CN115960302B - Acrylic acid ester copolymer, pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive product - Google Patents
Acrylic acid ester copolymer, pressure-sensitive adhesive composition, pressure-sensitive adhesive and pressure-sensitive adhesive product Download PDFInfo
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Abstract
The invention relates to the technical field of adhesives, and provides an acrylic ester copolymer, a pressure-sensitive adhesive composition, a pressure-sensitive adhesive and a pressure-sensitive adhesive product. The copolymer comprises the following raw material components: 50-90 parts by weight of soft monomer, 1-10 parts by weight of hard monomer and 5-40 parts by weight of functional monomer; the functional monomers include crosslinking monomers, hydrophobic monomers, and cyclic monomers. The acrylate copolymer has proper glass transition temperature and higher molecular weight, so that the prepared pressure-sensitive product has excellent adhesive property, high-temperature high-humidity (85 ℃) rebound resistance and good water vapor resistance.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to an acrylic ester copolymer, a pressure-sensitive adhesive composition, a pressure-sensitive adhesive and a pressure-sensitive adhesive product.
Background
With the development of technology, electronic products play an increasingly important role in our lives and works. Compared with the traditional pressure-sensitive adhesive, the pressure-sensitive adhesive is widely applied to the fields of packaging, commercial labels, product manufacturing processes, shipment protection and the like, and modern pressure-sensitive adhesives are more applied to various electronic products. In order to meet various demands of people, the electronic product improves visual effect and touch feeling, the curved surface screen and the curved surface glass are generated, and due to the characteristics of heating and rebound stress of the curved surface, when a general double-sided adhesive tape or a common rebound-resistant adhesive tape is used, the cohesive failure or adhesive failure of the adhesive tape can be caused under the action of long-term high-temperature creep and rebound stress to generate a warping phenomenon, and meanwhile, because water vapor in the atmosphere can corrode a precise element, the requirement on the waterproof vapor permeability of the electronic appliance adhesive is higher.
The acrylic polymers have a series of common characteristics of transparency, low toxicity, easy preparation and better cohesiveness, water resistance and durability, so that the acrylic resin is widely applied in adhesives. However, because the high temperature and the high humidity have a strong destructive effect on the ester group, the common acrylic ester adhesive is generally difficult to withstand long-time high temperature and high humidity tests to ensure that the sealing property is not reduced, and then the electronic device has moisture entering in the use process, so that the normal use of the electronic device is affected.
Therefore, the development of the pressure-sensitive adhesive and the adhesive tape with better rebound resistance and better steam resistance at high temperature and high humidity has important significance.
Disclosure of Invention
The present invention has been made to overcome the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide an acrylate copolymer, a pressure-sensitive adhesive composition containing the acrylate copolymer, a pressure-sensitive adhesive prepared from the composition, and a pressure-sensitive adhesive article (e.g., a tape) prepared from the pressure-sensitive adhesive. The acrylate copolymer has proper glass transition temperature and higher molecular weight, so that the prepared pressure-sensitive product has excellent adhesive property, high-temperature high-humidity (85 ℃) rebound resistance and good water vapor resistance.
In order to achieve the above object, the first aspect of the present invention provides an acrylic acid ester copolymer comprising the following raw material components: 50-90 parts by weight of soft monomer, 1-10 parts by weight of hard monomer and 5-40 parts by weight of functional monomer; the functional monomers include crosslinking monomers, hydrophobic monomers, and cyclic monomers.
In one example, the functional monomer further includes a polar monomer, which is an acrylate monomer containing a polar group.
In one example, the polar monomer is a monomer comprising-CN, -COOH, -CONH 2 or-OH polar groups, or a combination of at least two of the acrylic monomers;
in one example, the polar monomer is selected from one or a combination of at least two of beta-carboxyethyl acrylate, beta-hydroxypropyl acrylate, acrylic acid, methacrylic acid, hydroxyethyl acrylate, and hydroxyethyl methacrylate.
In one example, the soft monomer is selected from one or a combination of at least two of butyl acrylate, isooctyl acrylate, lauryl acrylate, and lauryl methacrylate.
In one example, the hard monomer is selected from one or a combination of at least two of methyl methacrylate, methyl acrylate, isobornyl acrylate, and isobornyl methacrylate.
In one example, the crosslinking monomer is selected from one or a combination of at least two of acrylic acid, methacrylic acid, hydroxyethyl acrylate, and hydroxyethyl methacrylate.
In one example, the hydrophobic monomer is selected from one or a combination of at least two of t-butyl acrylate, t-butyl methacrylate, hexafluorobutyl acrylate, and tridecyl acrylate.
In one example, the cyclic monomer is selected from one or a combination of at least two of glycidyl methacrylate, N-dimethylacrylamide, N-vinylpyrrolidone, tetrahydrofuranacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate.
In one example, the functional monomer includes: 1-10 parts by weight of a crosslinking monomer, 1-10 parts by weight of a hydrophobic monomer, 1-10 parts by weight of a cyclic monomer and 1-10 parts by weight of a polar monomer.
In one example, the acrylate copolymer further comprises an initiator; the initiator is selected from one or a combination of at least two of azo initiator, organic peroxide initiator and inorganic peroxide initiator.
In one example, the initiator is contained in an amount of 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the acrylate copolymer.
In one example, the molecular weight of the acrylate copolymer is 50-130 tens of thousands, preferably 75-120 tens of thousands.
