CN113528065B - Acrylic pressure-sensitive adhesive composition, product thereof and related preparation method - Google Patents
Acrylic pressure-sensitive adhesive composition, product thereof and related preparation method Download PDFInfo
- Publication number
- CN113528065B CN113528065B CN202010314227.9A CN202010314227A CN113528065B CN 113528065 B CN113528065 B CN 113528065B CN 202010314227 A CN202010314227 A CN 202010314227A CN 113528065 B CN113528065 B CN 113528065B
- Authority
- CN
- China
- Prior art keywords
- meth
- acrylate
- weight
- sensitive adhesive
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention provides an acrylic pressure-sensitive adhesive composition and an article thereof, comprising, based on 100 parts by weight of the acrylic pressure-sensitive adhesive composition: 45-99.9 parts by weight of a polymer A, wherein the polymer A is rosin resin grafted polyacrylate, and has a Tg of 0 ℃ or lower, a weight average molecular weight of 100,000 daltons (Dalton) or higher, and a polymer dispersibility index of 7 or higher; and the rosin resin is 1 to 15 parts by weight based on 100 parts by weight of the polymer A. The invention also relates to a method for synthesizing the acrylic pressure-sensitive adhesive composition. The acrylic pressure-sensitive adhesive composition and the product thereof are suitable for bonding the surfaces of low-surface-energy base materials, such as polyolefin and derivative materials such as polypropylene plates/films and polyethylene plates/films, and functional coatings such as self-cleaning coatings, and have high bonding strength and bonding stability after high-temperature aging.
Description
Technical Field
The invention relates to an acrylic acid series pressure-sensitive adhesive composition, a pressure-sensitive adhesive product containing the acrylic acid series pressure-sensitive adhesive composition, pressure-sensitive adhesive glue containing the acrylic acid series pressure-sensitive adhesive composition and a preparation method of rosin resin grafted polyacrylate which is used for synthesizing the acrylic acid series pressure-sensitive adhesive composition and has the weight-average molecular weight of more than 100,000 daltons (Dalton) and the polymer dispersibility index of more than 7.
Background
In the field of adhesives, bonding schemes for low surface energy substrates include: structural glues, foam tapes and Pressure Sensitive Adhesives (PSA). Structural glues have high adhesion but damage to the surface (usually resulting in surface swelling or corrosion) and are not suitable for bonding substrates of high appearance and thin thickness. The foam tape is thick, porous and expensive. In order to achieve good wetting ability on the surface of a low-surface-energy substrate, the conventional pressure-sensitive adhesive (PSA) needs to sacrifice the modulus and cohesion, so that the adhesive strength, the holding power and/or the adhesive stability are/is low, and the PSA cannot resist high temperature.
Aiming at the defects, a technical scheme is that micromolecule rosin resin is mixed in high-modulus pressure-sensitive adhesive to enhance the adhesive force between the pressure-sensitive adhesive and the low-surface-energy base material; meanwhile, the chain entanglement of the plasticized polymer enhances the chain movement of the polymer, thereby increasing the surface wetting capacity of the pressure-sensitive adhesive. However, the small-molecular rosin resin can migrate to the interface under the action of time and/or high temperature, and the adhesive force and the adhesive stability of the pressure-sensitive adhesive are reduced. The pressure-sensitive adhesive has poor permanent adhesion, bonding stability and high temperature resistance.
For this reason, attempts have been made to fix small-molecule rosin resins to polymer chains in order to reduce migration. For example, acrylate monomers are grafted onto rosin resins and further copolymerized with glue systems of acrylates. However, the rosin resin has a large number of active hydrogen atoms, and the acrylate monomer with the rosin resin side chain has great steric hindrance, which seriously affects the chain growth of the polymer. At present, only polyacrylate grafted with rosin with small molecular weight can be obtained, and is not suitable for being used as oligomer in an adhesive. For example, as for the method of modifying rosin resin with acrylate monomer, chinese patent application CN106479367A (contents [0004] and example [0007 ]) and CN107254023A (contents [0017], example [0065 ]) mention the modification of rosin resin with acrylate monomer, in which the rosin resin is mixed with acrylate monomer and then modified at high temperature (for example, 120 ℃ or higher) to obtain rosin resin grafted acrylate monomer.
