• 专利附录
  • 专利说明
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    • 专利摘要:
    The present invention relates to pressure sensitive adhesive compositions comprising poly (1-alkene) elastomers and multifunctional (meth) acrylate components. The invention also relates to articles comprising the compositions and methods of making the compositions.
    公开号:KR20040030418A
    申请号:KR10-2003-7004294
    申请日:2001-01-15
    公开日:2004-04-09
    发明作者:미셸 에이. 크래톤；패트릭 디. 하이드
    申请人:쓰리엠 이노베이티브 프로퍼티즈 캄파니；
    IPC主号:
    专利说明:

    Pressure sensitive adhesive comprising poly (1-alkene) elastomer and multifunctional (meth) acrylate, articles made therefrom and method for preparing the same (Pressure Sensitive Adhesive Comprising Poly (1-Alkene) Elastomer and Multifunctional (Meth) Acrylate, Articles Prepared Therefrom and a Method of Making}
    [2] Poly (1-alkenes) are alpha-olefin polymers, also called poly- (α-olefins). Poly (1-alkenes) are known in the art to be useful in various compositions such as pressure sensitive adhesives. However, each particular pressure sensitive adhesive typically does not have the necessary properties to meet the requirements of all of the many different specific applications that exist for the pressure sensitive adhesive. There is a continuing need for pressure sensitive adhesives with specific properties tailored to meet the requirements of a particular end use. For example, it is desirable to provide a poly (1-alkene) elastomer-based pressure sensitive adhesive that can adhere well to polar substrates. It is also desirable to have adequate cohesive strength so that such an adhesive can be removed cleanly from the end of the attachment without being separated from the back side (when used in tape form).
    [3] Summary of the Invention
    [4] The pressure sensitive adhesive composition of the present invention is bonded to a wide range of substrates with high adhesion to the back side of the tape, that is to say that the tape adheres to the surface but with the adhesive clear from the surface upon removal and still adhered to the back side. In an attempt to address the need for remaining pressure sensitive adhesives, it is appropriate to provide a unique balance of adhesive properties.
    [5] In one embodiment, the pressure sensitive adhesive composition of the present invention comprises a first region comprising a poly (1-alkene) elastomer; And a second region comprising a multifunctional component selected from a multifunctional (meth) acrylate monomer, a multifunctional (meth) acrylate oligomer, and combinations thereof, wherein the second region comprises the total weight of the second region. And at least about 30% by weight multifunctional component on a basis. In other embodiments, the pressure sensitive adhesive composition comprises at least 50% by weight of at least one poly (1-alkene) elastomer and at least one multifunctional (meth) acrylate component.
    [6] The pressure sensitive adhesive composition may comprise a wide range of substrates such as polar materials such as glass, metals and polar polymers; And nonpolar materials such as polyolefins, and can be tailored to provide a variety of cohesive strengths suitable for the desired end use. Optionally crosslinking the pressure sensitive adhesive composition in order to provide improved cohesive strength properties so that the tape can be removed cleanly from the substrate without the adhesive separating from the back side or the cohesiveness of the adhesive broken and leaving adhesive residue on the surface. You can.
    [7] This balance of adhesive properties is particularly suitable for applications such as paint shielding tape applications, where the adhesive is expected to not only be firmly attached to the shielded surface but also to be removed cleanly from the surface without being separated from the backside. Adhesive tapes used for paint shielding applications typically use high strength backings such as polyester.
    [1] The present invention relates to a pressure sensitive adhesive composition comprising a poly (1-alkene) elastomer and a multifunctional (meth) acrylate component. The invention also relates to articles comprising the compositions and methods of making the compositions.
    [8] Pressure sensitive adhesives of the invention comprise at least one poly (1-alkene) elastomer and at least one multifunctional (meth) acrylate. In a preferred embodiment, the poly (1-alkene) elastomer is present in an amount of at least 50 parts by weight, more preferably at least 60 parts by weight of the total composition. Preferably, the composition is about 0.1 to about 40 parts by weight, more preferably about 0.1 to 20 parts by weight, even more preferably about 1 to about 4 parts by weight, most preferably per 100 parts by weight of poly (1-alkene) elastomer Preferably from about 0.5 to about 10 parts by weight of the multifunctional component.
    [9] Preferably, the composition may be hot-melt (ie, the composition is a hot melt adhesive). As used herein, “hot melt adhesive” refers to an adhesive that has sufficient viscosity during softening so that the adhesive can be hot melt treated (eg applied to a substrate). Rather than needing to actually melt the adhesive at the processing temperature, the adhesive should soften to the point that allows the adhesive to flow at processing pressure. By controlling the treatment temperature, the viscosity of the adhesive can be easily adjusted for the application.
    [10] The hot melt adhesive can advantageously reduce or eliminate the use of organic solvents in the adhesive and its treatment. Hot melt adhesive systems are essentially 100% solids systems. Typically, such systems have up to about 5% organic solvent or water, more typically up to about 3% organic solvent or water. Most typically, this system does not have organic solvents and water. Advantageously, by reducing the use of organic solvents, the specific handling surroundings associated with it is reduced.
    [11] The composition of the present invention may be formed by mixing a poly (1-alkene) elastomer with a polyfunctional (meth) acrylate under mixing conditions sufficient to form a well dispersed but phase-separated mixture. For example, poly (1-alkene) elastomers can be melt-mixed with multifunctional (meth) acrylates under significant mixing as well as heating and shear stresses to form compositions. The composition may optionally further comprise a photoactive agent for curing or crosslinking the composition.
    [12] In particular, it is difficult to melt two or more materials with extremely different melt viscosities when one material is substantially insoluble in another, for example when one material is polar and the other material is nonpolar. Those skilled in the art of processing will generally understand. Surprisingly, under ambient and melt-treatment conditions, non-polar poly (1-alkene) elastomers are sufficiently mixed with polar and relatively low viscosity multifunctional (meth) acrylate monomers and / or oligomers to achieve phase-specific properties. It has been found that an isolated composition can be formed.
