manifold type is typically used. In the multi-manifold type, each material flows into the manifold itself and reaches a junction. Each individual manifold may also be specifically designed with respect to the rheology of each polymer resin and / or adhesive, and each manifold may also be controlled at different process temperatures.

The multi-manifold mold has a zero common land length so that the material does not come into contact with the mold tip or come out of the orifice.
d length). Alternatively, they can be designed to have short common flow channels, for example, up to about 10 mm, and preferably less than about 5 mm. Zero common lands are preferred when the melt stream has extreme viscosity differences and / or temperature requirements. Short common lands are generally advantageous. Because, while the melt is in this common land, high temperature and high pressure periods can improve the bond strength between the layers of the structure and minimize or eliminate AE processing. In a preferred embodiment of the present invention,
The manifold mold is selected such that the melt stream is joined approximately 1 mm before the mold lip.

Referring to FIG. 1, two or more layers of homogeneous molten structure 19 exit the extrusion mold 17 through an orifice 18, and the molten structure is fed to a solid substrate 21 supplied from a roll 21. (E.g., a release liner) so that the lower surface of the adhesive layer contacts the liner while the upper surface of the polymer film contacts the atmosphere. The liner 21 is partially wound on the first roll of the three chill roll stacks 22, 22A and 22B. Chill roll 22 also acts as a casting roll. The liner 21 contacts the surface of the casting roll 22 and is inserted between the surface of the casting roll and the adhesive layer of the melt stream 19. In the embodiment shown in FIG. 1, molten structure 19 is deposited on liner 21 and structure 23 (which is formed during this process) is then passed over chill rolls 22A and 22B. , And wound on a roll 24 or wound up by itself.

Casting / Cooling Roll 22 and Chill Rolls 22 A and 22
B is typically maintained at a temperature below the temperature of the homogeneous molten structure 19 to cool the molten structure after the molten structure has been deposited on the liner. Typically, this temperature ranges from about 5C to about 100C, preferably from about 20C to about 30C.

FIG. 1A is a cross-sectional view of an adhesive structure 23 according to one embodiment of the present invention, wherein the polymer film is a single layer. Accordingly, the adhesive structure 23 shown in FIG. 1A includes the polymer film layer 31, the adhesive layer 30, and the release liner 21. FIG. 1B is a cross-sectional view of the adhesive structure 23 'of the present invention, wherein the adhesive composition is provided to an extruder 10 and various polymer film materials are provided to extruders 11 and 12. You. The resulting adhesive structure, shown in FIG. 1B, includes polymer film layers 31 and 31A (derived from the materials supplied to extruders 11 and 12, respectively), adhesive layer 30, and release liner 21.

FIG. 2 illustrates another coextrusion procedure useful for preparing the bonded structures of the present invention. The apparatus shown in FIG. 2 utilizes four extruders 41, 42, 43 and 44, which comprise four molten streams of material (sometimes hereinafter referred to as stream A, B, C and D). Extruders 41, 42 and 43 provide melt streams 45, 46 and 47, respectively, to feedblock 49, and extruder 44 provides a melt stream 48 of the bonded structure directly to mold 50. According to the procedure shown in FIG. 1 and described above, the melt streams of polymer film material exiting extruders 41, 42 and 43 may be the same or different, In embodiments, it is preferred that the polymer film materials exiting extruders 41, 42 and 43 be the same. Using three extruders containing the same polymer film material, a coextrudate with a thicker polymer film is provided.

The feed block 49 in FIG. 2 combines the molten stream of polymer film material into a single flow channel. The feed block 49 delivers the molten structure to the extrusion mold 50, where the molten structure is combined with the adhesive stream 48,
And then the combined stream is reduced in height and increased in width as desired, thereby providing a relatively thin thick wide structure. An example of a useful feedblock is the Cloeren co-extruded feedblock (Cloeren
Company (commercially available from Orange, Texas). The above discussion (
1 (with regard to the choice of extrusion die used for the process of FIG. 1) is applicable to the process of FIG.

The two or more layers of homogeneous molten structure 52 are passed through an orifice 51
0 and the molten structure is fed to a solid substrate 54 (
(E.g., a release liner) so that the lower surface of the adhesive layer contacts the liner while the upper surface of the polymer film contacts the atmosphere. The liner 54 is partially wound on the first roll of the three chill roll stacks 55, 56 and 57. The chill roll 55 also functions as a casting roll. The liner 54 contacts the surface of the casting roll 55 and is inserted between the surface of the casting roll 55 and the adhesive layer of the melt stream 52. In the embodiment shown in FIG. 2, the molten structure 52 is deposited on a liner 54 and the structure 58 formed in this process is then passed over chill rolls 56 and 57 and wound on roll 59. Rolled up or rolled up by itself.