Although the effect of rosin resins can be partially masked by adding a core-shell structured substance to the emulsion polymerization, the masking effect is limited. The acrylate polymer of grafted rosin obtained by emulsion polymerization is mainly used as a dispersant of a water gel system. For example, with respect to the preparation of rosin resin modified acrylate water gels, the Chinese patent application CN103059212A (summary of the invention [0005 ]) mentions acrylate emulsions modified with hydrogenated rosin resins; CN107236496A (summary of the invention [0004 ]) refers to a rosin resin modified polyurethane-acrylate optically clear structural adhesive, in which acrylic acid, acrylate monomer and acrylamide are polymerized into a core in emulsion. However, in the current industrialized process, the reactive rosin resin can directly participate in the polymerization of acrylate, and the biggest difficulty is that the chain transfer effect of the rosin resin influences the molecular weight of the polymer, so that the glue for pressure-sensitive adhesive with strong enough cohesion can not be formed. In emulsion polymerization systems, this chain transfer effect is somewhat reduced by the core-shell structure (reaction from the inside to the outside), but the molecular weight (weight-average molecular weight < 100,000 daltons) and the tack-sustaining properties (70 ℃, 1x 1inch, tack time under 1kg weight < 1000 minutes) of the resulting product are insufficient for use as an adhesive.
Therefore, there is still a need in the art to provide a pressure-sensitive adhesive for bonding low surface energy substrates, which has better bonding strength, permanent adhesion and/or bonding stability, and high temperature aging resistance.
Disclosure of Invention
Aiming at the problem of bonding between the low-surface-energy base material and other materials (including the low-surface-energy material), the invention provides a novel acrylic pressure-sensitive adhesive composition, and a pressure-sensitive adhesive product obtained by using the novel acrylic pressure-sensitive adhesive composition has good bonding strength, bonding stability and high-temperature aging resistance on the low-surface-energy base material such as a polypropylene plate or film.
To this end, according to an aspect of the present invention, there is provided an acrylic pressure-sensitive adhesive composition comprising, based on 100 parts by weight of the acrylic pressure-sensitive adhesive composition: 45-99.9 parts by weight of a polymer A, wherein the polymer A is rosin resin grafted polyacrylate and has a Tg of below 0 ℃, a weight average molecular weight of above 100,000 daltons and a polymer dispersibility index of above 7; and the rosin resin is 1 to 15 parts by weight based on 100 parts by weight of the polymer A.
According to another aspect of the present invention, there is provided a pressure-sensitive adhesive article comprising: a substrate; and a coating layer of the above acrylic pressure-sensitive adhesive composition coated on at least one surface of the substrate.
According to still another aspect of the present invention, there is provided an acrylic pressure-sensitive adhesive water comprising the above acrylic pressure-sensitive adhesive composition and an organic solvent.
According to still another aspect of the present invention, there is provided a method for preparing a rosin resin-grafted polyacrylate having a weight average molecular weight of 100,000 daltons or more and a polymer dispersibility index of 7 or more, the method comprising:
1) Pre-polymerizing 50-89 weight portions of C4-C18 alkyl (meth) acrylate monomer (a), 5-12 weight portions of one or more of styrene or alpha-methyl styrene or cyclic ethylenic unsaturated (meth) acrylate monomer (b) and 0.85-9.5 weight portions of polymerizable acidic monomer (C) in an organic solvent to obtain a pre-polymer AA with the intrinsic viscosity of 0.6-1.0 dl/g;
2) 1-10 parts by weight of rosin resin modified free radical polymerizable monomer (d), 1-25 parts by weight of (methyl) acrylic acid C4-C18 alkyl ester monomer (a) and 0.15-0.5 part by weight of polymerizable acidic monomer (C) are added into the obtained prepolymer AA for polymerization, and the rosin resin grafted polyacrylate A with the weight average molecular weight Mw of more than 100,000 daltons and the polymer dispersibility index of more than 7 is obtained.