    [13] In addition, surprisingly, these materials can form useful compositions, such as phase-separated pressure-sensitive adhesive compositions with high cohesive strength. Preferred embodiments of the compositions of the present invention exhibit unexpected advantages. For example, when curing the composition of the present invention by exposure to an electron beam, it can be cured with higher gel fractions at significantly lower radiation doses compared to poly (1-alkenes) without polyfunctional (meth) acrylates. Figured out. It has a low molecular weight (having an intrinsic viscosity of less than about 1.6 dL / g) and a medium molecular weight (having an intrinsic viscosity of less than about 2.5 dL / g), which is the most easily melt-treated poly (1-alkene) When using poly (1-alkenes) it is most evident. Increasing the gel fraction at low doses can advantageously prevent degradation of radiation-sensitive substrates such as polypropylene in which the compositions of the invention are disposed, for example chain breakage of the polymer backbone.
    [14] In addition, the compositions of the invention preferably exhibit high adhesion to substrates such as polyacrylates and polyesters such as polyethylene terephthalate and polyethylene naphthalate. This is surprising because the poly (1-alkene) -based adhesives are relatively nonpolar, while the polyester and polyacrylate substrates are relatively polar.
    [15] domain
    [16] Preferably, the pressure sensitive adhesive composition comprises a first region (typically continuous) comprising poly (1-alkene) elastomer and at least about 30% by weight multifunctional (meth) acrylate in order to exhibit further improvement in the advantages of the present invention. Has a second region (typically discontinuous). Preferably, the second region is at least about 50% by weight, more preferably at least about 70% by weight, most preferably at least about 90% by weight, based on the total weight of the second region, multifunctional (meth) acrylate It includes.
    [17] In a preferred embodiment of the composition of the present invention, the first region comprising the poly (1-alkene) elastomer is a continuous region, while the second region comprising the multifunctional (meth) acrylate is a substantially discontinuous region within the first region. To form. Discontinuous areas may appear in a variety of forms, including but not limited to, droplets, spheres, fine stripes, flat discs, and combinations thereof. The size and shape of the discontinuous region can be determined by a number of variables, such as the amount of shear and external stress applied to the composition in the melt condition; Mixing time and temperature; And the time that elapses between composition formation and any curing.
    [18] The dimensions of the discontinuous region can vary and typically can range from submicrons to about 100 microns. Each region is a suitable microscope, for example a transmission electron microscope (TEM) capable of detecting structures up to about 1 nanometer in size or a scanning electron microscope (SEM) capable of detecting structures up to about 10 nanometers in size. It is measured by determining the smallest of the two dimensions visible through. As used herein, "region size" refers to the size of the upper limit of the size of at least about 80%, preferably at least about 90%, of the area of the representative composition sample as seen through TEM or SEM. For example, in a representative sample, an area size of about 5 microns means that at least about 80% of the area is less than about 5 microns. Preferably, the discrete region size is less than about 10 microns, more preferably less than about 5 microns, and most preferably less than about 1 micron.
    [19] When the area size on the multifunctional (meth) acrylate is less than about 1 micron, the pressure sensitive adhesive composition of the present invention has the following high shear strength, for example, at room temperature, as compared to the same composition without polyfunctional (meth) acrylate. Suspended shear times of at least about 500 minutes, preferably at least about 1000 minutes, more preferably at least about 5000 minutes, according to the shear strength tests 1-4.
    [20] After mixing, the composition of the present invention can be coated onto a substrate. After coating, it was observed that discontinuous areas could coalesce into larger areas over time. Preferably, the composition can be cured, for example by exposure to radiation, to maintain the desired phase separation. The composition may be cured immediately after coating with the desired final form, such as a tape article, or may be stored in the final form and then cured. In curing, it is preferred to cure the composition using electron beam radiation.
    [21] Poly (1-alkene) elastomer
    [22] Any suitable poly (1-alkene) elastomer can be used in accordance with the present invention. Poly (1-alkene) elastomers may be homopolymers or copolymers. Preferred poly (1-alkene) elastomers used in the present invention have a glass transition temperature (Tg) of about -70 ° C to about 0 ° C, more preferably about -60 ° C to about -25 ° C.
    [23] The poly (1-alkene) elastomer used in the present invention preferably has the following formula.
    [24] H (CH 2 -CRH) n -H
    [25] Wherein R is independently selected from monovalent hydrocarbyl groups, provided that at least about 60 mole%, preferably at least about 80 mole% of the R groups are 6-18 carbon atoms, more preferably 6-12 Contains carbon atoms; n is an integer ranging from about 80 to about 50,000. Examples of suitable poly (1-alkene) elastomers include, but are not limited to, poly (1-hexene), poly (1-heptene) and poly (1-octene).
    [26] Preferably, the poly (1-alkene) elastomers comprise essentially ethylenically saturated backbones, optionally with terminal ethylenically unsaturated groups. Most preferably, the poly (1-alkene) elastomer is saturated at least 99.5%, or even at least 99.9%. Such preferred elastomers contribute to the melt-treatment efficiency (in other words, the elastomers can be melt treated with the multifunctional component without a significant increase in thermally induced gelling). If too much ethylenic unsaturation is present in the elastomer, undesirably high levels of crosslinking may occur when the elastomer is melt treated with the multifunctional component, which potentially hinders the melt treatment of the composition.
    [27] Preferably, the poly (1-alkene) elastomer is derived from essentially all α-olefin monomers, most preferably monomers free of polyunsaturation (eg in the case of diene type monomers). It is also preferred that the poly (1-alkene) elastomer is essentially derived from non-aromatic monomers such as aliphatic monomers. Representative examples of α-olefin monomers that may be used to form poly (1-alkene) elastomers are ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and branched α -Olefins such as 2-methyl-1-butene, 2-ethyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-hexene, 2-ethyl-1-hexene, 5-methyl-1- Hexene, 5-ethyl-1-hexene and the like and combinations thereof.