In one example, the acrylate copolymer has a solids content of 20% to 60%, preferably 25% to 45%.
In one example, the viscosity of the acrylate copolymer is 1000-18000cps, preferably 2000-15000cps.
In a second aspect, the present invention provides a pressure sensitive adhesive composition comprising the acrylate copolymer of the first aspect of the present invention, and a tackifying resin and a curing agent; wherein the content of the tackifying resin is 5 to 20 parts by weight and the content of the curing agent is 0.3 to 1.4 parts by weight relative to 100 parts by weight of the acrylate copolymer.
In one example, the tackifying agent is selected from one or a combination of at least two of a resin terpene tackifying resin, a phenolic modified tackifying resin, a rosin tackifying resin, and a petroleum tackifying resin.
In one example, the tackifying resin is a combination of a high softening point tackifying resin and a medium softening point tackifying resin.
In one example, the curing agent is selected from the group consisting of epoxy curing agents and isocyanate curing agents in a mass ratio of 1 (0.5-1.5), preferably in a mass ratio of 1:1.
In one example, the epoxy curative is selected from at least one of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N '-tetraepoxypropyl-4, 4' -diaminodiphenylmethane, and diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate.
In one example, the isocyanate curing agent is selected from at least one of toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
In a third aspect, the present invention provides a pressure sensitive adhesive comprising or prepared from the composition of the first aspect of the present invention.
In a fourth aspect, the present invention provides a pressure-sensitive adhesive article comprising at least one of the acrylate copolymer of the first aspect of the invention, the composition of the second aspect of the invention, and the pressure-sensitive adhesive of the third aspect of the invention.
The technical scheme adopted by the invention has the following beneficial effects:
(1) The acrylic ester copolymer provided by the invention has a proper glass transition temperature, so that the pressure-sensitive adhesive containing the acrylic ester copolymer has higher cohesiveness and excellent high-temperature high-humidity rebound resistance;
(2) The acrylic ester copolymer provided by the invention has higher molecular weight, so that the prepared pressure-sensitive adhesive polymer has high cohesive strength and can meet the requirement of high shear performance;
(3) The pressure-sensitive product provided by the invention can ensure that the prepared pressure-sensitive product (such as pressure-sensitive adhesive tape) has excellent adhesive property and high-temperature high-humidity (85 ℃) rebound resistance through reasonable selection and matching use of the soft monomer, the hard monomer and the functional monomer and matching of tackifying resin with high softening point, medium softening point and low softening point;
(4) According to the pressure-sensitive product provided by the invention, the formed pressure-sensitive adhesive has higher crosslinking degree through the synergistic cooperation of the epoxy curing agent and the isocyanate curing agent, so that the prepared pressure-sensitive adhesive tape has good water vapor resistance.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Drawings
Fig. 1 is a schematic view showing the structure of the pressure-sensitive adhesive tape of the present invention.
Reference numerals: 1-a release material layer; 2-a functional coating; 3-substrate layer.
Detailed Description
Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention relates. The following explains some terms of the present invention.
The term "soft monomer" refers to acrylate monomers having a glass transition temperature below 0 degrees, for example, acrylate monomers having a glass transition temperature between-20 ℃ and-70 ℃ are referred to as soft monomers.
The term "hard monomer" refers to acrylate monomers having a glass transition temperature above 0 degrees.
The term "crosslinking monomer" refers to acrylate monomers that primarily function as crosslinks.
The term "hydrophobic monomer" refers to an acrylate monomer that has hydrophobicity and/or water resistance.
The term "cyclic monomer" refers to an acrylate monomer that can undergo ring-opening polymerization to undergo a crosslinking reaction under the action of an initiator or catalyst.
The term "polar monomer" refers to an acrylate monomer containing a polar group. Wherein the polarity of the polar group is the same as or similar to the polarity of the pressure-sensitive adhesive tape base material.
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The first aspect of the invention provides an acrylic ester copolymer, which comprises the following raw material components: 50-90 parts by weight of soft monomer, 1-10 parts by weight of hard monomer and 5-40 parts by weight of functional monomer; the functional monomers include crosslinking monomers, hydrophobic monomers, and cyclic monomers.
In the present invention, the soft monomer, the hard monomer, the functional monomer (crosslinking monomer, hydrophobic monomer and cyclic monomer) are comonomers for preparing the polyacrylic resin, and specific kinds of the soft monomer, the hard monomer and the functional monomer are not limited, and acrylate monomers conventionally used in the art may be selected.
Preferably, the soft monomer is an acrylic ester monomer with a glass transition temperature of-10 to-90 ℃; the hard monomer is selected from acrylate monomers with glass transition temperature of 5-120 ℃. The glass transition temperatures of the soft and hard monomers are preferred, allowing the acrylate copolymer to have a more suitable glass transition temperature.
Preferably, the acrylate copolymer comprises the following raw material components: 60-80 parts of soft monomer, 2-5 parts of hard monomer and 10-30 parts of functional monomer.
The proportion of the soft monomer, the hard monomer and the functional monomer in parts by weight is preferable, so that the effect of the three types of comonomers is better, and the adhesion performance of the acrylate copolymer obtained by copolymerization is better.
The inventor of the invention discovers that through reasonable selection and matching of soft monomers, hard monomers and functional monomers, the acrylate copolymer can have proper glass transition temperature, so that the pressure-sensitive adhesive containing the acrylate copolymer has higher cohesiveness and excellent high-temperature high-humidity rebound resistance.