Casting / Cooling Roll 55 and Chill Rolls 56 and 57
Is typically maintained at a temperature lower than the temperature of the homogeneous molten structure 52 to cool the molten structure after it has been deposited on the liner. Typically, this temperature ranges from about 5C to about 100C, preferably from about 20C to about 30C.

If desired, a number of additional steps may be performed on the co-extrudate as needed. Thus, for example, the coextrudate can be oriented uniaxially or biaxially (eg, by heat stretching and thermosetting). If it is desired to orient the coextruded adhesive structure of the present invention uniaxially or biaxially, such an orientation is preferably such that the coextrudate is supported by a support material (eg, release liner 21 and release liner 21). 54 (FIGS. 1 and 2 respectively). For example,
If it is desired to orient the co-extrudate, the process described with respect to FIGS. 1 and 2 is modified as follows. The flow of molten material into the mold and / or feed block is reconfigured so that uniform molten structures 19 and 52 (
1 and 2) each have an adhesive layer on top and the molten film layer comes into contact with the casting roll / chill roll 22 or 55, where the molten material is cast into a film and cooled. The chill rolls 22A and 22B in FIG. 1 and the chill rolls 56 and 57 in FIG. 2 are omitted or the adhesive surface of the cast film is reconfigured so that it does not come in contact with further chill rolls. After the cast film has cooled, the structure can be oriented and then laminated to the release surface of the release liner. In one preferred embodiment of the present invention, the adhesive structure is not oriented.

The longitudinal or biaxial orientation of the cooled cast film of the present invention prepared as described above, without the release liner, can be achieved by techniques known in the art. For example, these films have been used in tenter frames (te
can be oriented longitudinally using an interlacing frame. In a tenter frame, the clips at the edges of the tenter frame move more quickly in the machine direction, thereby stretching the film in the machine direction. Alternatively, these clips can be programmed to move more quickly in the machine direction or spread out in the cross direction, or to stretch in both directions to orient the film in both directions. If the film can be stretched using a tenter frame, the edges of the film are preferably free of adhesive so that the clips do not stick to the film. After orientation in the tenter frame, the co-extruded bonded structure is then
It can be laminated to a release liner.

The adhesive structure of the present invention as shown in FIGS. 1A and 1B can be controlled for further printing, top lamination and conversion at different times and / or geographic locations, or These structures can either be printed, top laminated, and / or routed to one or more other stations for conversion between the same operations. In the illustrated process, the adhesive structure 23 of FIG. 1 is wound on a roll 24 and further printed, top laminated and / or
Or saved for conversion. Prior to printing, it is often desirable to treat the exposed film surface of the adhesive structure of the present invention to make the exposed surface of the polymer film more susceptible to subsequent printing or marking. In an exemplary embodiment, the structure is treated by conventional surface treatment methods (eg, corona treatment, etc.) to increase the interfacial energy of the polymer film layer to promote wetting during the printing process.

An important feature of the adhesive structure of the present invention is the ability to deposit printed and / or other forms of marks on the upper surface of the film layer. Thus, the polymer film material selected for the exposed or top surface of the adhesive structure is sensitive to printing with ink using printing techniques (eg, flexographic, screen, offset, letterpress, thermal transfer, etc.). It should be a workable material and the applied ink should have acceptable adhesion to the surface of the adhesive structure.

In some cases, the characteristics of the very thin adhesive structure described above can be improved by laminating another polymer film over the coextruded polymer film.
In this embodiment, the very thin coextrudates of the present invention, including the polymer film and the adhesive, are sometimes referred to herein as "prelaminates".
minate) ". Prelaminates are less than about 1 mil in thickness, and more often. It is about 0.2-0.5 or 0.6 mil thick. The additional film on the prelaminate (coextrudate) polymer film is generally
It is referred to as "top laminated film" or "top laminated layer" and the adhesive structure comprising this top laminated film is sometimes referred to as "top laminated structure". The top laminated film can provide additional properties to the bonded structure, such as stiffness and weather resistance. The top laminated film also provides a transparent coating or film over the printed indicia to allow damage due to physical contact with adjacent objects, as well as exposure to moisture, water, or weather. Protect prints from damage.
The clear coating also increases the optical amount of the underlying printed indicia to provide a glossier and richer image. The upper laminated structure of the present invention,
It is inherently suitable for use as a label on a substrate that is subjected to subsequent liquid treatments (eg, bottle washing / rinsing, filling and pasteurization, or liquid immersion (eg, an ice bath)). It does not show bad results such as cloudiness.