    [28] The preparation of poly (1-alkene) elastomers from α-olefin monomers is described, for example, in US Pat. No. 5,112,882; 5,644,007 and 5,202,361. References demonstrate how poly (1-alkene) elastomers can be polymerized to the desired molecular weight, measurable by intrinsic viscosity (I.V.). The poly (1-alkene) elastomers preferably have a weight average molecular weight (Mw) of about 25,000 to about 10,000,000, more preferably about 100,000 to about 3,500,000, most preferably about 250,000 to about 1,000,000.
    [29] Multifunctional (meth) acrylate component
    [30] The multifunctional (meth) acrylate component contains two or more functional groups (eg, vinyl groups) that react with the poly (1-alkene) elastomer upon irradiation of the composition. Suitable materials can be used for the multifunctional (meth) acrylate component. The term "(meth) acrylate" includes acrylates as well as acrylates.
    [31] Typically, the multifunctional (meth) acrylate component is a non-polymer. Preferably, the multifunctional (meth) acrylate component is selected from multifunctional (meth) acrylate monomers, multifunctional (meth) acrylate oligomers (including dimers, trimers, etc.) and combinations thereof. Useful multifunctional (meth) acrylates include difunctional (meth) acrylates, trifunctional (meth) acrylates, tetrafunctional (meth) acrylates, and the like.
    [32] Examples of specific multifunctional (meth) acrylates include trimethylolpropane triacrylate as well as 1,6-hexanediol diacrylate; Pentaerythritol tetraacrylate; 1,2-ethylene glycol diacrylate; 1,2-dodecanediol diacrylate; Polyfunctional (meth) acrylates as disclosed in US Pat. No. 4,379,201, such as urethane diacrylate.
    [33] The polyfunctional (meth) acrylate is preferably about 0.1 to 40 parts by weight, more preferably about 0.1 to about 20 parts by weight, even more preferably about 0.5 to about 10 parts by weight of poly (1-alkene) elastomer It is present in parts by weight, most preferably about 1 to about 4 parts by weight.
    [34] additive
    [35] Suitable additives may be used in the pressure sensitive adhesive composition of the present invention. For example, especially if the composition of the invention is cured by actinic radiation, the composition of the invention may optionally further comprise a photoactive agent such as a photoinitiator or a photocrosslinker. The photoactive agent is typically included in an amount of about 0.1 to about 6 parts by weight, preferably about 0.1 to about 2 parts by weight per 100 parts by weight of the composition.
    [36] Similarly, one or more tackifying resins referred to herein as "adhesives" may optionally be included in the compositions of the present invention. The total amount of tacky resin in the composition is typically from 0 to about 150 parts by weight, preferably from about 5 to about 50 parts by weight, most preferably from about 25 to about 35 parts by weight, per 100 parts by weight of the poly (1-alkene) elastomer.
    [37] The composition may also contain other ingredients suitable for the desired end use of the adhesive. For example, other useful additives include fillers, pigments, dyes, plasticizers, fiber reinforcing agents, foaming agents, blowing agents, ceramic microspheres, glass microspheres, polymer microspheres, antioxidants, stabilizers, Processing oils, flame retardants, viscosity modifiers, and combinations thereof. Additives are added in amounts suitable to achieve the desired properties for the end use.
    [38] Manufacturing method
    [39] The pressure sensitive adhesive composition of the present invention may be prepared via a solvent-free method or a solvent-based method. Preferably, the composition is prepared via essentially a solvent-free, most preferably solvent-free method. The compositions of the present invention can be prepared using standard melt-mixing equipment such as, for example, reciprocating single screw extruders, twin screw extruders and kneaders. In some cases, it may be desirable to use two or more portions of the device in line to provide sufficient melt mixing of the composition.
    [40] In a preferred method, the poly (1-alkene) elastomer is melted in a hot melt mixer or single screw extruder and then fed to a twin screw extruder having a plurality of feed ports, through which the multifunctional (meth) acrylate and any additives For example, adhesive resin can be supplied to an extruder. Any additive may be introduced by itself through the feed port or may be premixed with other additives and then fed through the feed port. If the component added is a liquid, such as part of a multifunctional (meth) acrylate, it can be pumped into a pot and drained at a controlled rate using a peristaltic pump. The screw speed and the extruder temperature are set to produce sufficient shear and significant mixing at a sufficiently high temperature for a time sufficient to mix the poly (1-alkene) elastomer with the downstream components. Incompatible materials are blended together using a dispersing and distributing mixing action to preferably form a fine, uniform dispersion of multifunctional (meth) acrylate in a poly (1-alkene) elastomer.
    [41] The extruder body temperature is typically set at about 100 ° C. to about 180 ° C. while increasing the temperature profile. The temperature may vary depending on the particular composition and the amount of mixing desired. The composition is typically pumped out of the extruder body and pumped into a soft hose through a die with a hole set to provide the desired adhesive thickness.
    [42] Typically, an extruded film die is used to coat the composition of the present invention onto a suitable substrate. Preferably, a contact coating die is used. The coated composition can then be optionally cured, optionally immediately, or subsequently optionally cured. For example, the coated composition can be cooled and wound into a roll for later curing. Alternatively, the compounded extrudate may be pumped in the form of a rope or stick for subsequent remelting, remixing, and coating and curing to the substrate.
    [43] The coated composition can be cured by exposure to radiation such as electron beam, gamma or actinic radiation. Compared to actinic radiation, electron beam and gamma radiation are advantageously used to cure the composition without requiring the use of an initiator. A commonly available electron beam curing apparatus such as Wilmington, Delaware, USA Devices available from Energy Sciences Incorporated are suitable for carrying out the curing step. Preferred electron beam doses required to cure the compositions of the present invention typically range from about 1 to about 20 megarads (Mrads), preferably from about 2 to about 10 Mrads.
