• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    Pressure Sensitive Adhesive Tape, and Pressure Sensitive Adhesive Layer Preparation Method The present invention provides a pressure sensitive adhesive tape comprising: a layer of acrylic foam and rubber-based adhesive layers formed on both sides of said layer of acrylic foam, wherein the gel content of said rubber-based adhesive layers is 40% or more. furthermore, in order to realize the object of the present invention, a pressure-sensitive adhesive layer manufacturing method is provided, wherein the method comprises the steps of: manufacturing an acrylic foam layer; and forming rubber-based adhesive layers on one or both sides of said acrylic foam layer, wherein said step of forming the rubber-based adhesive layers comprises the steps of: manufacturing a styrene block copolymer, forming rubber-based adhesive layers by adding an adhesive agent and a plasticizer to said styrene block copolymer and setting the gel content of said rubber-based adhesive layers to 40% or more.
    公开号:BR112014008458B1
    申请号:R112014008458-0
    申请日:2012-10-11
    公开日:2021-06-22
    发明作者:Ae Jung Jang；Jang Soon Kim；Seung Min Yoo
    申请人:Lg Chem, Ltd.；
    IPC主号:
    专利说明:

    FIELD OF TECHNIQUE
    [001] The present invention relates to a pressure-sensitive adhesive tape, which includes an acrylic foam layer and rubber-based adhesive layers formed on both sides of the acrylic foam layer, wherein the adhesive layers based on rubber have a gel content of 40% or more. TECHNICAL BACKGROUND
    [002] Korean Patent Published No. 20070041896 describes a UV curable adhesive composition and an adhesive tape. Although the UV curing method has its merits such as instant cure, low curing temperature, no pollution/stability, uniformity of quality and the like, however, adhesive tape starting materials have high prices, a polymerization initiator or sensitizer is mixed and therefore there may be a problem in the fact that polymerization is carried out to change the quality of the tape when the tape is stored for a long period. Therefore, an innovative healing method is needed.
    [003] In addition, Korean Patent Published No. 2007-0004837 provides a pressure sensitive adhesive tape that has a center layer that includes a rubber-based pressure sensitive adhesive. Recently, however, as an automobile adhesive tape needs to withstand environments such as UV, rainwater and the like for a long time and also external physical impacts, vibrations and the like, an acrylic foam tape is applied. In this regard, there is an urgent need for a rubber-based adhesive and an acrylic foam tape that includes the rubber-based adhesive. DESCRIPTION OF THE INVENTION TECHNIQUE PROBLEM
    [004] It is an aspect of the present invention to provide a pressure sensitive adhesive tape that includes an acrylic foam layer that exhibits excellent impact absorption and a rubber-based adhesive layer that exhibits excellent adhesion even to substrates that have low energy of impact. surface. TECHNICAL SOLUTION
    [005] It is an aspect of the present invention to provide a pressure-sensitive adhesive tape, which includes: an acrylic foam layer and rubber-based adhesive layers formed on both sides of the acrylic foam layer, wherein the adhesive-based layers rubber products have a gel content of 40% or more.
    [006] It is an aspect of the present invention to provide a method of preparing pressure sensitive adhesive layers, which includes: preparing an acrylic foam layer; and forming one or more rubber-based adhesive layers on one or both sides of the acrylic foam layer, wherein forming one or more rubber-based adhesive layers includes: preparing a styrene block copolymer, forming of one or more rubber-based adhesive layers by adding a binder and plasticizer to the styrene block copolymer and setting the gel content of one or more rubber-based adhesive layers to 40% or more. ADVANTAGEOUS EFFECTS
    [007] According to the present invention, the pressure-sensitive adhesive tape that includes a rubber-based adhesive layer exhibits excellent impact absorption, particularly great adhesion to automobiles and excellent adhesion even to substrates that have low surface energy.