When in the form of a continuous film having a layer of adhesive material interposed between the continuous polymer film having an adhesive structure and the upper laminated film, the upper laminated film may be co-extruded by pressure. It can be laminated to a structure. If either the continuous polymer film or the top laminated film is formed from a material that forms its own adhesive surface for lamination when activated by heat, the top laminated film may include the addition of an adhesive Instead, it can be laminated by heat and pressure to a continuous polymer film having an adhesive structure. Alternatively, the top laminated film may be a curable (heat or radiant) liquid adhesive (eg, a UV curable varnish).
Can be applied. Alternatively, the top laminated film can be applied to the adhesive structure as a film-forming material, which subsequently cures to form a continuous film, by extrusion or coating techniques. The print indicia is located on the continuous polymer film surface and / or on the back side of the upper laminated film layer. As a further alternative, the top laminated adhesive structure of the present invention can be prepared by the following (a), (b): (a) separately extruding the two adhesive structures, each comprising:
A process comprising a continuous polymer film and an adhesive layer as described above, and (b)
) Combining the two co-extrudates to form a four layer structure, adhesive / film / adhesion / film. In another embodiment, the apparatus comprising four extruders as shown in FIG. 2 (or one extruder may be added to the apparatus of FIG. 1) comprises a first and a third extruder. Can be utilized with the polymer film forming material loaded into the second and fourth and fourth extruders. The result of such a coextrusion process is a film / adhesive / film / adhesive structure.

FIG. 3 illustrates another embodiment of a top laminated adhesive structure 40 prepared in accordance with the principles of the present invention. The top laminated adhesive structure 40 comprises an adhesive structure 23 as described above and as shown in FIG. 1A, which comprises a release liner 21, an adhesive layer 30, and a polymer film layer 31. The upper laminated structure 40 of FIG. 3 also includes a printed or other form of mark 3 disposed on the polymer film layer 31.
2, including a second adhesive layer 33 disposed on the print mark or mark 32, and an upper laminated film layer 34 disposed on the second adhesive layer 33. Second adhesive layer 33
Can be formed from the same types of adhesive materials discussed above for the adhesive structures of the present invention.

FIG. 4 is a side view of a cross section of another upper laminated adhesive structure 40A of the present invention. This upper laminate structure 40 has the release liner 21 and has been discussed above in FIG.
B includes an adhesive structure 23 ′, an adhesive layer 30, a first film layer 31, and a second film layer 31A. Further, the structure of FIG. 4 includes a layer of printed indicia 32, a second adhesive layer 33 and a top deposition layer 34.

It should be understood that the top laminate adhesive structure of the present invention can be configured based on each particular label end use. For example, in FIG.
It can be inserted between the second adhesive layer 33 and the upper laminated film layer 34 (eg, a reverse printed upper laminated film layer). Such a structure can generally be prepared by using a top laminate film 34 that is first reverse printed and subsequently has a layer of adhesive applied to the reverse printed surface. This upper laminated film is then laminated to the polymer film layer 31 or 31A via an adhesive layer by conventional pressure lamination techniques.

In another embodiment, a top laminated adhesive structure according to the present invention is prepared, and the upper laminated adhesive structure is similar to FIGS. 3 and 4 except that the second adhesive layer 33 has been removed.
Is similar to the structure shown in FIG. In this embodiment, the upper laminated film layer 3
4 is formed from a material that is heat activatable and provides its unique adhesive surface to the laminate. This material has sufficient "open tack" time to promote lamination at relatively low temperatures to avoid unnecessary thermal effects in the bonded structure. "Open tack" refers to the time during which the just activated film material remains viscous or susceptible to adhesive contact with adjacent surfaces.

The preparation of an adhesive structure according to the process of the present invention is shown in the following examples.