    [44] Compositions of the present invention comprising photoactive agents, such as photoinitiators and / or photocrosslinkers, utilize a source of actinic radiation of sufficient energy (ie, wavelength range) to generate free radicals when projected onto a particular selected photoactive agent. Can be cured. Although the wavelength range of the photoactive agent disclosed above is preferably about 150 to about 400 nanometers, wavelengths outside this range may be effectively used depending on the particular photoactive agent. The radiation energy in the preferred wavelength range is typically about 100 to about 1,500 milliJoules / cm 2 , preferably about 200 to about 800 milli Joules / cm 2 .
    [45] In the practice of the method of the invention, the composition is typically coated onto a substrate. The substrate may for example be a film, foam, woven web or nonwoven web. Suitable substrates include, but are not limited to, polymers, glass, ceramics, metals, and composites thereof. The substrate may be in a suitable form such as a sheet or a three-dimensional object.
    [46] A particularly useful substrate is the back side of the tape. Suitable tape backings include oriented and non-oriented polymeric films, woven and nonwoven fabrics, metal foils, polymeric foams, and the like. The back side may be made from a variety of materials, including but not limited to polyethylene, polypropylene, cellulose, polyester, polyacryl, and polyimide.
    [47] In a preferred embodiment of the article of the invention, the article comprises a tape back side with a cured coating of pressure sensitive adhesive thereon. In a very preferred embodiment, the cured pressure sensitive adhesive composition has a polyfunctional (meth) acrylate region size of about 3 microns, more preferably about 1 micron, and the composition is a polyester film substrate, for example polyethylene terephthalate Or polyester film substrates such as polyethylene naphthalate; Polyacryl film; Or coated and cured on a polyacrylic foam substrate. Such tapes preferably exhibit excellent adhesion to polyester and polyacrylic substrates, and the pressure sensitive adhesive more preferably exhibits relatively high shear strength when the multifunctional (meth) acrylate region has a region size of about 1 micron. Have
    [48] In addition, the pressure sensitive adhesive composition may be made of an adhesive transfer tape wherein a layer of the pressure sensitive adhesive composition is coated over a release liner. Suitable release liners include, but are not limited to, polymer films and papers that have been treated with a release agent such as silicone.
    [49] The coated composition on the release liner can be cured and the coated liner is wound with a roll. The roll is then released, the composition is applied onto the surface, and the release liner is removed to attach the composition to additional surfaces. Alternatively, a composition coated on the liner but not cured may be applied to the desired surface and then cured on the surface with or without the liner, depending on the type of liner and the method of curing. An uncured composition on the liner may be used to apply two substrates by applying, removing the liner, adhering the second substrate to the composition and curing the composition between the provided substrates, at least one of the substrates being cured It is transparent to the type of radiation used for.
    [50] The following non-limiting examples are intended to illustrate certain embodiments of the present invention. All materials are reported in parts by weight and equal to parts by weight per 100 parts by weight of poly (1-alkene).
    [51] Test Methods
    [52] 180 ° peel adhesion test
    [53] 1.25 cm width and 15 cm for 180 ° peel adhesion for panels of cleaned glass (glass), stainless steel (SS), coarse polypropylene (PP), low density polyethylene (LDPE) or anodized aluminum (Alum) A pressure sensitive adhesive tape sample of length was tested. The sample was adhered to the test surface by winding the tape with a 2.1 kilogram (kg) roller using four passes. After aging for about 24 hours at controlled temperature and humidity (CTH) conditions (about 22 ° C and 40% relative humidity), unless otherwise stated, the Model 3M90 slip / peel tester at 30.5 cm per minute in 180 ° geometry. The tape was tested using (available from Instruments Instruments, Inc., Hingham, Mass.). Results were determined in pounds per 0.5 inch and reported in N / dm. When the adhesive splits cohesively and residues are left on both the tape and the panel, the breakage is represented by "coh", when the adhesive is adhesively separated from the back, "adh" and the adhesive is adhesively separated from the panel. "Adhp" when present, and "mix" when one or more breakage patterns are present.
    [54] Shear strength test 1 to 4
    [55] Cut strength (determined by retention time) was measured for pressure-sensitive adhesive tape samples under CTH conditions. Very high shear strength (more than 10,000 minutes) is desirable when the sample is not only resistant to flow under load but also to be removed cleanly. Test 1 used a piece of 12.7 mm x 12.7 mm tape attached to a stainless steel sheet with a 2.1 kg roller using four passes. The panel was then suspended at -2 ° from the vertical position to identify the shear failure pattern. 1000 gram weight was suspended from the sample. The amount of time to drop further was recorded. The test was stopped after 10,000 minutes. All shear times are the average of two test samples.
    [56] Unless otherwise stated, all recorded break times are the result of cohesive breaks. Designated as "A" indicates a break in which 75 to 100% of the break is adhesive.
    [57] Test 2 was performed in the same manner as in test 1 except using a 12.7 mm × 25.4 mm sample. Test 3 was performed in the same manner as in test 1 except using a 25.4 mm × 25.4 mm sample. Test 4 was performed in the same manner as in test 2 except that 500 gram weight was used and the test temperature was 70 ° C.
    [58] Intrinsic Viscosity [(ASTM D 2857-70 (Reapproved 1977)]]
    [59] Intrinsic viscosity (I.V.) is directly related to polymer molecular weight. This test was used to characterize the various poly (1-octene) elastomers used herein. Using a Canon-Fenske 150 viscometer in a water bath adjusted to 25 ° C., 10 milliliters of I.V. per 0.1 gram (g / dL) of sample solution in toluene was measured. Record I.V. as dL / g. The solvent used was toluene.