    [008] According to the present invention, as the method of preparation of pressure-sensitive adhesive tapes includes curing by means of irradiation of electron beams, the method provides short curing time and high degree of cure and, therefore, has high utility in terms of environmental impact and production. DESCRIPTION OF THE FIGURES
    [009] Fig. 1 is a cross-sectional view of a pressure-sensitive adhesive tape according to an embodiment of the present invention. BEST FORM
    [010] The above and other aspects, features and advantages of the present invention will become apparent from the detailed description of the embodiments below in conjunction with the accompanying drawings. It should be understood that the present invention is not limited to the following embodiments, it may be embodied in different forms and that the embodiments are provided for the full description and understanding of the present invention by those skilled in the art. The scope of the present invention is defined only by the claims. Similar components will be indicated by similar reference numerals throughout the specification.
    [011] The embodiments of the present invention will be described in detail below.
    [012] Pressure sensitive adhesive tape:
    [013] The present invention provides a pressure-sensitive adhesive tape that includes: an acrylic foam layer and rubber-based adhesive layers formed on both sides of the acrylic foam layer.
    [014] Acrylic foam layer:
    [015] The acrylic foam layer includes an acrylic resin. In accordance with the present invention, the acrylic resin may include a (meth)acrylic acid ester monomer containing C1 to C12 alkyl group and acrylic acid, without limitation. At present, if the monomer includes a very long chain alkyl group, the adhesive may deteriorate in cohesion and have difficulty adjusting the glass transition temperature (Tg) or adhesion. Therefore, it is desirable to use the (meth)acrylic acid ester monomer which contains C1 to C12 alkyl group. The (meth)acrylic acid ester monomer and acrylic acid may be present in any amount without limitation, so long as the amount can provide the desired effects. The (meth)acrylic acid ester monomer may be present in an amount from 85% by weight to 95% by weight and the acrylic acid may be present in an amount from 5% by weight to 15% by weight. If the amount of acrylic acid is less than 5% by weight, the acrylic foam layer may deteriorate in adhesion, and if the amount of acrylic acid exceeds 15% by weight, the acrylic foam layer may deteriorate in cohesion.
    [016] Examples of the (meth)acrylic acid ester monomer may include alkyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylate of isopropyl, n-butyl(meth)acrylate, t-butyl(meth)acrylate, sec-butyl(meth)acrylate, pentyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, (metha) 2-ethylbutyl acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylate and tetradecyl (meth)acrylate, without limitation. These can be used alone or in combination.
    [017] In addition, acrylic acid copolymerizable with the ester monomer of (meth)acrylic acid is a polar monomer. Acrylic acid can include a carboxyl group-containing monomer and/or a nitrogen-containing monomer, without limitation. The carboxyl group-containing monomer, for example, can include at least one selected from the group consisting of (meth)acrylic acid, maleic acid and fumaric acid, and the nitrogen-containing monomer can include at least one selected from the group which consists of acrylamide, N-vinylpyrrolidone and N-vinyl caprolactam.
    [018] According to the present invention, the acrylic foam layer can additionally include a photoinitiator and a crosslinking agent in the composition that includes the (meth)acrylic acid ester monomer that contains C1 to C12 alkyl group and acrylic acid.
    [019] The photoinitiator can initiate the curing reaction of the composition by irradiation with UV light or similar in a process of forming the acrylic foam layer. The photoinitiator can be any one typically used in the art without limitation.
    [020] Examples of the photoinitiator may include at least one selected from the group consisting of benzoin methyl ether, 2,4,6-trimethylbenzoyl diphenylphosphino oxide, bis(2,4,6-trimethylbenzoyl) phenylphosphino oxide, a ,α-methoxy-α-hydroxyacetophenone, 2-benzoyl-2-(dimethylamino)-1-[4-(4-morphonyl)phenyl]-1-butanone and 2,2-dimethoxy-2-phenylacetophenone. The photoinitiator can be present in an amount of 0.01 parts by weight to one part by weight based on 100 parts by weight of the composition. If the amount of photoinitiator is less than 0.01 parts by weight, the composition cannot be sufficiently cross-linked and lacks improved cohesion, and if the amount of photoinitiator exceeds one part by weight, the composition may have significantly deteriorated initial adhesion.
    [021] The crosslinking agent can adjust adhesion in terms of increased cohesion. According to the present invention, the crosslinking agent can be a component that can participate in the reaction by irradiation with UV light or the like, without limitations.