Example 1 The equipment used in this example is generally similar to the equipment of FIG. 1, and has three extruders (Killion 1 ″ single screw extruder (Stream A), three / 4 "Brabender single screw extruder (stream B), and 27 mm Leistritx twin screw extruder in co-rotating mode (stream C)), and 6" Cloeren,
It consists of three layers, three manifold vane types. The adhesive for the adhesive layer of the structure of the present invention is 145 ° C, 155 ° C, 160 ° C, 160 ° C, 160 ° C, 16 ° C.
It is fed to a Leistritz twin screw extruder with 9 heating zones, maintained at 0 ° C, 160 ° C, 155 ° C and 155 ° C. The adapter is also heated to 155 ° C. and the zone of the first extruder is not heated. 0.1 phr of a stabilizer (Irgafos) was added to Kraton D1320X.
168 and Irganox 565) and fed through the first zone solids feed port at a rate of 447 g / hr. Kra
Ton LVSI-101 was heated to 120 ° C. and fed to zone 4 at a rate of 57 g / hr. Escorez 1310 was heated to 135 ° C. and fed to zone 6 at a rate of 407 g / hr. The twin screw extruder is operated at 450 rpm, which requires 2.8 amps. The Brabender extruder operated at 5 rpm is filled with Unirez 2623. The temperature profiles are 150 ° C., 155 ° C. and 165 ° C. in three zones with a head pressure of 600 kPa. Additional Unirez 2623
Is charged to a Killion extruder operated at 5 rpm. Killi
Heat the third zone of the extruder to 165 ° C. and 1380 kPa
Hold at head pressure. The melt streams of the three extruders are combined inside a Cloeren mold set at a temperature of 165 ° C., so that two melt streams of polyamide (streams A and B) are combined with a melt stream of adhesive (stream C), and these streams meet inside the mold in such a way that the adhesive, including the sides, contacts the release liner as soon as it exits the mold. This release liner is composed of glassine paper coated at one end with a GE7000 series silicone release. This liner is partially covered around the bottom chill roll (also a forming roll) of the three chill roll stacks, which is held in a closed nip position. This chill roll is about 22
The melt stream, kept at 0 ° C and exiting the mold, is cast on a liner covered on the bottom chill roll. The line speed is about 12 m / min. The resulting extrudate is about 7.5 cm wide and about 0.5 mil (12 microns) thick.

Example 2 The procedure of Example 1 was followed except that Unirez 2623 was replaced with polypropylene 5E66 from Union Carbide and extruder and mold temperatures were increased to 210. Killion extruder is 5rpm
And head pressure is 4800 kPa. The Brabender extruder is operated at 8 rpm and the head pressure is 4300 kPa. Leis
The tritz extruder uses the same temperature profile as in Example 1 and uses Kraton D1320X, LVSI 101 and Escorex 259.
6 is operated in the same manner as in Example 1, except that the feed rates are 670 g / h, 76 g / h and 543 g / h, respectively. Leistritz
The head pressure of the twin screw is 1310 kPa and the melting temperature is 166 ° C. The adhesive structure is wound with a liner at 12 m / min and the adhesive structure is about 11.5 cm wide and about 0.5 mil (12 microns) thick.

Examples 3-6 In these embodiments, the apparatus used is the same as the apparatus of FIG. 2
Two Killion 1 '' extruders are used for streams A and C. The Davis-Standard 1.5 "extruder is a stream B
Used for A Leistritz twin screw extruder is used for stream D. The Killion extruder is operated at 200 ° C and the Davis-Standard extruder is operated at 215 ° C. Le
The istritz extruder is heated according to the following pro-reel: unheated, 145 ° C, 160 ° C, 160 ° C, 170 ° C, 170 ° C, 175 ° C, 175 ° C,
180 ° C and 180 ° C. The adapter is heated to 210 ° C. The speed of the extruder is varied according to the desired product. Streams A, B and C are U
The stream is composed of polypropylene 5E66 from Nion Carbide, and these streams are passed through a feedblock to an 11 "Producti.
On Components is supplied to one manifold of a dual manifold extrusion mold. Stream D is a pressure sensitive adhesive, which is fed directly to the other manifold of the extruder. The extrudate is cast with the adhesive in contact with the release liner and stream A in contact with the chill roll 56. The chill roll stack is kept at about 90 ° C., and the mold gap for the ABC layer is set at about 380 microns. The gap for the adhesive layer is about 2
50 microns. Further details regarding these four examples, as well as product details, are summarized in Table III below.

[0102]

[Table 4] As described above, the composite structure of the present invention can be combined with a release liner by contacting the release liner with the substrate adhesive layer to form a label stock. Release liners that can be used in the label construction are composed of any of a variety of materials known to those skilled in the art to be suitable as release liners. 1
In one preferred embodiment, the release liner comprises a silicone-coated paper substrate. Coated polymer film substrates can also be used as release liners.

[0103] The label stock can then be converted to labels by procedures well known to those skilled in the art. Thus, the label stock can be printed and stamped into individual labels. This printing step can occur before or after the step of mating the adhesive structure with the release liner of the present invention, but before punching the facestock into individual labels. The film may be used during the printing process (e.g., between subsequent printing and a different dyeing process) so that the image or text may be of high quality, and so that the image or text is properly positioned on the label. Between the printing and the subsequent stamping process, the exact register must remain. The film may be stretched during the printing process, causing the temperature to rise somewhat, for example, if the UV ink is cured, and the film must retain longitudinal dimensional stability. Must.