By the combination of the soft monomer, the hard monomer and the functional monomer, the acrylate copolymer with better performance can be obtained. One or more of these features may be further preferred in order to further enhance the performance of the acrylate copolymer.
In one example, the soft monomer is selected from one or a combination of at least two of butyl acrylate, isooctyl acrylate, lauryl acrylate, and lauryl methacrylate.
In a preferred embodiment, the soft monomer is a combination of butyl acrylate and isooctyl acrylate in a mass ratio of (0.5-12): 1, preferably (1-8): 1.
In one example, the hard monomer is selected from one or a combination of at least two of methyl methacrylate, methyl acrylate, isobornyl acrylate, and isobornyl methacrylate. Preferably, the hard monomer is methyl methacrylate.
In one example, the crosslinking monomer is selected from one or a combination of at least two of acrylic acid, methacrylic acid, hydroxyethyl acrylate, and hydroxyethyl methacrylate.
In a preferred embodiment, the crosslinking monomer is acrylic acid.
The crosslinking monomer has strong polar functional groups, so that the adhesive property of the pressure-sensitive adhesive containing the acrylic ester copolymer is obviously improved, and the cohesive strength, heat resistance and ageing resistance of the pressure-sensitive adhesive can be greatly improved by the physical and chemical crosslinking.
In one example, the hydrophobic monomer is selected from one or a combination of at least two of t-butyl acrylate, t-butyl methacrylate, hexafluorobutyl acrylate, and tridecyl acrylate.
In one example, the cyclic monomer is selected from one or a combination of at least two of glycidyl methacrylate, N-Dimethylacrylamide (DMAA), N-vinylpyrrolidone, tetrahydrofuranacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate.
The present inventors have studied and found that adding a hydrophobic monomer in the synthesis of an acrylate copolymer can give the acrylate copolymer excellent water resistance. Taking hydrophobic monomer tert-butyl acrylate (TBA) as an example, the tert-butyl steric hindrance structure of the TBA provides beneficial hydrophobic performance, and as the content of the TBA increases, the water contact angle of the pressure-sensitive adhesive film surface formed by the acrylate copolymer increases, so that the hydrophobicity and the water resistance of the pressure-sensitive adhesive are finally improved.
The inventor of the present invention further studied and found that the mixed curing agent of the epoxy curing agent and the isocyanate curing agent is used for crosslinking in the process of preparing the pressure-sensitive adhesive, and the added mixed curing agent is crosslinked with carboxyl and hydroxyl in the functional monomer in the acrylate copolymer, so that the pressure-sensitive adhesive maintains a high crosslinking degree. Meanwhile, the cyclic monomer in the acrylic ester copolymer is also subjected to ring opening and reaction with hydroxyl and carboxyl groups, so that the crosslinking degree of the polymer is further improved, and the polymer with a high-compactness structure is generated, so that the hydrophobicity and the water resistance of the pressure-sensitive adhesive are further improved.
In one example, the functional monomer further includes a polar monomer, which is an acrylate monomer containing a polar group. The polarity of the polar group of the polar monomer is the same as or similar to that of the pressure-sensitive adhesive tape base material, so that the cohesiveness of the pressure-sensitive adhesive can be improved.
In one example, the polar monomer is a monomer comprising-CN, -COOH, -CONH 2 and-OH polar groupOr a combination of at least two.
In a preferred embodiment, the polar monomer is selected from one or a combination of at least two of beta-carboxyethyl acrylate, beta-hydroxypropyl acrylate, acrylic acid, methacrylic acid, hydroxyethyl acrylate and hydroxyethyl methacrylate.
In a preferred embodiment, the polar monomer is beta-carboxyethyl acrylate. When the adhesive tape base material is PET commonly used in the field, the polarity of the beta-carboxyethyl acrylate is similar to that of the PET base material, so that the cohesiveness of the pressure-sensitive adhesive can be further improved.
In one example, the functional monomer includes 1-10 parts by weight of a crosslinking monomer, 1-10 parts by weight of a hydrophobic monomer, 1-10 parts by weight of a cyclic monomer, and 1-10 parts by weight of a polar monomer.
In one example, the acrylate copolymer further includes an initiator to cause the soft monomer, the hard monomer, and the functional monomer to undergo copolymerization.
In one example, the initiator is selected from one or a combination of at least two of azo-type initiators, organic peroxide initiators, and inorganic peroxide initiators.
In one example, the initiator is selected from one or a combination of at least two of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, dimethyl azobisisobutyrate, and benzoyl peroxide.
In one example, the initiator is contained in an amount of 0.1 to 1.5 parts by weight, preferably 0.2 to 0.8 parts by weight, relative to 100 parts by weight of the acrylate copolymer.
In one example, the acrylate copolymer further includes a first solvent capable of providing a contact environment for the copolymerization of the monomers.
In one example, the first solvent may be selected from one or more of ethyl acetate, toluene, butanone, acetone, and isopropanol.
In one example, the first solvent is contained in an amount of 200 to 600 parts by weight, preferably 300 to 400 parts by weight, with respect to 100 parts by weight of the acrylate copolymer.