    [022] Examples of the crosslinking agent may include at least one selected from the group consisting of polyfunctional acrylate crosslinking agents such as 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, 1,2-diacrylate ethylene glycol and 1,12-dodecanediol acrylate; polyfunctional isocyanate crosslinking agents; and polyfunctional epoxy crosslinking agents, without limitation. The crosslinking agent can be present in amounts of 0.1 parts by weight to two parts by weight based on 100 parts by weight of the composition. If the amount of crosslinking agent is less than 0.1 parts by weight, the composition may deteriorate in adhesion, and if the amount of crosslinking agent exceeds two parts by weight the composition may deteriorate in cohesion.
    [023] The acrylic foam layer can additionally include other additives, such as porous fillers, coupling agents, antistatic agents, surfactants, binders, processed oil and the like, in addition to the photoinitiator and crosslinking agent. These additives can be additives typically used in the art and be suitably added within an appropriate range for the object of the present invention.
    [024] Rubber-based adhesive layer:
    [025] The present invention provides a pressure-sensitive adhesive tape that includes a rubber-based adhesive layer, which has a gel content of 40% or more. Particularly, the rubber-based adhesive layer preferably contains 40% to 80% gel content in terms of peel strength and high temperature retention. If the gel content of the rubber-based adhesive layer is less than 40%, the rubber-based adhesive layer may have deteriorated heat resistance, which allows the layer to withstand high temperature without changing shape or quality and may suffer deterioration from high temperature retention. More specifically, if the gel content of the rubber-based adhesive layer is less than 40%, the rubber-based adhesive layer has a loose crosslinking structure, which can be significantly distorted and easily deformed when subjected to external force or stress, where the rubber-based adhesive layer can significantly deteriorate in durability under high temperature or high temperature and humidity. On the other hand, if the rubber-based adhesive layer contains more than 80% gel content, the rubber-based adhesive layer may have deteriorated adhesion to a substrate to be joined.
    [026] The gel content indicated by % by weight indicates a percentage of solvent-insoluble rubber-based adhesive after the reaction that provides adhesion. Generally, the gel content is high for a polymer that is cross-linked to an extremely high degree, and as the cross-linking degree increases, the gel content also increases.
    [027] The rubber-based adhesive layer is cured by means of electron beam irradiation. As the rubber-based adhesive layer is polymerized and solidified due to the generation of radicals through electron beam irradiation, there is no need for polymerization initiator and the like and there is substantially no concern about quality changes. In addition, as electron beam curing provides higher energy use efficiency and faster cure speed than UV curing, high productivity can be expected.
    [028] In addition, electron beam irradiation is performed in irradiation dosages from 300 kGy to 500 kGy. If the irradiation dosage is less than 300 kGy, as not enough energy for curing is provided, the gel content is reduced to less than 40% and thus the rubber-based adhesive layer may exhibit insufficient cohesion. If the irradiation dosage is more than 500 kGy, the rubber-based adhesive layer may exhibit insufficient adhesion due to the high degree of cure and there may be a problem of product damage due to strong energy beam.
    [029] As the use of the rubber-based adhesive layer that contains a gel content of 40% or more increases the initial adhesion to a certain level, the compatibility of the rubber-based adhesive layer with the acrylic foam layer that has polarity can be improved. Furthermore, as the gel content of the rubber-based adhesive layer is kept at 40% or more, the rubber-based adhesive layer can exhibit better adhesion than the acrylic adhesive layer. Furthermore, as the rubber-based adhesive layer exhibits high peel strength and high temperature retention, the rubber-based adhesive layer can be bonded to materials such as metal-coated plastics and the like.
    [030] Furthermore, according to the present invention, the rubber-based adhesive layer includes a styrene block copolymer and may additionally include a binder and a plasticizer.
    [031] Styrene block copolymer is a styrene-isoprene-styrene block copolymer (SIS). SIS block copolymer is a type of rubber-based adhesive, has an ABA-type polymer structure and is a thermoplastic styrene elastomer that has a molecular structure in which A of an end block is polystyrene and B of an intermediate block it is polyisoprene.