The pressure-sensitive adhesive composition is prepared by taking the rosin resin grafted acrylate polymer A with Tg of less than 0 ℃, weight-average molecular weight of more than 100,000 daltons and polymer dispersibility index of more than 7 as a raw material. The pressure sensitive adhesive composition has high adhesive strength and high adhesive stability to low surface energy substrates (e.g., polypropylene sheets, polyethylene films, self-cleaning coatings, low surface energy coatings, etc.) and exhibits an excellent combination of properties including: 180 degree peel force, high temperature adhesion, high temperature and high humidity aging resistance, etc.
Furthermore, the formula of the pressure-sensitive adhesive composition can also adapt to different surfaces and different bonding requirements by compounding the rosin resin grafted acrylate polymer A with other raw materials/auxiliaries. As the rosin resin is grafted on the polyacrylate polymer with high molecular weight, obvious and stable plasticizing effect exists, and the pressure-sensitive adhesive composition provided by the invention has the lasting adhesion performance and the aging resistance at ultrahigh temperature (more than 100 ℃).
Detailed Description
Aiming at the problem of bonding between a low-surface-energy substrate and other materials, the rosin-grafted acrylate polymer A with sufficiently large molecular weight and polymer dispersity index and relatively low glass transition temperature is polymerized in a solvent environment. The rosin resin grafted acrylate polymer A has higher intrinsic viscosity (intrinsic viscosity) and higher molecular weight, and is blended with a polymer B with relatively high glass transition temperature or other raw materials such as a cross-linking agent or a tackifier to prepare the acrylic pressure-sensitive adhesive composition.
As used herein, the term "(meth) acrylic" refers to acrylic, methacrylic, or both. Likewise, the term "(meth) acrylate" refers to an acrylate, a methacrylate, or both. The term "(meth) acrylate polymer" refers to a polymer of polymerizable monomers primarily acrylic acid/esters and/or methacrylic acid/esters. Correspondingly, a C4-C18 alkyl (meth) acrylate monomer means a C4-C18 alkyl acrylate monomer and/or a C4-C18 alkyl methacrylate monomer, and a cyclic ethylenically unsaturated (meth) acrylate monomer means an aliphatic or aromatic cyclic acrylate monomer and/or an aliphatic or aromatic cyclic methacrylate monomer.
As used herein, C4-C18 alkyl refers to alkyl groups having 4-18 carbon atoms, including isomeric forms thereof, such as n-butyl, t-butyl, isodecyl, n-hexadecyl, 2-octadecyl, and the like.
Polymer A
The acrylic pressure-sensitive adhesive composition provided by the invention comprises a polymer A, wherein the polymer A is rosin resin grafted polyacrylate, the glass transition temperature of the polymer A is below 0 ℃, the weight average molecular weight Mw of the polymer A is above 100,000 daltons, and the polymer dispersity index of the polymer A is above 7. The polymer A comprises 1 to 15 parts by weight of a rosin resin based on 100 parts by weight of the polymer A.
According to certain embodiments of the present invention, preferably, the polymer a has a Polymer Dispersity Index (PDI) of 3 or more, or 7 or more; the polymer A has a polymer dispersibility index of 11 or less, or 10 or less. If PDI is too small, for example, less than 3, the balance of adhesive and cohesive strength as a pressure-sensitive adhesive component is too poor, and it is difficult to balance the permanent adhesion and surface wettability; if PDI is too large, for example, more than 11, the small molecular weight distribution as a pressure-sensitive adhesive component is too large, cohesion is insufficient, and a permanent adhesive effect is hardly exerted.
According to certain embodiments of the present invention, preferably, the glass transition temperature of the polymer A is below 0 ℃, or below-30 ℃, or below-40 ℃, or below-50 ℃. If the glass transition temperature is greater than 0 ℃, the polymer is difficult to generate chain motion at room temperature and cannot effectively wet the bonding surface.
According to certain embodiments of the invention, the polymer A has a weight average molecular weight M w Is greater than 100,000 daltons, preferably greater than 300,000 daltons, or greater than 400,000 daltons; preferably, the weight-average molecular weight M of the polymer A w Is less than 1,000,000 daltons, or less than 700,000 daltons. If the Mw value is too small, for example, less than 100,000 daltons, the chain entanglement effect as an adhesive is insufficient, sufficient cohesive force cannot be generated, and thus effective peel force and tack-holding force cannot be provided.