    [60] Gel Content [ASTM D 3616-82]
    [61] Gel content was determined by placing a square test specimen (3.8 cm × 3.8 cm) containing about 0.06 grams of the composition in a 120 mesh stainless steel basket of about 4.4 × 4.4 × 1.3 cm. The content was measured at approximately 0.1 mg and then immersed in a beaker with a stopper containing enough toluene to cover the specimen. After extraction for 24 hours, the basket (with sample) was removed, drained and placed in an oven at 93 ° C. Baskets and specimens were dried to constant weight. The gel content was determined from the amount of material extracted as follows:
    [62] (a)% of extract = (weight lost during extraction / weight of original sample) × 100
    [63] (b)% gel content = 100 −% extract
    [64] The gel content of the composition was corrected for the back side weight, but not for the weight of the pressure sensitive adhesive.
    [65] Materials Used in the Examples
    [66] Arkon TM P-115-hydrogenated aliphatic tacky resin available from Arakawa Chemicals, Houston, Texas, USA
    [67] Regales TM 1126-Hydrogenated aliphatic adhesive resin available from Hercules Inc. of Wilmington, Delaware, USA
    [68] Irganox ™ 1010-antioxidant tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4'-) available from Ciba-Geigy Corporation, Switzerland. Hydroxyphenyl) -propionate] methane
    [69] TMPTA-trimethylolpropane triacrylate (Sartomer SR-351) is a tri-functional monomer available from Sartomer Company Incorporated of Exton, Pa.
    [70] HDDA-1,6-hexanedioldiacrylate (Sartomer SR-238) is a bifunctional monomer available from Sartomer Company Inc. of Exxon, PA.
    [71] PETA-pentaerythritol tetraacrylate (Sartomer SR-295) is a tetrafunctional monomer available from Sartomer Company Inc. of Exxon, PA.
    [72] Example 1-3
    [73] Methods for making poly (1-octenes) are disclosed in US Pat. No. 5,644,007. 25% solid triethylaluminum (AlEt 3 ) in heptane (Albemarle Corp., Baron Rouge, Louisiana, USA) and a 66: 1000 ratio promoter of purified 1-octene and Lynx TM 900 catalyst (Available from Catalyst Resources Inc., Pasadena, Texas, USA) and a 63.6: 10,000 ratio catalyst suspension of hexanes were fed to a 20 L capacity stirred tubular reactor described in US Pat. No. 5,644,007. The purified 1-octene feed rate was 350.0 g / min, the cocatalyst solution feed rate was 22.13 g / min, and the catalyst suspension feed rate was 25.30 g / min The monomer and cocatalyst solution were fed through a t-pipe linker. Were mixed, preheated to about 70 ° C. and pressurized to the reactor, a continuous stirred catalyst suspension under nitrogen was introduced using a peristaltic pump to prevent stratification and oxygen contamination. The temperature of the reaction mixture in the reactor zone of was maintained at about 70 ° C. The quenched reaction mixture was collected, the volatile components were removed, and the IV of the polymer was determined to be 2.0 dL / g.
    [74] Bonnot extruder (available from the Bonnot Company, Uniontown, Ohio, USA) at a feed rate of 94.4 grams / minute (g / minute) of 2.0 dL / g IV poly (1-octene) elastomer From the feed to the first body section of the twin screw extrusion compounding device. The Bonnot temperature was adjusted to 93 ° C. and equipped with a weighing Zenith gear pump (available from Zenith Products Company, West Newton, Mass.). The twin screw extruder (TSE) was fully engaged and operated in a co-rotating manner. TSE was available from Warner & Pfleiderer, Lamsey, NJ, and was a model ZSK 30 with 12 body sections and 30 mm diameter and 36: 1 length to diameter ratio. A dry powder blend of 19 parts of tacky resin (Arcon ™ P-115) and 1 part of antioxidant (Irganox ™ 1010) is available from K-Tron ™ International, Pittman, NJ, USA. - a torch TM 50/50 split using a gravimetric feeder ratio (by weight) was supplied to the opening of the body 3 and 7. The total feed rate of the pressure-sensitive adhesive was 18.2 g / min. Master in combination with L / S TM 14 standard pump heads (model numbers LC-07553-80 and LC-07014-20, available from the Cole-Parmer Instrument Company, Vernon Hills, Illinois, USA) Using a Masterflex ™ L / S ™ Variable Speed Modular Drive, trifunctional acrylate (trimethylolpropane triacrylate (TMPTA)) was drained into an opening in body 5 at a feed rate of 1.14 g / min. The peristaltic pump was equipped with an L / S ™ 14 Tygon ™ fuel and lubricant tube (available from Norton Performance Plastics, Wayne, NJ) with a 1.6 mm inner diameter. Set the TSE screw speed to 200 revolutions per minute (rpm), and the temperature profile is 0 ° C, 100 ° C, 30 ° C, 135 ° C, 0 ° C, 150 ° C, 0 ° C, 165 ° C, 165 ° C at the trunks 1-12, respectively. , 164 ° C, 177 ° C and 177 ° C. A Zenith gear pump was used to discharge the molten composition from the TSE into the soft hose and then into the contact rotary rod die. The gear pump, soft hose and contact die temperatures were set to 166 ° C. respectively. Gear pump rpm and film delivery speed were adjusted to provide a 29.3 g / m 2 coating weight over a 25 micrometer thick polyethylene terephthalate (PET) film.
    [75] The pressure sensitive adhesive obtained had a composition of 100 parts poly (1-octene) elastomer, 19 parts sticky resin, 1.2 parts TMPTA and 1 part antioxidant. The gel content of the composition after extrusion was 0.3%, indicating that negligible gelation occurred in the extrusion process. The negligible gel content demonstrates that the heat treatment of TMPTA with the tacky resin and poly (1-octene) does not cause significant thermal gelation or crosslinking. Thermal gelling is undesirable for melt processing because it can lead to poor extrusion quality.