    [032] According to the present invention, the SIS block copolymer can generally have solution viscosity (MPa^s [cps], 25°C) of about 100 to about 3000, without limitations. The SIS block copolymer can be present in an amount of 10% by weight to 30% by weight in a total composition of the rubber-based adhesive layer. If the amount of SIS block copolymer is less than 10% by weight, the rubber-based adhesive layer may exhibit insufficient cohesion, and if the amount of SIS block copolymer is more than 30% by weight, the adhesive layer rubber-based may exhibit insufficient adhesion. Particularly, the styrene block copolymer can include from 15% by weight to 30% by weight of styrene. Styrene is a hard segment and an amount of styrene can influence the properties of a general rubber. As the amount of styrene increases, rubber exhibits greater thermoplasticity. If the amount of styrene is less than 15% by weight, the rubber-based adhesive layer may exhibit insufficient cohesion, and if the amount of styrene is more than 30% by weight, the rubber-based adhesive layer may exhibit insufficient adhesion. Particularly, styrene is preferably present in an amount of 15% by weight to 25% by weight.
    [033] Examples of the binder may include substituted saturated hydrocarbon resins (synthetic petroleum resins), pitch ester derivatives, terpene resins, phenol resins and the like, without limitation. At this point, substituted saturated hydrocarbon resins are not particularly limited. These can be used alone or in combination.
    [034] The binder may be present in amounts of 10 parts by weight to 150 parts by weight based on 100 parts by weight of the styrene block copolymer of the rubber-based adhesive layer, without limitations. If the amount of binder is less than ten parts by weight, the rubber-based adhesive layer may exhibit insufficient adhesion, and if the amount of binder exceeds 150 parts by weight, the rubber-based adhesive layer may exhibit excessively strong adhesion and therefore transfer external substances to a substrate when peeled.
    [035] Examples of the plasticizer may include: higher alcohols such as liquid paraffin, hardened oil, hardened castor oil, octyldodecanol and the like; and fatty acid esters such as squalane, squalene, castor oil, liquid rubber (polybutene), isopropyl myristic acid and the like, without limitation. These can be used alone or in combination.
    [036] The plasticizer can be present in an amount of 1 part by weight to 10 parts by weight based on 100 parts by weight of the styrene block copolymer of the rubber-based adhesive layer. If the amount of plasticizer is less than one part by weight, the adhesive layer may be excessively cured and therefore exhibit insufficient adhesion. Furthermore, if the amount of plasticizer exceeds ten parts by weight, the adhesive layer may be excessively softened, causing stiffness or residue.
    [037] The rubber-based adhesive layer may additionally include an outer skin layer. The outer skin layer can include a variety of plastic films, papers, non-woven fabrics, glass and metal, without limitation. Preferably, the outer skin layer is a plastic film such as polyethylene terephthalate (PET) film.
    [038] Pressure-sensitive adhesive tape preparation method:
    [039] The present invention provides a method of preparing pressure-sensitive adhesive layer, which includes: preparing an acrylic foam layer; and forming one or more rubber-based adhesive layers on one or both sides of the acrylic foam layer, wherein forming one or more rubber-based adhesive layers includes: preparing a styrene block copolymer, forming of one or more rubber-based adhesive layers by adding a binder and plasticizer to the styrene block copolymer and setting the gel content of one or more rubber-based adhesive layers to 40% or more.
    [040] The operation of preparing an acrylic foam layer may include: preparing a composition by thermal polymerization of an ester monomer of (meth)acrylic acid and acrylic acid; preparing a mixture by adding a photoinitiator and a crosslinking agent to the composition; carrying out photopolymerization by means of UV irradiation of the mixture; and preparing an acrylic foam layer by heating the light-cured material.
    [041] In addition, the method may include forming the rubber-based adhesive layer(s) on one or both sides of the acrylic foam layer. The operation of forming the rubber-based adhesive layer(s) may include: preparing a styrene block copolymer, forming one or more rubber-based adhesive layers by adding a binder and a plasticizer to styrene block copolymer and setting the gel content of one or more rubber-based adhesive layers to 40% or more.