In one example, the molecular weight of the acrylate copolymer is 50-130 tens of thousands, preferably 75-120 tens of thousands. The acrylic ester copolymer has higher molecular weight, so that the prepared pressure-sensitive adhesive polymer has high cohesive strength and can meet the requirement of high shear property.
In one example, the acrylate copolymer has a solids content of 20% to 60%, preferably 25% to 45%.
In one example, the viscosity of the acrylate copolymer is 1000-18000cps, preferably 2000-15000cps.
The present invention also provides a method for preparing the acrylate copolymer, comprising the steps of:
accurately weighing the soft monomer, the hard monomer and the functional monomer as reaction raw materials, and putting the raw materials into a reaction kettle; introducing inert gas and continuously stirring the reaction raw materials, adding an initiator, and stably reacting for 5-10 hours at 50-90 ℃.
In one example, a method of preparing the acrylate copolymer comprises the steps of:
accurately weighing the soft monomer, the hard monomer and the functional monomer as reaction raw materials, and putting the raw materials into a 1000ml glass reaction kettle; introducing nitrogen and continuously stirring, and adding an initiator to perform stable reaction for 6-8 hours at the temperature of 60-80 ℃.
The molecular weight (Mw) of the acrylic ester copolymer is controlled to be 50-130 ten thousand, the solid content is 20-60% and the viscosity is 1000-18000cps (25 ℃), by the reaction process and the formula. Wherein the molecular weight Mw is measured by GPC (polystyrene standard, THF mobile phase). And (3) solid content testing: reference is made to GB/T2793-1995 for determination of the non-volatile content of adhesives. Viscosity was measured using a Brookfield rotational viscometer (25 ℃ C.).
In one example, a method of preparing the acrylate copolymer comprises the steps of:
(1) Accurately weighing the soft monomer, the hard monomer and the functional monomer as reaction raw materials, and putting the raw materials into a 1000ml reaction kettle; introducing nitrogen, heating to 55-65 ℃ and continuously stirring, and adding a first initiator to perform stable reaction for 200-280 minutes;
(2) Heating to 70-75 ℃, and adding a second initiator to react for 40-80 minutes;
(3) And heating to 75-80 ℃, and finally adding a third initiator to react for 150-200 minutes to prepare the acrylic ester copolymer.
Wherein the first initiator, the second initiator, and the third initiator may be the same or different; the ratio of the addition amounts of the first initiator, the second initiator and the third initiator is 1 (0.2-1.2): 1-1.5.
In one example, the total content of the first initiator, the second initiator, and the third initiator is 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the acrylate copolymer.
Preferably, the first initiator, the second initiator and the third initiator are the same, more preferably azobisisobutyronitrile.
The present inventors have found that in the process of synthesizing an acrylic acid ester copolymer, a long-time high-temperature reaction causes a double increase in the decomposition rate of an initiator in radical polymerization, and the molecular weight of the synthesized acrylic acid ester copolymer is too low. Meanwhile, the long-time low-temperature reaction can lead to the multiple slow decomposition rate of the initiator during the free radical polymerization, so that the molecular weight of the acrylic ester copolymer is too large and even gel is formed. According to the invention, azobisisobutyronitrile with a half-life period of 10h at 65 ℃ is adopted to carry out free radical polymerization, the low temperature reaction of 55-65 ℃ is adopted for about 4h, so that the molecular weight of the polymer is large, and then the reaction of 70-80 ℃ is carried out for about 4h to eliminate the monomer which does not participate in the reaction, so that the acrylic ester copolymer with the expected molecular weight is prepared.
In a second aspect, the present invention provides a pressure sensitive adhesive composition comprising the acrylate copolymer of the first aspect of the present invention, and a tackifying resin and a curing agent; wherein the content of the tackifying resin is 5 to 20 parts by weight and the content of the curing agent is 0.3 to 1.4 parts by weight relative to 100 parts by weight of the acrylate copolymer.
Preferably, the tackifying resin is contained in an amount of 8 to 15 parts by weight and the curing agent is contained in an amount of 0.5 to 0.8 part by weight with respect to 100 parts by weight of the acrylate copolymer.
In one example, the pressure-sensitive adhesive composition further includes a second solvent in an amount of 20 to 80 parts by weight, preferably 25 to 35 parts by weight, relative to 100 parts by weight of the acrylate copolymer.
In one example, the second solvent may be selected from one or more of ethyl acetate, toluene, butanone, acetone, and isopropanol.
The tackifying resin of the present invention may be a variety of tackifying resins known to those of skill in the art. Preferably, the tackifying resin is selected from one or a combination of at least two of phenolic tackifying resins, phenolic modified tackifying resins, rosin tackifying resins, petroleum tackifying resins and terpene tackifying resins.
In one example, the tackifying resin has an acid number in the range of 5 to 65 mgKOH/g.
In the present invention, the tackifying resin may be classified into a high softening point tackifying resin, a medium softening point tackifying resin and a low softening point tackifying resin according to softening points. Wherein the softening point is 145-155 ℃ and is called high softening point tackifying resin, the softening point is 98-125 ℃ and is called medium softening point tackifying resin, and the softening point is 80-95 ℃ and is called low softening point tackifying resin.
In one example, the high softening point tackifying resin may be selected from the group consisting of Sichuan 803L (about 150 ℃), sumitomo PR-12603 (about 150 ℃), arisaema KRARON 1150 (about 150 ℃), kemao KP150 (about 150 ℃), and the like; the parenthesis refers to the softening point temperature of the corresponding tackifying resin.