The label stock is stamped into a series of open pressure sensitive labels held by a release liner. This step may be performed in a well-known manner by a rotary cutting mold, and this step is followed by a ladder-shaped matrix of excess or trim material around the formed label when the label is stamped. A peeling step (the "ladder" of the ladder represents the gap between successive labels). The labels then remain on the liner in spaced relation to one another. One mode of failure in this operation involves the poorly punched label remaining with the matrix when the matrix is peeled off. In this manner, as the release level decreases, poor punching appears to leave the label on the matrix material and to be removed from the liner along with the matrix during peeling of the matrix. Another mode of failure that occurs when the film is punched is insufficient strength. As the strength of the matrix material decreases, the matrix around the stamped label is pulled from the liner, making it more likely to tear. The films of the present invention have sufficient strength to eliminate or reduce breakage during matrix upstripping.

[0105] In one embodiment of the present invention, the composite structure is a peel-back.
k) It advantageously has sufficient stiffness so that the use of unnecessary equipment commercially available, such as ends, is not required. In a preferred embodiment of the present invention, the composite structure does not require a peel plate. As mentioned above, the unnecessaryness includes the steps of peeling the label from the liner, and subsequently applying the label to the substrate surface.

The coextruded adhesive structures of the present invention are useful for a variety of applications, including signs, labels, tags, decals, and the like. As noted above, these structures are particularly useful in preparing labels. These structures can also be used as decals, for example, as in the case of thin vertical stripes in automobiles and trucks, especially when these structures are very thin (eg, without surfaces). The thermoplastic elastomer adhesives described above are used for surfaceless structures, these structures exhibit reduced bleeding of the adhesive around the edges, and edging or decals or fine vertical stripes are applied. Later, almost invisible. These structures are also useful for outdoor signs and decals, for example, for application to glass windows. The thin structure of the present invention can be stamped and the signature and decal can be manually removed from the release layer. Fast implementation (and thus stiffness) is not a problem in these applications. Highly adapted (flexible) films (eg, medical films) can also be prepared from the adhesive structures of the present invention. Such films prepared using thermoplastic elastomer adhesives exhibit low water vapor permeability, which can be further improved by the choice of a particular FFM. These adhesive structures are also useful in preparing tamper-evident labels or seals for containers (eg, bottles that may contain printed words such as VOIDs). For example, the top of the bin and the top of the capped bin with the film around the cap are unscrewed and the film is pulled down on the bin rather than breaking and forming sharp edges.

Although the present invention has been described with reference to preferred embodiments thereof, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the present specification. Accordingly, the invention disclosed herein is intended to cover such modifications as would fall within the scope of the appended claims.

[Brief description of the drawings]

FIG. 1 is a schematic side elevation view of a method for manufacturing an adhesive structure of the present invention.

FIG. 1A is a side cross-sectional view of the adhesive structure of the present invention prepared in FIG.

FIG. 1B is a side cross-sectional view of another adhesive structure of the present invention prepared in FIG.

FIG. 2 is a schematic side elevational view of another method for manufacturing the bonded structure of the present invention.

FIG. 3 is a side sectional view of the upper laminated adhesive structure of the present invention.

FIG. 4 is a side cross-sectional view of another upper laminated adhesive structure of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) // C09J 153/02 C09J 153/02 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI GB, GE, GH, GM, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN , MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU, ZW ( 72) Inventor Sun, Edward I. United States California 91006, Arcadia, East Wisteria Avenue 300 (72) Inventor Burgas, Steven Jay. United States California 91325, Northridge, Lassen Street No. 307 17831 (72) Inventor Mendez, Jose Rius United States California 91706, Baldwin Park, Stewart Avenue 4247 F-term (reference) 4F100 AK01A AK01D AK03A AK07A AK12A AK21A AK22A AK41A AK41A AK41A AK70A AL01A AL02C AL04C AL05A AL05C AL09C AT00A AT00C AT00D BA03 BA04 BA07 BA10C CA16C CA16H CA30A CA30H CB05B CB05G EH20 EJ37 EJ38 GB90 HB31 JB16C JK01 JK02A JK08A J04A04A14 Y04A04 Y14A04 DN072 EL012 JA09 JB09 KA26

Claims (88)