    [042] The operation of setting the gel content of the rubber-based adhesive layer(s) by 40% or more can be performed by curing the adhesive layer(s) ) based on rubber by means of electron beam irradiation. Particularly, when electron beams have high energy and exhibit high transmission in the direction of the thickness of an adhesive, one can also apply electron beam curing to a thick adhesive layer. As the use of a rubber-based adhesive layer that contains a gel content of 40% or more increases the initial adhesion to a certain level, the compatibility of the rubber-based adhesive layer with the acrylic foam layer having polarity can be improved (exclusion). In addition, the rubber-based adhesive layer has gel content maintained at 40% or more and can therefore exhibit better adhesion than the acrylic adhesive layer. Furthermore, as the rubber-based adhesive layer exhibits high peel strength and high temperature retention, the rubber-based adhesive layer can also be bonded to materials such as metal-coated plastics and the like.
    [043] In addition, one can perform electron beam irradiation of the rubber-based adhesive layer at irradiation dosage of 300 kGy to 500 kGy. If the irradiation dosage is less than 300 kGy, not enough energy is provided for curing, such that the gel content is reduced to less than 40%, in order to provide insufficient cohesion. If the irradiation dosage is more than 500 kGy, the rubber-based adhesive layer may exhibit insufficient adhesion due to the high degree of cure and the product may be damaged due to strong energy beam.
    [044] Specific examples of the styrene block copolymer, the binder and the plasticizer of the rubber-based adhesive layer are as described above.
    [045] The composition can be prepared by drying the solvent before adding the binder and plasticizer to the styrene block copolymer. Examples of the solvent may include ethyl acetate, isopropanol, ethanol, hexane, heptanes and toluene. The solvent serves to reduce the viscosity of the composition to allow for easy pouring of the composition from one container to another container. In addition, the solvent is added in sufficient quantity to reduce the viscosity of the composition to less than about 100 Pascal-seconds (pa*s).
    [046] The solvent is added in sufficient quantity to provide solids content of about 20% by weight to 40% by weight in the composition. The composition having solids content of more than 40% by weight can exhibit high viscosity and the composition having solids content of less than 20% by weight requires excess solvent above a sufficient amount of solvent to reduce the viscosity of the composition up to a level for easy work. Proper viscosity depends on a method of introducing the composition into an extruder and a type of solvent removal system.
    [047] According to the present invention, pressure-sensitive adhesive tape is particularly useful in joining components, such as molded side articles of vehicles, emblems, strips and other objects, to an external surface of substrates, such as automobiles, motorcycles, bicycles, boats (such as ships, yachts, personal boats and ships), aircraft and other types of land, sea and air vehicles.
    [048] Pressure sensitive adhesive tape exhibits resistance to components such as petroleum substances including gasoline, lubricants, water-based substances including detergents, front glass cleaning liquids, rainwater, salt water and their mixtures, that such vehicles can often encounter when using a substrate that includes such substances. In addition, because pressure sensitive adhesive tape exhibits resistance to physical force and greater resistance to peeling, adhesive tape prevents removal of an object from the substrate due to physical force such as impact, trapping, breakage, or other force.
    [049] The present invention is explained in more detail below with reference to some examples. It should be understood that these examples are provided for illustration only and are not intended to be construed in any way as limiting the present invention. EXAMPLE 1
    [050] Preparation of acrylic foam layer:
    [051] 90 parts by weight of 2-ethylhexyl acrylate and 10 parts by weight of a polar acrylic acid monomer were thermally polymerized in a one-liter glass reactor to obtain a syrup having a viscosity of 3500 cPs. 0.5 parts by weight of Irgacure 651 (α,α-methoxy-α-hydroxyacetophenone) as photoinitiator and 0.35 parts by weight of 1,6-hexanediol diacrylate (HDDA) as crosslinking agent were mixed with the syrup based in one hundred parts by weight of the syrup, followed by sufficient stirring. Five parts by weight of glass bubbles and two parts by weight of silica were mixed, followed by stirring until uniform mixing of the components. The resulting mixture was subjected to vacuum degassing using a vacuum pump, in order to prepare a 1.0 mm thick acrylic foam tape using a microbar.