    [76] The coated composition of Example 1 was subjected to an ELECTROCURTAIN model CB-175 (Wilmington, Mass., USA) operating at 175 kilovolt (kV) increasing voltage and 4 Megarad dose immediately after coating. Electron beam (EB) radiation from Co., Ltd.). The gel content of the cured composition was 35%. Examples 2 and 3 were prepared in the same manner as in Example 1, except that they were aged for two weeks under CTH conditions and then EB cured at 175 kV and 6-8 rads, respectively. Examples 1-3 were tested for adhesive properties and the results are shown in Table 1.
    [77] ExampleEB Dose (Mrads)Shear strength (min)180 ° peel adhesive (N / dm) (break mode, if applicable) Exam 2Exam 3Board LDPEPPGlass One432610,000+419778 2661670264841 3811194542-(coh)67
    [78] The electron beam cured sample immediately after coating (Example 1) was not only high adhesion to both polypropylene and glass but also high adhesion compared to the cured samples (Examples 2 and 3) after aging in CTH for 2 weeks. Shear resistance was shown. This example demonstrates the effect of composition immediately after coating and immediate curing and off-line curing at later time on the pressure sensitive adhesive properties.
    [79] Example 4 and Comparative Examples C1-C3
    [80] Examples 1 to 3, except that a poly (1-octene) elastomer having an IV of 2.5 dL / g was pumped into the torso 1 of the TSE using a Bonnot equipped with a Zenith gear pump operating at 77 ° C. Example 4 and Comparative Examples C1 to C4 were prepared using the same mixing and coating method as described for. Arcon ™ P-115 adhesive resin was fed into the opening in trunk 5 as dry powder. TMPTA was drained into the opening in Body 2 using a Masterflex ™ peristaltic pump. TSE temperature profiles were 0 ° C., 100 ° C., 30 ° C., 135 ° C., 45 ° C., 150 ° C., 0 ° C., 165 ° C., 170 ° C., 175 ° C., 177 ° C. and 177 ° C. at the trunk 1-12, respectively. The soft hose and die temperatures were maintained at 165 ° C. and the TSE screw speed was 200 rpm. The gear pump release rate and coating rate (9.2 meters per minute) were adjusted to provide a coating thickness of 59 g / m 2 over the polyethylene terephthalate film. The composition of Example 4 was 100 parts of 2.5 dL / g IV poly (1-octene) and 4 parts of TMPTA. The compositions of Examples C1 to C3 were 100 parts of 2.5 dL / g IV poly (1-octene). All examples were EB cured immediately after coating at 175 kV at the doses shown in Table 2. Adhesives were tested for shear strength and peel adhesion. The results are shown in Table 2.
    [81] ExampleEB Dose (Mrads)Shear strength in minutes (break mode, if applicable)180 ° peel adhesive (N / dm) (break mode, if applicable) Exam 2Exam 4Board GlassLDPEPPAlum C1425-(coh)-(coh)-(coh)74 (adh) C261422038565966 (adh) C3845342019485158 (adh) 48161 (A)7630 (A)8.2121382 (coh)
    [82] Inclusion of polyfunctional (meth) acrylates improves ambient temperature and elevated temperature shear strength. The data also demonstrates the excellent adhesion of the compositions of the present invention to PET films, as indicated by the cohesive failure pattern on anodized aluminum. In addition, the compositions of the present invention demonstrate high shear strength at room temperature (22 ° C.) and elevated temperature (70 ° C.) compared to compositions without polyfunctional (meth) acrylates at the same EB dose.
    [83] Examples 5-8
    [84] A similar mixing and coating method as in Examples 1 to 3 was used except for the use of different TSEs (30 mm diameter, 45/1 length to diameter ratio, 10 body sections, co-rotating Warner and Playderer model number ZSK-30). To prepare Examples 5-8. Examples 5 and 6 used poly (1-octene) elastomers with IV of 1.6 dL / g, while Examples 7 and 8 used poly (1-octene) elastomers with IV of 3.3 dL / g. The poly (1-octene) elastomer was pumped into the torso 1 of the TSE using Bonnot equipped with a Zenith gear pump operating at 104 ° C. Regalrez ™ 1126 tacky resin was melted at 163 ° C. and pumped into trunk 3 using a heated Zenith gear pump. TMPTA was drained into the opening in trunk 5 using a Masterflex ™ peristaltic pump. The screw speed was set to 200 rpm. The TSE was inclined from 93 ° C. at trunks 1 and 2 to 163 ° C. at trunks 7 and 8 and maintained at 149 ° C. at trunks 9 and 10 via a discharge Zenith gear pump, soft hose and die. The melting temperature at the inlet of TMPTA was kept below 149 ° C. to minimize degassing of TMPTA. Coating weight was adjusted by adjusting the line speed and gear pump discharge rate. 30.5 The samples were coated with a coating weight of 147 g / m 2 over-micrometer-thick PET film. The coated film was immediately exposed to electron beam radiation at 175 kV and 4 Mrads. The composition of the adhesive is shown in Table 3. After aging for 24 hours at CTH, the adhesive properties were measured and are shown in Table 3.
    [85] ExamplePoly (1-alkene) (part)Adhesive resin (part)TMPTA (part)180 ° peel adhesive (N / dm) (break mode, if applicable)Shear strength (min) BoardExam 2Exam 3 GlassPPLDPE 5100252166 (coh)186171 (coh)27282 6100552203 (coh)214 (coh)1561,1623,359 7100252117112652,6117,435 810055215817312110,000+10,000+
    [86] The adhesive properties shown in Table 3 can be modified by the selection of poly (1-alkene) elastomers and by varying the amount of adhesive resin to provide cohesive failure or adhesion failure or to increase shear strength. Demonstrate that you can. If no breakage pattern was observed, the adhesive was peeled off cleanly from the panel.
