PSA containing olefin block copolymers and styrene block copolymers

Abstract

The invention relates to storage-stable hot-melt adhesive containing 15 to 70 wt % of a mixture of at least one copolymer based on ethylene and/or propylene and at least one C4 to C20 α-olefin which is obtainable as a block copolymer by metallocene-catalyzed polymerization, and at least one styrene block copolymer, 10 to 70 wt % of at least one tackifying resin, 0 to 40 wt % of further additives, wherein the total of the percentages should amount to 100% and the tackifying resin is entirely or in part a soft resin.

Claims

1. A hot-melt adhesive comprising: (A) a mixture of (i) 15 to 30 wt % a metallocene-catalyzed block copolymer, which is an ethylene and/or propylene and at least one C4 to C20 α-olefin, and (ii) 5 to 25 wt % of a styrene block copolymer; (B) 10 to 40 wt % of at least one tackifying resin, wherein the at least one tackifying resin is entirely liquid at room temperature; and (C) 0 to 40 wt % of further additives selected from plasticizer, wax, stabilizer, adhesion promoter, antioxidant, light stabilizer, colorant, rheological agent, and mixtures thereof; wherein the total amount of the at least one tackifying resin and the plasticizer is from 10 to 35 wt %; wherein the sum of the %-shares should amount to 100%; and wherein the viscosity of the hot-melt adhesive is between 10000 mPas and 50,000 mPas at 150° C.

2. The hot-melt adhesive according to claim 1 wherein the styrene block copolymer is selected from non-hydrogenated block copolymers.

3. The hot-melt adhesive according to claim 2 wherein the styrene block copolymer is selected from the group consisting of SIS, SBS and SIBS.

4. The hot-melt adhesive according to claim 1 wherein the hot-melt adhesive is cloudy at room temperature.

5. The hot-melt adhesive according to claim 1 wherein the plasticizer include a nonpolar plasticizers selected from the group consisting of synthetic oils, paraffinic oils, naphthenic oils, poly(isobutylene) oils and mixtures thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The thus obtained (co)polymers have a molecular weight of 2000 up to 250,000 g/mol, in particular from 5000 up to 100,000 g/mol (number average molecular weight, M.sub.n determined by GPC). These (co)polymers are characterised in that they have a narrow molecular weight distribution. The molecular weight distribution, expressed as M.sub.w/M.sub.n, should be 2.5 for example, especially less than 2.3. Such polymers are known in the literature and can be commercially obtained from various manufacturers. Exemplary suitable polymers are commercially available under the trade names VISTAMAX® or INFUSE®.

(2) The suitable copolymers according to the invention are block copolymers. In this regard the blocks possess a different monomer composition. In one embodiment the suitable hot-melt adhesives according to the invention possess one glass transition temperature; in another embodiment the copolymers should possess two glass transition temperatures. The first glass transition temperature (T.sub.g) (measured by DTA) should be in the range between −100 to 0° C., especially between −80 to −10° C. The second glass transition temperature should be in particular below −100° C.

(3) In particular, those olefinic block copolymers are suitable that are manufactured by catalysis with metallocene compounds. The melt index of these polymers should be from 5 g/10 min to 200 g/10 min, preferably up to 100 g/10 min (measured at 190° C., 2.16 kg, DIN ISO 1133). The softening point of the polymers should be above 130° C., in particular above 160° C. The amount of these copolymers should range from 5 to 50 wt %, relative to the hot-melt adhesive, in particular between 15 and 30 wt %. The (co)polymer can concern one polymer, but it is also possible to employ a mixture.

(4) A pressure-sensitive adhesive (PSA) according to the invention has to comprise at least one thermoplastic elastic styrene block copolymer as an additional ingredient. This preferably concerns a triblock copolymer, although diblock copolymers may be employed or also mixtures of both types. Such block copolymers are poorly compatible with the olefin block copolymers.

(5) Various types of styrene block copolymers may be concerned.

(6) Examples of these are styrene-isoprene block copolymers (SIS), styrene-isoprene-butadiene block copolymers (SIBS), styrene-butadiene block copolymers (SBS), hydrogenated forms of the copolymers, such as SBBS, SEBS, SEPS, SIPS or their mixtures, as well as the corresponding diblock copolymers. Such polymers are known to the person skilled in the art and are commercially available. They have a molecular weight (M.sub.n) of 10,000 to 500,000 g/mol, in particular 70,000 to 300,000 g/mol. In particular, non-hydrogenated forms are preferred.

(7) The amount of additionally contained styrene block copolymers to the olefin block copolymers ranges from 3 to 35 wt %, in particular from 5 to 25 wt %, relative to the hot-melt adhesive. The amount of these block copolymers influences the elasticity of the adhesive. If the amounts of the block copolymers are too high, then the adhesive is too elastic and can be difficult to process. Moreover, incompatibilities are increasingly observed which lead to poor adhesive properties. If the amount is too low, then the cohesion of an adhesive layer is decreased.