    [052] Preparation of rubber-based adhesive layer:
    [053] A composition having 20% solids content was prepared from a SIS linear block copolymer that includes 10% styrene using a toluene solvent. 150 parts by weight of an adhesion enhancing binder were added to the composition based on one hundred parts by weight of the linear block copolymer SIS, followed by stirring. Then, the mixture was subjected to degassing and then coated on a silicone release PET film, followed by drying in an oven at 80 °C for one minute and then in an oven at 110 °C for two minutes in order to prepare a 50 μm thick rubber-based adhesive layer. Then, the rubber-based adhesive layer was cured by irradiation with an electron beam (EB) having various intensities (300, 400 and 500 kGy).
    [054] Preparation of acrylic foam tape:
    [055] The rubber-based adhesive layer and the acrylic foam layer were subjected to lamination using a 5 kg roller, in order to prepare an acrylic foam tape. EXAMPLE 2
    [056] An acrylic foam tape was prepared in the same way as in Example 1, except that the linear block copolymer SIS included 20% styrene in the preparation of the rubber-based adhesive layer. EXAMPLE 3
    [057] An acrylic foam tape was prepared in the same way as in Example 1, except that the linear block copolymer SIS included 30% styrene in the preparation of the rubber-based adhesive layer. EXAMPLE 4
    [058] An acrylic foam tape was prepared in the same way as in Example 1, except that the linear block copolymer SIS included 40% styrene in the preparation of the rubber-based adhesive layer. COMPARATIVE EXAMPLE
    [059] An acrylic foam tape was prepared in the same way as in Example 1, except for adding a polymerization initiator and performing UV curing in preparing the rubber-based adhesive layer. EXPERIMENTAL EXAMPLE 1
    [060] Measurement of gel content:
    [061] Each of the rubber-based adhesive layers of Example 1 and Comparative Example was cut into a sample having a size of 60 mm x 60 mm, followed by weighing. Then, the rubber-based adhesive layer was placed in a PET bottle, followed by filling the PET bottle with 50 ml of toluene as solvent and then holding it at room temperature for two days. The adhesives swelled completely for two days and were filtered through a 200 mesh 130 mm x 130 mm sieve, followed by drying in an oven at 110°C for four hours. The difference between the initial and final weights of each adhesive was calculated, in order to measure the final gel content. TABLE 1

    [062] From the result, it can be seen that, as the dosage of EB irradiation and the dosage of UV irradiation increased, the gel content increased, as shown in Table 1. In addition, the adhesive layer with base The EB-curable rubber of Example 1 had gel content of 40% or more, while the UV-curable rubber-based adhesive layer of Comparative Example had gel content of less than 40%. EXPERIMENTAL EXAMPLE 2
    [063] Measurement of peel strength at 180° (N/m):
    [064] An ABS board and a painted board with a width of 50 mm and a length of 120 mm were cleaned with an isopropyl solution, followed by drying. A PET film 0.02 mm thick and 30 mm wide was laminated onto a surface of each of the rubber-based adhesive layers of Example 1 and Comparative Example so as to form on a side surface of the cover . Each of the prepared samples was placed on top of each of the ABS plate and the painted plate, followed by rolling five times in each direction using a 2 kg roller and then kept at room temperature for about thirty minutes. Then, the peeling resistance at 180° was measured on each sample at room temperature at a speed of 300 mm/min and the average value of five samples was recorded. TABLE 2


    [065] From the result, it can be seen that the peeling resistance varied depending on the dose of UV irradiation and the dose of EB irradiation. In the sample from Example 1, the highest adhesion was obtained at 300 kGy, corresponding to the lowest gel content, and the acrylic foam layer was broken when the adhesive tape was peeled from the ABS board and the painted board. Furthermore, as the measured peel strength corresponded to the foam breaking strength of the acrylic foam layer only and not the adhesion of the rubber-based adhesive layer, higher peel strength would be expected if the adhesive layer were separated of the boards without breaking the acrylic foam layer.
    [066] On the other hand, in the Comparative Example, the highest adhesion was obtained at 2100 mJ/cm2, corresponding to the lowest gel content among the results. The reason is that gel content, initial adhesion and peel strength are correlated with each other. As higher gel content generally provides better cure reaction between adhesive polymers, however, adhesive tape has greater durability. In this case, however, the adhesive tape exhibits less peeling resistance, as the adhesive tape becomes relatively hard. On the other hand, if the gel content becomes lower, the peel strength of the adhesive polymer can be relatively increased due to the low degree of cure. In this case, however, the adhesive tape exhibits low high temperature retention due to deterioration in durability.