[Claims] 1. A stampable and matrix-peelable adhesive structure, comprising: A. A continuous polymer film having upper and lower surfaces, and a thickness of about 0.1 mil to about 1 mil; An adhesive layer having an upper surface and a lower surface, wherein the upper surface of the adhesive layer is adhesively bonded to the lower surface of the polymer film. 2. The structure according to claim 1, wherein the polymer film (A) is a multilayer film. 3. The structure according to claim 1, wherein the polymer film is formed of polystyrene, polyolefin, polyamide, polyester, polycarbonate, polyurethane, polyacrylate, polyvinyl alcohol, poly (ethylene vinyl alcohol), or polyvinyl. The structure selected from the group consisting of acetates, ionomers, and mixtures thereof. 4. The structure according to claim 1, wherein the polymer film (A) is a polyolefin. 5. The structure according to claim 1, wherein the polymer film (A) is a propylene polymer or a copolymer. 6. The structure of claim 1, wherein said polymer film (A) has a high speed tensile strength of at least about 1 pound per inch width. 7. The structure of claim 1, wherein said polymer film (A) has an elongation of less than about 200%. 8. The structure of claim 1, wherein said polymer film includes at least one nucleating agent. 9. The structure of claim 1, wherein said adhesive layer comprises a pressure-sensitive adhesive. 10. The structure of claim 1, wherein said adhesive layer (B) has a coat weight ranging from about 0.5 to about 20 g / m ² . 11. The structure of claim 1, wherein the polymer film has a hot melt viscosity of about 0 at a shear rate experienced during the co-extrusion process.
. A structure having a hot melt viscosity that is within a factor of from about 07 to about 15 times. 12. The structure of claim 1, wherein the co-extrudate is not uniaxially or biaxially oriented. 13. The structure of claim 1, wherein the co-extrudate is oriented in a machine direction. 14. The structure of claim 1, wherein the coextrudate is biaxially oriented. 15. The structure of claim 1, further comprising, in addition to the co-extrudate, a flexible substrate having a release surface adhered to a lower surface of the adhesive layer (B). 16. The structure according to claim 1, wherein the upper surface of the polymer film (A) is printed with ink. 17. The structure according to claim 1, wherein the structure also comprises an upper laminated film layer disposed on an upper surface of the polymer film (A), and the first polymer film (A). ) And a printed mark inserted between the upper laminated film layer. 18. The structure according to claim 1, wherein the adhesive layer comprises an adhesive composition including a thermoplastic elastomer component and a solid tackifying resin component. 19. The structure of claim 18, wherein said adhesive composition also comprises at least one liquid rubber component. 20. The structure of claim 1, wherein said adhesive layer comprises about 40
% To about 80% by weight of the thermoplastic elastomer component and about 20% to about 60% by weight.
A structure comprising a pressure-sensitive adhesive composition that includes weight percent of a solid tackifying resin component. 21. The structure of claim 18, wherein said thermoplastic elastomer component comprises at least one thermoplastic elastomer block copolymer. 22. The structure of claim 21, wherein said thermoplastic block copolymer is selected from the group consisting of a linear copolymer, a branched copolymer, a graft copolymer, or a radial copolymer. 23. The structure of claim 18, wherein the thermoplastic elastomer component of the adhesive has a melt index of less than about 10. 24. A die-cuttable and matrix-peelable adhesive structure, comprising: A. A continuous polymer film having upper and lower surfaces, and a thickness from about 0.1 mil to about 2 mils; An adhesive layer having an upper surface and a lower surface, wherein the upper surface of the adhesive layer comprises an adhesive layer adhesively bonded to a lower surface of the polymer film; and Comprises a thermoplastic elastomer component and a solid tackifying resin component. 25. The structure according to claim 24, wherein the polymer film (A) is a multilayer film. 26. The structure according to claim 24, wherein the polymer film is formed of polystyrene, polyolefin, polyamide, polyester, polycarbonate, polyurethane, polyacrylate, polyvinyl alcohol, poly (ethylene vinyl alcohol), or polyvinyl. The structure selected from the group consisting of acetates, ionomers, and mixtures thereof. 27. The polymer film (A) is a polyolefin,
A structure according to claim 24. 28. The structure of claim 24, wherein the polymer film is subject to a shear rate of about 0.07 to about 15 times the hot melt viscosity of the adhesive during a co-extrusion process. A structure having a hot melt viscosity that is within the factor 29. The structure of claim 24, further comprising a flexible substrate having a release surface adhered to a lower surface of the adhesive layer (B), in addition to the coextrudate. 30. The structure of claim 24, wherein said adhesive composition also includes at least one liquid rubber component. 31. The structure according to claim 24, wherein the adhesive layer comprises about 4