    [87] Examples 9-15
    [88] Examples 9-15 were manufactured using the apparatus described in Examples 1-3. Using Bonnot equipped with a gear pump set at 77 ° C., a poly (1-octene) elastomer with an IV of 2.5 dL / g was pumped into trunk 1 of the TSE. TMPTA or HDDA was drained into the opening of trunk 3 with a Masterflex ™ peristaltic pump. Regalez ™ 1126 tacky resin was melted at 177 ° C. and drained into the opening of trunk 7. TSE temperatures were set to 0 ° C., 150 ° C., 150 ° C., 130 ° C., 130 ° C., 140 ° C., 135 ° C., 145 ° C., 130 ° C., 130 ° C., 140 ° C. and 150 ° C. in the trunks 1 to 12, respectively. The soft hose and die temperature was set to 165 ° C. As shown in Table 4, the TSE thread speed varied from 100 to 400 rpm. The gear pump rpm and coating speed were adjusted to provide a 29 gram / m 2 or 58 gram / m 2 coating weight (Ct.Wt.) on a 25 micrometer thick PET film. The composition was EB cured immediately after coating at 175 kV and 4 Mrads. The adhesive composition is shown in Table 4. The test results are shown in Table 5.
    [89] ExamplePoly (1-octene) (part)Regalez TM 1126 (part)TMPTA (part)HDDA (part)Ct.Wt. (g / m 2 )TSE thread speed (rpm) 9100204029400 10100206029400 111002010029400 12100200429400 13100552058100 14100552058200 15100552058400
    [90] Example180 ° peel adhesive (N / dm)Shear strength in minutes (break mode, if applicable) BoardExam 1Exam 2Exam 3Exam 4 GlassPPLDPE 952431738 (A)10,000+10,000+2,716+ 1035393037 (A)1,55410,000+2,715+ 112226397 (A)126 (A)5,249 (A)134 1219261922 (A)10,000+10,000+2,697+ 1310871671226,07810,000+280 14102606528710,000+10,000+1,535 15102606372810,000+10,000+600
    [91] The data in Table 5 shows how varying levels of TMPTA addition and screw speed changes can change the adhesive and shear properties of the adhesive.
    [92] Examples 16-19
    [93] In a Brabender sigma vane mixer at 170 ° C., powdered photocrosslinker (2,4-bis- (trichloromethyl) -6- (3 ', 4'-dimethoxyphenyl) -sim-triazine ) Were prepared by combining a poly (1-octene) elastomer with an IV of 1.6 dL / g and a tacky (Regalez TM 1126) resin. Specific compositions are shown in Table 6. The blended mixture was fed into an 18 mm diameter, corotating and fully engaged Leistritz TSE (model micro 18, available from Leastrichs AG, Germany) using Bonnot equipped with a Zenith gear pump. All extruder zones were set to 177 ° C. Masterflex ™ peristaltic pump was used to drain tetrafunctional acrylate (PETA) into the opening of the TSE. TSE screw speed was set to 100 rpm. The composition was coated at 50 g / m 2 on a 51 micron thick PET film. After the coating step using a UV-cured lamp with an H-bulb (Model No. 3461, Fusion Systems Inc., Rockville, Midland, USA) at a distance sufficient to provide 200 or 400 mJ / cm ` USA dose from the web. The coating was immediately examined. Table 6 shows the composition, UVA dose and peel adhesion test results.
    [94] ExamplePoly (1-octene) (part)Adhesive resin (part)Triazine (part)PETA (part)UVA dose (mJ / cm 2 )180 ° peel adhesion to aluminum (N / dm) (break mode) 16100280.150.2240099 (coh) 17100280.150.2220093 (coh) 18100280.150.1320095 (coh) 19100280.100.1340099 (coh)
    [95] The data in Table 6 illustrates how the use of tetrafunctional acrylate (PETA) with a photocrosslinker provides excellent adhesion to panels and backsides.
    [96] Example 20
    [97] 1.75 except that does not use (Micro Pearl (Micropearl) TM F100D available from Pierce Stevens, American Buffalo, New York (Pierce Stevens)) wt% F100D expansion obtain microspheres, and curing the foam sheet EB, 6,103,152 of U.S. Patent A 1,000 micron thick foamed acrylic sheet was prepared according to Example 1 using a hot melt composition. Example 20 was prepared by coating the pressure sensitive adhesive composition of Example 15 on a foam sheet 50 microns thick. Directly after coating, the coated composition was EB cured at 175 kV and 6 Mrads.
    [98] The application of a piece of 3M TM # 371 adhesive tape (available from Minnesota Minig and Manufacturing Company, St. Paul, Minn.) Directly to the pressure sensitive adhesive layer, Adhesion was tested. After a 5 minute residence time, the tape was removed without the pressure sensitive adhesive being transferred to the 3M ™ # 371 adhesive tape. This demonstrated the good adhesion of the poly (1-octene) pressure sensitive adhesives of the present invention to foamed acrylic substrates.
    [99] Example 21 and C4
    [100] Example 21 was prepared using the method of Examples 16-19 except that the extruder screw speed was 400 rpm. The composition was 100 parts of poly (1-octene) with an IV of 1.9 dL / g, 20 parts of sticky resin (Regalez TM 1126) and 4 parts of HDDA. Example C5 was prepared in the same manner using the same composition except without using HDDA. The adhesive was coated with a coating weight of 29 grams / m 2 . Both examples were cured and tested with electron beams at 175 keV and 4 Mrads. The results are shown in Table 7.
    [101] Example% Gel180 ° peel adhesive (N / dm)Shear strength (min) BoardExam 1Exam 4 GlassPPLDPE 215710131010,000+2,700+ C5441434840.1
    [102] Reasonable variations and changes may be made from the above disclosure without departing from the spirit or scope of the invention as defined in the claims.
    权利要求:
    Claims (28)
    [1" claim-type="Currently amended] A first region comprising a poly (1-alkene) elastomer; And
    A second region comprising a multifunctional component selected from a multifunctional (meth) acrylate monomer, a multifunctional (meth) acrylate oligomer, and combinations thereof; And the second region comprises at least about 30% by weight multifunctional component based on the total weight of the second region.