    [067] In this way, the acrylic foam layer was broken when the EB-cured rubber-based adhesive layer of Example 1 was peeled off from the ABS board and the printed board, while the Comparative Example adhesive layer was separated from the boards. It can be seen, therefore, that although the rubber-based adhesive layer of the Comparative Example exhibited high peel strength, the rubber-based adhesive layer subjected to EB irradiation curing exhibited better peel strength. EXPERIMENTAL EXAMPLE 3
    [068] Measurement of high temperature retention at 90 °C:
    [069] Painted plates with a width of 25 mm and a length of 60 mm were cleaned with an isopropyl solution, followed by drying. The painted boards were laminated onto both sides of each of the rubber-based adhesive layers of Example 1 and Comparative Example. Each of the prepared samples was rolled five times using a 5 kg roller. Each of the samples was kept at room temperature for about thirty minutes. Then, a weight of 500 g of each of the samples was suspended under a high temperature of 90 °C, in order to measure the retention in the form of duration time until the adhesive layer separated from the plate. The mean value of three samples was then recorded. TABLE 3

    [070] From the results, it can be seen that the high temperature retention of 90 °C varied depending on the dose of UV irradiation and the dose of EB irradiation. The rubber-based adhesive layer of Example 1 exhibited the highest 90°C high temperature retention at 300 kGy, corresponding to the lowest gel content.
    [071] On the other hand, it can be seen that although the rubber-based adhesive layer of the Comparative Example exhibited the 90 °C higher high temperature retention at 6200 mJ/cm2 corresponding to the highest gel content , the rubber-based adhesive layer of Comparative Example exhibited lower high temperature retention than the samples of Example 1, including the EB-cured rubber-based adhesive layer. In this way, it can be seen that even the rubber-based adhesive layer of the same constitution exhibited variable high temperature retention with the curing methods, that is, the EB irradiation-cured rubber-based adhesive layer exhibited better high temperature retention. EXPERIMENTAL EXAMPLE 4
    [072] Measurement of peel strength at 180° (N/m) of the rubber-based adhesive layer:
    [073] An ABS board with a width of 50 mm and a length of 120 mm was cleaned with a solution of isopropyl alcohol, followed by drying. A PET film 0.02 mm thick and 30 mm wide was laminated onto a surface of each of the rubber-based adhesive layers of Examples 1 to 4 so as to form on a side surface of the cover. At this point, the rubber-based adhesive layers were cured by means of 300 kGy EB irradiation. Each of the prepared samples was placed on the ABS plate, followed by rolling five times in each direction using a 2 kg roller and then kept at room temperature for about thirty minutes. Then, the peeling resistance at 180° was measured on each sample at room temperature at a speed of 300 mm/min and the average value of five samples was recorded. TABLE 4

    [074] It was confirmed that as the rubber-based adhesive layers of Examples 1 to 4 included 10% by weight to 40% by weight of the styrene of the SIS block copolymer, the rubber-based adhesive layers exhibited peel strength at a certain level or higher. The styrene included in the SIS block copolymer exhibits relatively hard properties and the softness of the rubber-based adhesive layer can be adjusted by changing the amount of styrene. If the amount of styrene is outside the above range, although the rubber-based adhesive layer itself exhibits elasticity, the rubber-based adhesive layer may exhibit insufficient wetting capacity when bonded to a substrate.
    [075] Specifically, the rubber-based adhesive layers of Examples 2 to 3, corresponding to 20% by weight and 30% by weight of the styrene of the SIS block copolymer, respectively, showed peel strength of about 3700 N/m and could exhibit excellent peeling resistance. Furthermore, it was confirmed that the rubber-based adhesive layers of Examples 1 and 4, corresponding to 10% by weight and 40% by weight of the styrene of the SIS block copolymer, respectively, exhibited peel strength of about 3200 N /m and exhibited slightly lower peel strength than the rubber-based adhesive layers of Examples 2 and 3.