0% to about 80% by weight of the thermoplastic elastomer component and about 20% to about 6% by weight.
A structure comprising a pressure sensitive adhesive composition comprising 0% by weight of a solid tackifying resin component. 32. A stampable and matrix-peelable pressure-sensitive adhesive label structure comprising: A. A coextrudate comprising: A-1. A continuous polymer film having upper and lower surfaces, and a thickness of about 0.1 mil to about 1 mil, A-2. A. Co-extrudate having a pressure-sensitive adhesive layer having an upper surface and a lower surface, wherein the upper surface of the adhesive layer comprises an adhesive layer adhesively bonded to a lower surface of the polymer film; A substrate having a release surface, wherein the release surface is in contact with a lower surface of an adhesive layer of the coextrudate. 33. The structure according to claim 32, wherein the polymer film (A-1) is a multilayer film. 34. The structure according to claim 32, wherein the polymer film (A) is formed of polystyrene, polyolefin, polyamide, polyester, polycarbonate, polyurethane, polyacrylate, polyvinyl alcohol, or poly (ethylene vinyl alcohol). ), Polyvinyl acetate, ionomers, and mixtures thereof. 35. The structure according to claim 32, wherein the polymer film (A-1) is a polyolefin. 36. The structure according to claim 32, wherein the polymer film material of the first layer (A-1) is a propylene polymer or copolymer. 37. The structure of claim 32, wherein said polymer film (A-1) has a melt index of less than about 10. 38. The structure of claim 32, wherein said polymer film (A-1) has a high speed tensile strength of at least about 1 pound per inch width. 39. The structure of claim 32, wherein said polymer film comprises at least one nucleating agent. 40. The structure of claim 32, wherein said polymer film (A-1) has an elongation of less than about 200%. 41. The structure of claim 32, wherein said adhesive layer (A-2) has a coat weight ranging from about 0.5 to about 20 g / m ² . 42. The structure of claim 32, wherein the polymer film layer (A-1) has a hot melt viscosity of the adhesive at a shear rate experienced during coextrusion of the coextrudate. A structure having a hot melt viscosity that is within a factor of from about 0.07 to about 15 times. 43. The structure of claim 42, wherein said factor is 1 to about 10. 44. The structure of claim 32, wherein the coextrudate is not uniaxially or biaxially oriented. 45. The structure of claim 32, wherein the co-extrudate is oriented longitudinally. 46. The structure of claim 32, wherein the coextrudate is biaxially oriented. 47. The structure according to claim 32, wherein an upper surface of the polymer film (A-1) is printed with ink. 48. The structure of claim 32, wherein the structure is also disposed on an upper surface of a first layer of the polymer film material (A-1), and A structure comprising a printed indicia inserted between the first polymer film (A-1) and the upper laminated film layer. 49. The structure according to claim 32, wherein the adhesive layer (A-2)
) Comprising an adhesive composition comprising a thermoplastic elastomer component and a solid tackifying resin component. 50. The structure of claim 49, wherein said adhesive composition also comprises at least one liquid rubber component. 51. The structure according to claim 32, wherein the adhesive layer comprises about 4
0% to about 80% by weight of the thermoplastic elastomer component and about 20% to about 6% by weight.
A structure comprising a pressure sensitive adhesive composition comprising 0% by weight of a solid tackifying resin component. 52. The structure of claim 51, wherein said adhesive composition also includes at least one liquid rubber component. 53. The structure of claim 32, wherein said thermoplastic elastomer component comprises at least one thermoplastic elastomer block copolymer. 54. The structure of claim 53, wherein said thermoplastic block copolymer is selected from the group consisting of a linear copolymer, a branched copolymer, a graft copolymer, or a radial copolymer. 55. A label stamped from the co-extruded adhesive structure of claim 1. 56. A label stamped from the coextruded adhesive structure of claim 24. 57. A label stamped from the co-extruded pressure-sensitive adhesive label structure of claim 32. 58. A process for preparing a punchable and matrix-peelable adhesive structure for label application, the process comprising: (A) providing a removable substrate having a release surface. (B) depositing a melt co-extrudate on the release surface, the melt co-extrudate comprising: (B-1) an upper surface and a lower surface; A continuous polymer film having a thickness of about 1 mil; and (B-2) an adhesive layer having an upper surface and a lower surface, wherein the upper surface of the adhesive layer is adhesively bonded to the lower surface of the polymer film; Including an adhesive layer, wherein a lower surface of the adhesive layer is adhesively bonded to a release surface of the removable substrate.