In one example, the medium softening point tackifying resin may be selected from Ha Lima NH-2000 (around 100 ℃), arizona RE-100L (around 100 ℃), kemao KB-120 (around 120 ℃), and the like.
In one example, the low softening point tackifying resin may be selected from arizona RE85GB (around 85 ℃), GA-90 (around 90 ℃), TP96 (around 95 ℃), and the like.
In one example, the tackifying resin is a combination of a high softening point tackifying resin and a medium softening point tackifying resin.
The inventors of the present invention have found that the more the tackifying resin is added to some extent, the greater the cohesive force. Meanwhile, the acid value in the tackifying resin can influence the adhesive force of the adhesive tape on different plates, so that reasonable collocation is needed when the tackifying resin is added to achieve the expected performance. Meanwhile, the high-temperature high-humidity (85 ℃ and 85%) rebound resistance requires that the pressure-sensitive adhesive cannot be too hard or too soft, the colloid is too hard and strong in stress, the stress generated when the back-attached object is deformed cannot be sufficiently absorbed, the colloid is too soft, the double-sided adhesive tape cannot have enough adhesive force on the attached object, and finally the rebound resistance experiment fails. Finally, the invention can lead the prepared pressure-sensitive adhesive and pressure-sensitive adhesive tape to have excellent adhesive property and high-temperature high-humidity (85 ℃) rebound resistance through reasonable selection and matched use of the soft monomer, the hard monomer and the functional monomer and matching of the tackifying resin with high softening point, medium softening point and low softening point.
In one example, the curing agent is selected from the group consisting of epoxy curing agents and isocyanate curing agents in a mass ratio of 1 (0.5-1.5), preferably in a mass ratio of 1:1.
In one example, the epoxy curative is selected from at least one of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N '-tetraepoxypropyl-4, 4' -diaminodiphenylmethane, and diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylate.
In one example, the isocyanate curing agent is selected from at least one of toluene diisocyanate, hexamethylene Diisocyanate (HDI) and isophorone diisocyanate (IPDI).
In a preferred embodiment, the curing agent is a combination of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane and toluene diisocyanate in a mass ratio of 1 (0.8-1.2).
In the pressure-sensitive adhesive, the epoxy curing agent and the isocyanate curing agent are combined, and the mixed crosslinking agent (curing agent) is crosslinked with carboxyl and hydroxyl in the acrylic ester copolymer to form a reticular crosslinking structure, so that the formed pressure-sensitive adhesive has high crosslinking degree, and the prepared pressure-sensitive adhesive has good water vapor resistance.
It will be appreciated that the pressure sensitive adhesive composition provided in the second aspect of the present invention is limited in formulation and not in the form of materials, i.e. the components may be mixed with each other or stored separately. If the reaction is not performed at an improper timing, whether to mix or store the mixture may be selected as needed.
It will be appreciated that the composition of the present invention may be free of solvent for ease of manufacture, transportation and sale, and that the purchaser may prepare and add solvent during the process of preparing the pressure sensitive adhesive.
In a third aspect, the present invention provides a pressure-sensitive adhesive, which is characterized in that the pressure-sensitive adhesive contains the pressure-sensitive adhesive composition according to the second aspect of the present invention, or is prepared from the pressure-sensitive adhesive composition.
The pressure-sensitive adhesive disclosed by the invention can contain the pressure-sensitive adhesive composition, and can also contain auxiliary materials, auxiliary agents, solvents and other components which are added conventionally in the field, and the pressure-sensitive adhesive can be added in actual need.
In a fourth aspect, the present invention provides a pressure-sensitive adhesive article comprising at least one of the acrylate copolymer according to the first aspect of the present invention, the pressure-sensitive adhesive composition according to the second aspect of the present invention, and the pressure-sensitive adhesive according to the third aspect of the present invention.
The specific product form of the pressure-sensitive adhesive article is not limited as long as the pressure-sensitive adhesive of the present invention is contained. For example, the pressure-sensitive adhesive article may be a pressure-sensitive adhesive tape, pressure-sensitive adhesive label paper, pressure-sensitive adhesive sheet, or the like.
In one example, the pressure-sensitive adhesive article is a pressure-sensitive adhesive tape, preferably a double-sided pressure-sensitive adhesive tape.
The invention provides a pressure-sensitive adhesive tape, which comprises a substrate layer and a functional coating coated on the surface of the substrate layer; the functional coating is prepared from the pressure-sensitive adhesive composition according to the second aspect of the invention or contains the pressure-sensitive adhesive according to the third aspect of the invention.
Preferably, the thickness of the functional coating is 80 μm to 150 μm, more preferably 90 μm to 120 μm.
In the present invention, the material of the base material layer is not particularly limited, and materials used as a base material for an adhesive tape in the art may be selected. For example, the substrate layer may be a polyethylene terephthalate (PET) film, a Polyimide (PI) film, or the like.
In one example, the substrate layer has a thickness of 5 μm to 20 μm, preferably 10 μm to 15 μm.
In one example, the surface of the functional coating on the side remote from the substrate layer is covered with a release material layer. The release material layer may be selected from one or more of PET, PE (polyethylene) and OPP (bi-directional polypropylene).