(8) The pressure-sensitive adhesive according to the invention contains at least one tackifying resin as an additional component. The resin causes an additional tackiness to the adhesive. It is added in an amount of 10 to 60 wt %, preferably 10 to 40 wt %. It is according to the invention necessary that the resins at least partially contain a soft resin that is liquid or flowable below 50° C. This can be determined from the dropping point. In this regard, resins can be selected from aromatic, aliphatic or cycloaliphatic hydrocarbon resins, as well as modified or hydrogenated derivatives. Other resins that can be employed in the context of the invention are polyterpene resins, phenolic or aromatic modified polyterpene resins, modified natural resins such as resin acids from balsamic resin, tall oil resin or wood rosin, optionally also hydroabietyl alcohol and its esters, acrylic acid copolymers, such as styrene-acrylic acid copolymers and resins based on functional hydrocarbon resins.

(9) Usual resins have a low molecular weight of less than 2000 g/mol, especially less than 1500 g/mol. They can be chemically inert or they can optionally comprise functional groups, such as for example OH groups, carboxylic groups or double bonds. According to the invention, soft resins that have a dropping point below 50° C., particularly below 35° C., should therefore be selected (Mettler dropping point according to ASTM D-3104). As additional resins, those resins that have a softening point between 70 and 130° C. (ring and ball method, DIN 52011) can also be employed. Preferably rosins and in particular fully or partially hydrogenated hydrocarbon resins are employed. In this regard, the amount of resins that are solid at room temperature can be up to 50% of the total quantity of resin.

(10) Plasticizers are preferably used to adjust the viscosity or the flexibility and are generally comprised in a concentration of 0 to 25 wt %, preferably 2 to 15 wt %. Suitable non-polar plasticizers include synthetic oils, paraffin oils, naphthenic oils or polyisobutylenes. They concern for example medicinal white oils, naphthenic mineral oils, polypropylene-, polybutene-, polyisoprene oligomers, hydrogenated polyisoprene- and/or polybutadiene oligomers, paraffinic hydrocarbon oils.

(11) In order to obtain a high tack and good cohesion it is preferred that the sum of soft resin and plasticizer is from 10 to 35 wt %.

(12) As additional components, the pressure-sensitive hot-melt adhesive according to the invention contains additives that can influence certain properties of the adhesive, such as e.g. cohesion strength, viscosity, softening point or processing viscosity. In this regard, for example stabilizers, waxes, adhesion promoters, antioxidants, light stabilizers, color pigments, rheological agents or similar additives are concerned. The amount should be up to 15 wt %. A plurality of additives can also be incorporated as a mixture. In addition, fillers may be incorporated to increase strength. Minor amounts of plasticizers as the glycerin, benzoate or phthalate esters or polyglycol ethers can also be employed to adjust the properties.

(13) Waxes in quantities of 0 to 5 wt % may optionally be added to the pressure-sensitive hot-melt adhesive. The quantity is measured such that, on the one hand, the viscosity is adjusted, on the other hand, the adhesion is not adversely affected. The wax may be of natural or synthetic origin. Employable as natural waxes are vegetable waxes, animal waxes; mineral waxes or petrochemical waxes are employable as synthetic waxes. However, waxes should preferably not be comprised.

(14) Stabilizers are another group of additives. They serve to protect the polymers from decomposition during the processing. In this regard, the antioxidants are in particular noteworthy. They are usually added to the pressure sensitive hot-melt adhesive in quantities of up to 3 wt %, preferably in quantities of about 0.1 to 1 wt %. Such additives are known in principle to the person skilled in the art.

(15) He can make a selection according to the desired properties of the hot-melt adhesive.

(16) Moreover, the pressure-sensitive hot-melt adhesive according to the invention can contain adhesion promoters. Adhesion promoters are substances that improve the adhesion of the hot-melt adhesive to the substrate being bonded. In particular, adhesion promoters are intended to improve the ageing behavior of adhesive bonds under the influence of humid atmospheres. Typical adhesion promoters are, for example, ethylene/acrylamide comonomers, polymeric isocyanates, reactive organosilicon compounds or phosphorus derivatives. They can also influence the wetting characteristics of the adhesive and thus the adhesion behavior on the substrates.

(17) A preferred embodiment of the pressure-sensitive hot-melt adhesive contains 15 to 30 wt % of a block copolymer based on ethylene and/or propylene and optionally at least one C4 to C20 α-olefin which is obtained by metallocene-catalyzed polymerization, and 5 to 35 wt % of at least one styrene block copolymer, 5 to 35 wt % of at least one tackifying resin that is liquid below 50° C., 0 to 25 wt % of a non-polar plasticizer as well as 0 to 15 wt % of other additives, wherein the sum of the percentage shares should be 100%.

(18) The pressure-sensitive hot-melt adhesive according to the invention is manufactured by means of known processes by blending in the melt. In this regard, all the components can be charged, and heated together at the same time and then homogenized, or the lower melting components can be charged and blended, and then the additional resin components are added. It is also possible to manufacture the hot melt adhesive continuously in an extruder. The suitable hot-melt adhesive is solid and, apart from impurities, free of solvents.