And (C) cooling the co-extrudate. 59. The process of claim 58, wherein the melt coextrudate is formed in a multi-layer vane mold and the melt coextrudate exiting the mold is on a release surface of the removable substrate. Process that supports itself until it is deposited on 60. The process of claim 58, wherein said melt co-extrudate is formed on a multi-manifold mold having a common land length of 0 to about 10 mm. 61. The process of claim 58, wherein said polymer film (B-1) has a thickness of about 0.2 mil to about 1 mil. 62. The process according to claim 58, wherein said polymer film (B-1) is a multilayer film. 63. The process according to claim 58, wherein the polymer film (B-1) comprises polystyrene, polyolefin, polyamide, polyester, polycarbonate, polyurethane, polyacrylate, polyvinyl acetate, ionomer, and the like. A process selected from the group consisting of a mixture of 64. The process according to claim 58, wherein said polymer film (B-1) is a polyolefin. 65. The process of claim 58, wherein said adhesive layer comprises a pressure sensitive adhesive. 66. The process of claim 58, wherein said adhesive layer (B-2) has a coat weight ranging from about 0.5 to about 20 g / m ² . 67. The process of claim 58, wherein the polymer film (B-1) is within a factor of about 1 to about 15 times the hot melt viscosity of the adhesive. Having a process. 68. The process according to claim 58, wherein the upper surface of the polymer film (B-1) is subsequently printed with ink. 69. The process according to claim 58, wherein an upper laminated film layer is subsequently laminated on the upper surface of the polymer film (B-1) and a printed mark is formed on the polymer film (B-1). B-1) and inserting between the upper laminated film layer. 70. The process of claim 58, wherein the adhesive layer comprises an adhesive composition that includes a thermoplastic elastomer component and a solid tackifying resin component. 71. The process of claim 70, wherein said adhesive composition also comprises at least one liquid rubber component. 72. The process of claim 58, wherein the adhesive layer comprises about 40% to about 80% by weight of a thermoplastic elastomer component and about 20% to about 60% by weight of a solid tackifying resin. A process comprising a pressure-sensitive adhesive composition comprising the components. 73. The process of claim 70, wherein said thermoplastic elastomer component comprises at least one thermoplastic elastomer block copolymer. 74. The process according to claim 58, wherein said polymer film material of said film (B-1) has a melt index of less than about 10. 75. A process for preparing a punchable and matrix-peelable adhesive structure for label application, the process comprising: (A) providing a removable substrate having a release surface. (B) depositing a melt co-extrudate on the release surface, the melt co-extrudate comprising: (B-1) an upper surface and a lower surface; A continuous polymer film having a thickness of about 2 mils; and (B-2) an adhesive layer having an upper surface and a lower surface, wherein the adhesive comprises:
A thermoplastic elastomer component, and a solid tackifying resin component, wherein an upper surface of the adhesive layer is adhesively bonded to a lower surface of the polymer film, and a lower surface of the adhesive layer is a release surface of the removable substrate. Including an adhesive layer, which is adhesively bonded to
And C) cooling the co-extrudate. 76. The process of claim 75, wherein the melt coextrudate is formed in a multi-layer vane mold and the melt coextrudate exiting the mold is on a release surface of the removable substrate. Process that supports itself until it is deposited on 77. The process of claim 75, wherein said melt co-extrudate is formed on a multi-manifold mold having a common land length of 0 to about 10 mm. 78. The process according to claim 75, wherein said polymer film (B-1) is a multilayer film. 79. The process according to claim 75, wherein said polymer film (B-1) comprises polystyrene, polyolefin, polyamide, polyester, polycarbonate, polyurethane, polyacrylate, polyvinyl acetate, ionomer, and the like. A process selected from the group consisting of a mixture of 80. The process according to claim 75, wherein said polymer film (B-1) is a polyolefin. 81. The process of claim 75, wherein said adhesive layer comprises a pressure-sensitive adhesive. 82. The process of claim 75, wherein said adhesive layer (B-2) has a coat weight ranging from about 0.5 to about 20 g / m ² . 83. The process according to claim 75, wherein the polymer film (B-1) is within a factor of about 1 to about 15 times the hot melt viscosity of the adhesive. Having a process. 84. The process according to claim 75, wherein the upper surface of the polymer film (B-1) is subsequently printed with ink. 85. The process according to claim 75, wherein an upper laminated film layer is subsequently laminated on the upper surface of the polymer film (B-1) and a printed mark is formed on the polymer film (B-1). A process of inserting between B-1) and the upper laminated film layer. 86. The process of claim 75, wherein said adhesive composition also comprises at least one liquid rubber component. 87. The process of claim 75, wherein the adhesive layer comprises about 40% to about 80% by weight of a thermoplastic elastomer component and about 20% to about 60% by weight of a solid tackifying resin. A process comprising a pressure-sensitive adhesive composition comprising the components. 88. The process of claim 75, wherein said thermoplastic elastomer component comprises at least one thermoplastic elastomer block copolymer.