According to certain embodiments of the present invention, the polymer a is contained in the acrylic pressure-sensitive adhesive composition of the present invention in an amount of not less than 45 parts by weight, or not less than 80 parts by weight, or not less than 90 parts by weight, based on 100 parts by weight of the acrylic pressure-sensitive adhesive composition; and the content of polymer A is not more than 99.9 parts by weight. When the lower limit of the content of the polymer A is in the above range, the pressure-sensitive adhesive system may have a good wettability; when the upper limit of the content of the polymer A is in the above range, the pressure-sensitive adhesive system has good high-temperature properties and permanent adhesion. Also, the acrylic pressure-sensitive adhesive composition containing the polymer a in the above content has high adhesive strength and high adhesive stability, and can exhibit excellent overall properties: including 180 degree peel force, high temperature adhesion, high temperature and high humidity aging resistance, etc.
According to certain embodiments of the present invention, and based on 100 parts by weight of the polymer a, the polymer a comprises 1 part by weight or more of rosin resin. In order to control the molecular weight of the polymer A more favorably, the content of the rosin resin in the polymer A is preferably 5 parts by weight or more but 15 parts by weight or less. Since the content of the rosin resin is too high, it may be difficult to control chain growth and grafting, and may result in too low a molecular weight, so that the tack strength and stability of the pressure-sensitive adhesive composition may be deteriorated.
According to certain embodiments of the present invention, preferably, the polymer a is polymerized from polymerizable monomers, and the polymerizable monomers comprise 75 to 90 parts by weight of one or more of C4-C18 alkyl (meth) acrylate monomer (a), 5 to 12 parts by weight of styrene or α -methylstyrene or cyclic ethylenically unsaturated (meth) acrylate monomer (b), 1 to 10 parts by weight of polymerizable acidic monomer (C), and 1 to 10 parts by weight of rosin resin-modified radical polymerizable monomer (d), based on 100 parts by weight of the polymerizable monomers.
According to some embodiments of the present invention, preferably, the C4-C18 alkyl (meth) acrylate monomer (a) comprises one or more selected from the group consisting of: n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, 2-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 4-methyl-2-pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-octyl (meth) acrylate, isononyl (meth) acrylate, isoamyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, 2-propylheptyl (meth) acrylate, isotridecyl (meth) acrylate, isostearyl (meth) acrylate, octadecyl (meth) acrylate, 2-octadecyl (meth) acrylate, lauryl (meth) acrylate, and heptadecyl (meth) acrylate.
The glass transition temperature of the cyclic ethylenically unsaturated monomer (b) of (meth) acrylic acid is not particularly limited, and when measured as a homopolymer, the glass transition temperature is preferably 60 to 190 ℃. Which is an ethylenically unsaturated monomer having a cyclic structure in the molecule. As the ring in the cyclic ethylenically unsaturated monomer, both an aromatic ring and a non-aromatic ring may be used, but a non-aromatic ring is suitably selected. Examples of the above aromatic ring include aromatic hydrocarbon rings (e.g., benzene ring, condensed ring in naphthalene, etc.) and various heteroaromatic rings. Further, examples of the above-mentioned non-aromatic ring include non-aromatic aliphatic rings (e.g., cycloalkane rings such as cyclopentane, cyclohexane, cycloheptane, cyclooctane; cycloalkene rings such as cyclohexene rings) and non-aromatic crosslinked rings (e.g., crosslinked hydrocarbon rings such as an ant cycloalkane ring including pinane, pinene, camphane, norbornane and the like; a tricyclic hydrocarbon ring in adamantane; a tetracyclic hydrocarbon ring). Specifically, include non-aromatic ring-containing (meth) acrylates such as cyclic alkyl (meth) acrylates (e.g., cyclohexyl (meth) acrylate) and isobornyl (meth) acrylate; aromatic ring-containing (meth) acrylates, for example, aryl (meth) acrylates such as phenyl acrylate, aryloxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate, and arylalkyl (meth) acrylates such as benzyl (meth) acrylate.