    权利要求:
    Claims (8)
    [0001]
    1. PRESSURE-SENSITIVE ADHESIVE TAPE, characterized in that it comprises: - an acrylic foam layer comprising a (meth)acrylic acid ester monomer containing a C1 to C12 alkyl group and an acrylic acid; and - rubber-based adhesive layers formed on both sides of the acrylic foam layer; wherein the rubber-based adhesive layers comprise a styrene block copolymer comprising 15% by weight to 30% by weight of styrene, and wherein the rubber-based layers contain a gel content between 40% and 80%, being cured by means of electron beam irradiation at irradiation dosages of 300 kGy to 500 kGy.
    [0002]
    ADHESIVE TAPE, according to claim 1, characterized in that the (meth)acrylic acid ester monomer containing a C1 to C12 alkyl group is present in an amount of 85% by weight to 95% by weight and the acrylic acid is present in an amount from 5% by weight to 15% by weight.
    [0003]
    ADHESIVE TAPE, according to claim 1, characterized in that the acrylic foam layer comprises: 0.01 parts by weight to 1 part by weight of a photoinitiator; and 0.1 parts by weight to 2 parts by weight of a crosslinking agent, based on 100 parts by weight of a composition comprising a (meth)acrylic acid ester monomer containing a C1 to C12 alkyl group and acrylic acid.
    [0004]
    ADHESIVE TAPE, according to claim 1, characterized in that the rubber-based adhesive layers additionally comprise a binder and a plasticizer.
    [0005]
    ADHESIVE TAPE, according to claim 1, characterized in that the styrene block copolymer is present in an amount of 10% by weight to 30% by weight in a total composition of the rubber-based adhesive layer.
    [0006]
    ADHESIVE TAPE according to claim 4, characterized in that the binder is present in an amount of 10 parts by weight to 150 parts by weight and the plasticizer is present in an amount of 1 part by weight to 10 parts by weight, based on 100 parts by weight of the styrene block copolymer of the rubber-based adhesive layers.
    [0007]
    ADHESIVE TAPE, according to claim 1, characterized in that the styrene block copolymer is a styrene-isoprene-styrene (SIS) block polymer.
    [0008]
    8. METHOD OF PREPARING A PRESSURE-SENSITIVE ADHESIVE LAYER, as defined in claims 1 to 7, characterized in that it comprises: - preparation of an acrylic foam layer comprising a (meth)acrylic acid ester monomer containing a C1 to C12 alkyl group and an acrylic acid; and - forming rubber-based adhesive layers on one or both sides of the acrylic foam layer; wherein the step of forming the rubber-based adhesive layers comprises: - preparing a styrene block copolymer comprising from 15% by weight to 30% by weight of styrene; - formation of the rubber-based adhesive layers by adding a binder and a plasticizer to the styrene block copolymer; and - definition of the gel content of the rubber-based adhesive layers at 40% to 80%, being carried out by curing the rubber-based adhesive layer(s) by means of beam irradiation. electrons at irradiation dosages of 300 kGy to 500 kGy.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014008458B1|2021-06-22|PRESSURE-SENSITIVE ADHESIVE TAPE, E, PRESSURE-SENSITIVE ADHESIVE LAYER PREPARATION METHOD
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    同族专利:
    公开号 | 公开日
    EP2767567B1|2020-01-01|
    JP2014534303A|2014-12-18|
    WO2013055122A2|2013-04-18|
    BR112014008458A2|2017-04-11|
    EP2767567A2|2014-08-20|
    CA2851479C|2017-03-28|
    JP5960273B2|2016-08-02|
    CA2851479A1|2013-04-18|
    CN103857764A|2014-06-11|
    US20140234612A1|2014-08-21|
    KR101393860B1|2014-05-14|
    KR20130039064A|2013-04-19|
    WO2013055122A3|2013-06-13|
    EP2767567A4|2015-03-18|
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    法律状态:
    2017-08-15| B25A| Requested transfer of rights approved|Owner name: LG CHEM, LTD (KR) |
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-01-05| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-22| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 11/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    KR10-2011-0103502|2011-10-11|
    KR1020110103502A|KR101393860B1|2011-10-11|2011-10-11|Adhesive tape for automobile|
    PCT/KR2012/008260|WO2013055122A2|2011-10-11|2012-10-11|Adhesive tape for car|
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