    [2" claim-type="Currently amended] The composition of claim 1 wherein the composition is cured.
    [3" claim-type="Currently amended] The composition of claim 1, wherein the second region comprises at least about 50% by weight multifunctional component based on the total weight of the second region.
    [4" claim-type="Currently amended] The composition of claim 1, wherein the second region comprises at least about 70% by weight multifunctional component based on the total weight of the second region.
    [5" claim-type="Currently amended] The composition of claim 1, wherein the second region comprises at least about 90% by weight multifunctional component based on the total weight of the second region.
    [6" claim-type="Currently amended] The composition of claim 1, wherein the first region is continuous and the second region is discontinuous.
    [7" claim-type="Currently amended] The composition of claim 1 wherein the composition is a hot melt adhesive.
    [8" claim-type="Currently amended] The composition of claim 1, wherein the poly (1-alkene) elastomer essentially comprises a saturated hydrocarbon backbone.
    [9" claim-type="Currently amended] The composition of claim 1, wherein the poly (1-alkene) elastomer is essentially derived from an α-olefin monomer that is not essentially polyunsaturated.
    [10" claim-type="Currently amended] The composition of claim 1, wherein about 0.1 to about 40 parts by weight of the multifunctional component is present per 100 parts by weight of the poly (1-alkene) elastomer.
    [11" claim-type="Currently amended] The composition of claim 1, wherein from about 0.1 to about 20 parts by weight of the multifunctional component is present per 100 parts by weight of the poly (1-alkene) elastomer.
    [12" claim-type="Currently amended] The composition of claim 1, wherein about 0.5 to about 10 parts by weight of the multifunctional component is present per 100 parts by weight of the poly (1-alkene) elastomer.
    [13" claim-type="Currently amended] The composition of claim 1, wherein about 1 to about 4 parts by weight of the multifunctional component is present per 100 parts by weight of the poly (1-alkene) elastomer.
    [14" claim-type="Currently amended] The composition of claim 1 wherein the poly (1-alkene) elastomer is selected from poly (1-hexene), poly (1-heptene), poly (1-octene), and combinations thereof.
    [15" claim-type="Currently amended] The method of claim 1, wherein the multifunctional component is trimethylpropane triacrylate; A composition selected from 1,6-hexanediol diacrylate and pentaerythritol tetraacrylate.
    [16" claim-type="Currently amended] The composition of claim 1 further comprising a photoactive agent.
    [17" claim-type="Currently amended] The composition of claim 1, further comprising an adhesive.
    [18" claim-type="Currently amended] At least 50 weight percent poly (1-alkene) elastomer; And
    Multifunctional component selected from multifunctional (meth) acrylate monomers, multifunctional (meth) acrylate oligomers and combinations thereof
    Pressure sensitive adhesive composition comprising a.
    [19" claim-type="Currently amended] Board; And
    The composition of claim 18 coated on at least a portion of the substrate
    Article comprising a.
    [20" claim-type="Currently amended] Board; And
    The composition of claim 1 coated on at least a portion of a substrate
    Article comprising a.
    [21" claim-type="Currently amended] The article of claim 20, wherein the substrate comprises a polyester.
    [22" claim-type="Currently amended] The article of claim 20, wherein the substrate is selected from films, foams, woven webs, and nonwoven webs.
    [23" claim-type="Currently amended] Board; And
    The composition of claim 2 coated on at least a portion of the substrate
    Article comprising a.
    [24" claim-type="Currently amended] The article of claim 23, wherein the substrate comprises a polyester.
    [25" claim-type="Currently amended] The article of claim 23, wherein the substrate is selected from films, foams, woven webs, and nonwoven webs.
    [26" claim-type="Currently amended] A first region comprising a poly (1-alkene) elastomer; And
    A multifunctional component selected from a multifunctional (meth) acrylate monomer, a multifunctional (meth) acrylate oligomer, and combinations thereof, and comprising at least about 30% by weight of the multifunctional component based on the total weight of the second region Second area
    Forming a pressure sensitive adhesive composition comprising;
    Applying the pressure sensitive adhesive composition to at least a portion of the substrate.
    [27" claim-type="Currently amended] 27. The method of claim 26, further comprising curing the pressure sensitive adhesive composition.
    [28" claim-type="Currently amended] At least 50% by weight of at least one poly (1-alkene) elastomer; And
    At least one multifunctional component selected from multifunctional (meth) acrylate monomers, multifunctional (meth) acrylate oligomers, and combinations thereof
    Forming a pressure sensitive adhesive composition comprising;
    Applying the pressure sensitive adhesive composition to at least a portion of the substrate.
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    同族专利:
    公开号 | 公开日
    JP2004510030A|2004-04-02|
    CN1466617A|2004-01-07|
    CA2423387A1|2002-04-04|
    AU2950001A|2002-04-08|
    WO2002026907A8|2003-03-13|
    MXPA03002547A|2003-10-15|
    US6544643B1|2003-04-08|
    BR0114112A|2004-02-10|
    EP1328598A1|2003-07-23|
    WO2002026907A1|2002-04-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-09-26|Priority to US09/670,068
    2000-09-26|Priority to US09/670,068
    2001-01-15|Application filed by 쓰리엠 이노베이티브 프로퍼티즈 캄파니
    2001-01-15|Priority to PCT/US2001/001380
    2004-04-09|Publication of KR20040030418A
    优先权:
    申请号 | 申请日 | 专利标题
    US09/670,068|US6544643B1|2000-09-26|2000-09-26|Pressure sensitive adhesive comprising poly elastomer and multifunctional acrylate, articles prepared therefrom and a method of making|
    US09/670,068|2000-09-26|
    PCT/US2001/001380|WO2002026907A1|2000-09-26|2001-01-15|Pressure sensitive adhesive comprising poly elastomer and multifunctional acrylate, articles prepared therefrom and a method of making|
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