In an example, the pressure-sensitive adhesive tape is a double-sided tape, has a multi-layer structure, and as can be seen by referring to the schematic structural diagram of fig. 1, the pressure-sensitive adhesive tape sequentially includes a release material layer, a functional coating layer, a substrate layer, a functional coating layer, and a release material layer from top to bottom.
The invention also provides a method for preparing the pressure-sensitive adhesive tape, which comprises the following steps:
and (3) weighing the acrylic ester copolymer, tackifying resin, curing agent and second solvent, mixing uniformly, stirring for 60min, standing for defoaming for 30min, coating on release paper by using a coater, and pressing onto a PET (polyethylene terephthalate) substrate to prepare the pressure-sensitive adhesive double-sided tape.
When the thickness of the PET base film is 12 mu m and the thickness of the adhesive tape using layer is 100 mu m, the peeling force of the double-sided adhesive tape to a steel plate reaches more than 3000 gf/inch.
The technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The invention is described in detail below in connection with specific embodiments, which are intended to be illustrative rather than limiting.
In the examples below, unless otherwise specified, all of the ingredients used were commercially available analytical grade. 1 part by weight represents 1g.
Example 1
1. Preparation of acrylate copolymers
1. The raw material components are as follows:
soft monomer: butyl acrylate, 70 parts by weight; 10 parts by weight of isooctyl acrylate;
hard monomer: isobornyl methacrylate, 4 parts by weight;
crosslinking monomer: acrylic acid, 5 parts by weight;
hydrophobic monomer: t-butyl acrylate, 4 parts by weight;
cyclic monomer: 5 parts of N, N-dimethylacrylamide;
polar monomer: beta-carboxyethyl acrylate, 2 parts by weight;
a first solvent: 300 parts by weight of ethyl acetate;
2. the synthesis method comprises the following steps:
(1) Putting the raw materials into a 1000ml reaction kettle, heating to 60 ℃ under the atmosphere of nitrogen, uniformly stirring for 30min, and adding 0.1% of initiator azodiisobutyronitrile for stable reaction for 240 min;
(2) Heating to 65 ℃, adding 0.05% of initiator azodiisobutyronitrile, and reacting for 60 minutes;
(3) Then heating to 75 ℃, adding 0.1% of initiator azodiisobutyronitrile, and reacting for 180 minutes to obtain an acrylic ester copolymer A; the acrylate copolymer viscosity was controlled to 8000cps (25 ℃ C.), solids content 25%, mw (molecular weight) by controlling the reaction exotherm: about 120 ten thousand, tg (glass transition temperature) = -45 ℃;
wherein the amount of the initiator added in the steps (1) to (3) is based on the total weight of the monomers involved in the reaction (the same as in the examples described below).
2. Preparation of double-sided pressure-sensitive adhesive tapes
1. The raw material components are as follows:
acrylic ester copolymer: 100 parts by weight of the acrylic copolymer A;
tackifying resin: japanese Sumitomo PR-12603,7 parts by weight; ha Lima NH-2000,8 parts by weight;
curing agent: toluene diisocyanate, 0.25 parts by weight; 0.25 part by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane;
a second solvent: ethyl acetate, 30 parts by weight;
2. the preparation method comprises the following steps:
mixing the raw materials together, uniformly stirring for 60min by using a stirrer, and standing for defoaming for 30min to obtain the mixed acrylic pressure-sensitive adhesive; the pressure-sensitive adhesive is coated on release paper by a coater, and then PET base material with the thickness of 12 mu m is pressed to prepare the PET double-sided adhesive tape with the total thickness of 100 mu m.
Example 2
1. Preparation of acrylate copolymers
1. The raw material components are as follows:
soft monomer: butyl acrylate, 40 parts by weight; isooctyl acrylate, 30 parts by weight;
hard monomer: methyl acrylate, 3 parts by weight;
crosslinking monomer: methacrylic acid, 3 parts by weight; hydroxyethyl acrylate, 4 parts by weight;
hydrophobic monomer: 10 parts by weight of tert-butyl acrylate;
cyclic monomer: 5 parts by weight of N-vinyl pyrrolidone;
polar monomer: 5 parts by weight of beta-hydroxypropyl acrylate;
a first solvent: 300 parts by weight of ethyl acetate;
2. the synthesis method comprises the following steps:
(1) Putting the raw materials into a 1000ml reaction kettle, heating to 65 ℃ under the atmosphere of nitrogen, uniformly stirring for 30min, and adding 0.15% of initiator azodiisobutyronitrile for stable reaction for 240 min;
(2) Heating to 70 ℃, adding 0.05% of initiator azodiisobutyronitrile, and reacting for 60 minutes;
(3) Heating to 80 ℃, adding 0.2% of initiator azodiisobutyronitrile, and reacting for 180 minutes to obtain an acrylic ester copolymer B; the acrylate copolymer viscosity was controlled to 4000cps (25 ℃) by controlling the reaction exotherm, solids content 25%, mw: about 75 Mo Zuo, tg= -50 ℃.
2. Preparation of double-sided pressure-sensitive adhesive tapes
1. The raw material components are as follows:
acrylic ester copolymer: 100 parts by weight of the acrylic copolymer B;
tackifying resin: 1150,4 parts by weight of arizona KRARON; arizona RE-100L,4 parts by weight;
curing agent: toluene diisocyanate, 0.4 parts by weight; 0.4 part by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane;
a second solvent: ethyl acetate, 30 parts by weight;
2. the preparation method comprises the following steps: the same as in example 1.