(19) The viscosity of the suitable hot-melt adhesive according to the invention should be from 3000 to 50,000 mPas, preferably from 5000 to 30,000, in particular greater than 10,000 mPas, measured at the application temperature. This is between 140 and 190° C. (Brookfield, EN ISO 2555, measured at the stated temperature).

(20) The pressure-sensitive hot-melt adhesives according to the invention are suitable for bonding the all kinds of materials. Thus, materials such as polyolefin films can be bonded to one another, for example polyethylene films or polypropylene films, polyolefin nonwovens, for example polyethylene nonwovens or polypropylene nonwovens, polyurethane films, polyurethane foams, films of cellulose derivatives, polyacrylate or polymethacrylate films, polyester films, in particular polylactide, polycaprolactone, polyester amide. In this regard, the molten adhesive is applied onto a substrate and then adhesively bonded to a second substrate.

(21) Another preferred embodiment applies the adhesive according to the invention as an adhesive layer onto a carrier. The carriers concern the known flexible films that are also suitable as an adhesive tape. These non-tacky films are coated with a hot-melt adhesive according to the invention on one or both surfaces. The layer thickness of the applied adhesive ranges for example from 50 to 500 g/m.sup.2 (ca. 50 to 500 μm). The layer thickness is particularly intended to be from 100 to 350 g/m.sup.2.

(22) These adhesive layers posses a good adhesion to the carrier material. Such carrier films usually possess a non-stick coated back side that can be easily separated from the pressure-sensitive adhesive layer.

(23) A specific category of usage of the hot-melt adhesives in accordance with the invention is the coating of self-adhesive films, tapes or labels with an adhesive layer. Here, tapes or films, based for example on polyolefins or polyesters, are coated with the inventively suitable hot-melt adhesive. In this case, a permanently sticky adhesive layer is obtained by choosing an appropriate adhesive. These materials can then be converted. Permanent adhesive films, labels and tapes can be manufactured in this way. The thus obtained self-adhesive surfaces can optionally be covered by non-adhesively coated materials.

(24) The adhesives according to the invention are cloudy. At room temperature a 1 cm thick layer is opaque. However, there is no bleeding of the individual ingredients, thus the bond strength of the nonbonded layer or to adhesively bonded substrates is also not diminished. Adhesives according to the invention are stable in the melt and no phase separation occurs in the molten state even with longer storage times. The adhesives used according to the invention exhibit a good tack. The layers are elastic and exhibit a good cohesive bond. The two block copolymers form a stable mixture that does not lead to a phase separation. Thus one obtains high adhesion.

(25) The adhesives according to the invention are known as a coating for film applications. The corresponding coated products can be employed in many areas of application, for example as adhesive tapes or labels, multi-layer films for use as tamper-proof seals, for packaging, in sanitary products or in medical applications.

EXAMPLES

Example 1

(26) TABLE-US-00001 20 parts ethylene/octene (Infuse D 9808) OBC copolymer  5 parts SBS (Kraton D 1118) styrene block copolymer  5 parts SIS (Kraton D 1126) styrene block copolymer 30 parts resin (Escorez 5320) 10 parts soft resin, (Sylvatac RE12) liquid resin 20 parts naphthenic oil (Nyflex 222B)  1 part stabilizer (Irganox B 225) antioxidant Viscosity: 27 500 mPas, 150° C. Viscosity: 15 300 mPas, 170° C.

(27) In a thin layer the adhesive is cloudy in the solid or molten state (visual assessment).

(28) A backing film (PE, 50 μm) was coated with ca. 250 g.

(29) Once cooled, a film was bonded to a glass plate, pushed with a roller (1 kg) and stored for 24 hours at 25° C. The bond strength was then measured at specified times.

(30) TABLE-US-00002 20 min 50 N/25 mm 24 h 60 N/25 mm  3 d 60 N/25 mm

(31) The adhesion remained constant even after storage and no bleeding of the incompatible components occurred.

Comparative Example 2

(32) TABLE-US-00003 20 parts ethylene/octene (Infuse D 9808) OBC copolymer  8 parts SBS (Kraton D 1118) styrene block copolymer  8 parts SIS (Kraton D 1126) styrene block copolymer 43.5 parts   resin (Regalite R 1125) 20 parts polyisobutylene (Parapol 1300) 0.5 parts  stabilizer (Irganox B 225) antioxidants Viscosity: 51 200 mPas, 170° C.

(33) In a thin layer the adhesive is cloudy in the solid or molten state (visual assessment).

(34) The bond strength of a coated film is low (measured as loop tack, ASTM D 6195).

Comparative Example 3

(35) TABLE-US-00004 20 parts ethylene/octene (Infuse D 9808) OBC copolymer  5 parts SBS (Kraton D 1118) styrene block copolymer  5 parts SIS (Kraton D 1126) styrene block copolymer 40 parts resin (Escorez 5320) 10 parts resin (Foral 85) 10 parts naphthenic oil (Nyflex 222B) 0.5 parts  stabilizer (Irganox B 225) antioxidants Viscosity: 42 700 mPas, 150° C. Viscosity: 19 200 mPas, 170° C.

(36) The bond strength of a coated film (loop tack) is low.