Example 3
1. Preparation of acrylate copolymers
1. The raw material components are as follows:
soft monomer: butyl acrylate, 60 parts by weight; isooctyl acrylate, 20 parts by weight;
hard monomer: methyl methacrylate, 2 parts by weight;
crosslinking monomer: acrylic acid, 3 parts by weight; hydroxyethyl acrylate, 2 parts by weight;
hydrophobic monomer: t-butyl acrylate, 5 parts by weight;
cyclic monomer: 5 parts of glycidyl methacrylate;
polar monomer: beta-carboxyethyl acrylate, 3 parts by weight;
a first solvent: 300 parts by weight of ethyl acetate;
2. the synthesis method comprises the following steps:
(1) Putting the raw materials into a 1000ml reaction kettle, heating to 60 ℃ under the atmosphere of nitrogen, uniformly stirring for 30min, and adding 0.2% of initiator azodiisobutyronitrile for stable reaction for 240 min;
(2) Heating to 65 ℃, adding 0.2% of initiator azodiisobutyronitrile, and reacting for 60 minutes;
(3) Heating to 80 ℃, adding 0.2% of initiator azodiisobutyronitrile, and reacting for 180 minutes to obtain an acrylic ester copolymer C; the acrylate copolymer viscosity was controlled to 5000cps (25 ℃ C.), solids content 25%, mw by controlling the reaction exotherm: about 100 ten thousand, tg= -50 ℃.
2. Preparation of double-sided pressure-sensitive adhesive tapes
1. The raw material components are as follows:
acrylic ester copolymer: 100 parts by weight of the acrylic copolymer C;
tackifying resin: 803L of barren river and 6 parts by weight; kyowa KB-120,6;
curing agent: toluene diisocyanate, 0.3 parts by weight; 0.3 part by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane;
a second solvent: ethyl acetate, 30 parts by weight;
2. the preparation method comprises the following steps: the same as in example 1.
Example 4 group
This set of examples is intended to illustrate the effect of adjustment of the curative content on the performance of double-sided tape.
Specifically:
example 4a: referring to example 3, the curing agent ratios employed were: toluene diisocyanate 0.2 parts by weight; 0.2 parts by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane;
example 4b: referring to example 3, the curing agent ratios employed were: toluene diisocyanate 0.5 parts by weight; 0.5 part by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane;
example 4c: referring to example 3, the curing agent ratios employed were: toluene diisocyanate 0.15 parts by weight; 0.3 parts by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane;
example 4d: referring to example 3, the curing agent ratios employed were: toluene diisocyanate 0.45 parts by weight; 0.3 part by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane.
Example 5 group
This set of examples is intended to illustrate the effect of adjustment of the type of curing agent on the performance of the double-sided tape.
Specifically:
example 5a: referring to example 3, the curing agent used was of the type and content: 0.3 part by weight of N, N, N ', N ' -tetraepoxypropyl-4, 4' -diaminodiphenyl methane; hexamethylene diisocyanate trimer (HDI), 0.3 parts by weight;
example 5b: referring to example 3, the curing agent used was of the type and content: 0.3 part by weight of N, N, N ', N ' -tetraepoxypropyl-4, 4' -diaminodiphenyl methane; 0.3 part by weight of diglycidyl 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid;
example 5c: referring to example 3, the curing agent used was of the type and content: hexamethylene diisocyanate trimer (HDI), 0.3 parts by weight; isophorone diisocyanate (IPDI), 0.3 parts by weight.
Example 6
Referring to example 3, the difference is that: the polar monomer beta-carboxyethyl acrylate is not added.
Example 7 group
This set of examples is intended to illustrate the effect of the adjustment of the type of tackifying resin on the performance of the double-sided tape.
Specifically:
example 7a: referring to example 3, the difference is that the tackifying resin is high softening point resin block 803l,12 parts by weight;
example 7a: referring to example 3, the tackifying resin is a mid-softening point resin of the family metallocene KB-120, 12 parts by weight;
example 7c: referring to example 3, the tackifying resin was a mid-softening point resin of the family metallocene KB-120,6 parts by weight; 6 parts by weight of low softening point resin arizona RE85 GB.
Comparative example 1
Referring to example 3, the difference is that: no hydrophobic monomer t-butyl acrylate was added.
Comparative example 2
Referring to example 3, the difference is that: no cyclic monomer glycidyl methacrylate was added.
Comparative example 3
Referring to example 3, the difference is that: 0.6 part by weight of toluene diisocyanate using a single curing agent.
Comparative example 4
Referring to example 3, the difference is that: 0.6 part by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane was used as a single curing agent.
Comparative example 5
Referring to example 3, the difference is that: toluene diisocyanate 0.15 parts by weight; 0.15 part by weight of 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane.
Test case
(1) The steel plate peel strength and PC plate peel strength of the adhesive tapes provided in examples and comparative examples were tested with reference to GB/T2792-2014 Standard of test method for adhesive tape peel strength, and the results are recorded in Table 1.
(2) Test of anti-rebound Performance
The rebound resistance of the adhesive tape on a 30-degree curved surface was tested under the following conditions:
result evaluation criteria: rebound resistance: corresponding to the tilting height of 0.ltoreq.h.ltoreq.5 mm, indicating "very good"; the corresponding tilting height is more than 5 and less than or equal to 15 and mm, which indicates good; the corresponding tilting height is more than 15 and less than or equal to 25 and mm, and represents 'general'; the corresponding tilting height is more than 25 and less than or equal to 35 and mm, which indicates 'worse'; the corresponding cocking height is h > 35 mm, which means "very bad". The results are recorded in table 1.
(3) Shear force test
The testing method comprises the following steps: GB/T4851-2014 test method for adhesive tape holding Property. The results are recorded in table 1.
(4) Water vapor resistance test
The adhesive tape was tested for its moisture resistance under the following conditions:
result evaluation criteria: the water vapor resistance corresponds to the red time of the color developing agent: t > 24 h, representing "very good"; t is more than 18 and less than or equal to 24 and h, which is "good"; 12 < t is less than or equal to 18 h, which represents "general"; t is more than 6 and less than or equal to 12 and h, which represents 'poor'; t is more than or equal to 0 and less than or equal to 6 and h, which means 'very bad'. The results are recorded in table 1.
TABLE 1
As can be seen from Table 1, the invention adopts the mode of combining the epoxy curing agent and the isocyanate curing agent, and the added curing agent is crosslinked with carboxyl and hydroxyl in the polymer, so that the colloid keeps high crosslinking degree, and simultaneously, the ring-opening of the cyclic monomer in the polymer is reacted with the hydroxyl and carboxyl groups, thereby further improving the crosslinking degree of the polymer, and generating the polymer with a high-compactness structure to improve the hydrophobicity and the water resistance of the adhesive tape. By adding the hydrophobic monomer, the polymer has excellent water resistance, because the hydrophobic monomer adopts tert-butyl acrylate, and the tert-butyl steric hindrance structure provides beneficial hydrophobic performance, and as the content of the hydrophobic monomer increases, the water contact angle of the surface of the adhesive film increases, so that the hydrophobicity and the water resistance of the adhesive tape are improved.
The adhesive tape prepared by the embodiment of the invention has excellent adhesive property, high-temperature and high-humidity (85 ℃) rebound resistance and good water vapor resistance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is to be construed as including any modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (7)
1. A pressure sensitive adhesive composition comprising an acrylate copolymer, a tackifying resin and a curing agent; the content of the tackifying resin is 5-20 parts by weight and the content of the curing agent is 0.3-1.4 parts by weight relative to 100 parts by weight of the acrylic acid ester copolymer;
the acrylic ester copolymer comprises the following raw material components: 50-90 parts by weight of soft monomer, 1-10 parts by weight of hard monomer and 5-40 parts by weight of functional monomer; the functional monomer comprises 1-10 parts by weight of crosslinking monomer, 1-10 parts by weight of hydrophobic monomer, 1-10 parts by weight of cyclic monomer and 1-10 parts by weight of polar monomer;
wherein the soft monomer is selected from one or a combination of at least two of butyl acrylate, isooctyl acrylate, lauryl acrylate and lauryl methacrylate;
the hard monomer is selected from one or a combination of at least two of methyl methacrylate, methyl acrylate, isobornyl acrylate and isobornyl methacrylate;
the crosslinking monomer is selected from one or a combination of at least two of acrylic acid, methacrylic acid, hydroxyethyl acrylate and hydroxyethyl methacrylate;
the hydrophobic monomer is selected from one or a combination of at least two of tert-butyl acrylate, tert-butyl methacrylate, hexafluorobutyl acrylate and tridecyl acrylate;
the cyclic monomer is selected from one or a combination of at least two of glycidyl methacrylate, N-vinyl pyrrolidone, tetrahydrofuran acrylic ester, cyclohexyl acrylate and cyclohexyl methacrylate;
the polar monomer is beta-carboxyethyl acrylate and/or acrylic acid-beta-hydroxypropyl ester;
the curing agent is selected from the combination of epoxy curing agent and isocyanate curing agent with the mass ratio of 1 (0.5-1.5);
the epoxy curing agent is at least one selected from 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N, N, N ', N ' -tetraepoxypropyl-4, 4' -diaminodiphenyl methane and 4, 5-epoxycyclohexane-1, 2-diglycidyl ester;
the tackifying resin is a combination of a high softening point tackifying resin and a medium softening point tackifying resin; the softening point of the high softening point tackifying resin is 145-155 ℃, and the softening point of the medium softening point tackifying resin is 98-125 ℃.
2. The composition of claim 1, wherein the acrylate copolymer further comprises an initiator; the content of the initiator is 0.1 to 1.5 parts by weight relative to 100 parts by weight of the acrylate copolymer;
the initiator is selected from one or a combination of at least two of azo initiator, organic peroxide initiator and inorganic peroxide initiator.
3. The composition of claim 1 or 2, wherein the acrylate copolymer has a molecular weight of 50-130 tens of thousands;
the solid content of the acrylic ester copolymer is 20% -60%;
the viscosity of the acrylate copolymer is 1000-18000 cps.
4. The composition of claim 1, wherein the tackifying resin is selected from one or a combination of at least two of terpene tackifying resins, phenolic modified tackifying resins, rosin tackifying resins, and petroleum tackifying resins.
5. The composition of claim 1, wherein the isocyanate curing agent is selected from at least one of toluene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
6. A pressure sensitive adhesive comprising the composition of any one of claims 1-5.
7. A pressure sensitive adhesive article comprising the composition of any one of claims 1-5, or the pressure sensitive adhesive of claim 6.
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