According to certain embodiments of the present invention, preferably, the cyclic ethylenically unsaturated (meth) acrylate monomer (b) includes one or more selected from the group consisting of a cyclic alkyl (meth) acrylate (e.g., cyclohexyl (meth) acrylate), isobornyl (meth) acrylate, an aryl (meth) acrylate (e.g., phenyl acrylate), an aryloxyalkyl (meth) acrylate, and an arylalkyl (meth) acrylate, or a mixture thereof with styrene and/or α -methylstyrene.
According to certain embodiments of the present invention, the polymerizable acidic monomer (c) refers to a polymerizable monomer containing an acidic functional group (typically a carboxyl group), preferably including one or more selected from the group consisting of: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, citraconic acid, maleic acid, oleic acid, beta-carboxyethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and vinyl phosphonic acid.
According to certain embodiments of the present invention, rosin resin-modified free radical polymerizable monomer refers to a monomer in which the rosin resin is attached to the free radical polymerizable monomer by grafting. Preferably, it is typical that the rosin resin modifies the acrylic monomer by grafting the rosin resin to the acrylic monomer.
In the present invention, according to certain embodiments, polymer a may be synthesized in a two-step process:
a first step of polymerizing all of styrene or alpha-methylstyrene or (meth) acrylic cyclic ethylenically unsaturated monomer (b) and most of C4-C18 alkyl (meth) acrylate monomer (a) and most of polymerizable acidic monomer (C) to increase the molecular weight to a sufficient length to obtain a prepolymer AA, using an effective temperature and solid content (effective temperature and solid content means temperature and solid content for controlling the molecular weight of the prepolymer in the first polymerization step) without adding rosin resin-modified radical polymerizable monomer (d); wherein the inherent viscosity of the prepolymer AA is in the range of 0.6 to 1.0 dl/g.
In the second step, the entire rosin resin-modified free radical polymerizable monomer (d) and the remaining monomers (a) and (c) are added to the prepolymer AA obtained in the previous step together with the required initiator, and the temperature and solids content are adjusted with a solvent so that the monomer (d) is linked to a long-chain polymer or forms a new short chain with the remaining monomers, thereby forming a broad molecular weight distribution. In subsequent coating, the addition of a curing agent can further fix the rosin resin on a long molecular chain to form an acrylate polymer of grafted rosin with a molecular weight of more than 100,000 daltons.
More specifically, a method for preparing a rosin resin-grafted polyacrylate having a weight average molecular weight of 100,000 daltons or more and a polymer dispersibility index of 7 or more includes:
1) Pre-polymerizing 50-89 weight portions of (methyl) acrylic acid C4-C18 alkyl ester monomer (a), 5-12 weight portions of (methyl) acrylic acid cyclic ethylenic unsaturated monomer (b) and 0.85-9.5 weight portions of polymerizable acid monomer (C) in an organic solvent to obtain a performed polymer AA with the intrinsic viscosity of 0.6-1.0 dl/g;
2) 1-10 parts by weight of rosin resin modified free radical polymerizable monomer (d), 1-25 parts by weight of (methyl) acrylic acid C4-C18 alkyl ester monomer (a) and 0.15-0.5 part by weight of polymerizable acidic monomer (C) are added into the obtained prepolymer AA for polymerization, and rosin resin grafted polyacrylate A with the weight average molecular weight Mw of more than 100,000 daltons and the Polymer Dispersity Index (PDI) of more than 7 is obtained.
According to certain embodiments of the present invention, preferably, the solids content of the prepared polymer A solution is 40 to 50% by weight. The solids content can be adjusted by means of suitable solvents.
The polymer A prepared by the invention is rosin resin grafted polyacrylate with the weight average molecular weight of more than 100,000 daltons and the Polymer Dispersibility Index (PDI) of more than 7. Unlike simple blends of rosin resins and acrylic monomers. According to the polymer A prepared by the invention, the absorption peak on a visible spectrum is obviously changed through NMR detection, and the absorption peak corresponding to the acrylic double bond of the polymer A is obviously disappeared, so that the rosin resin is successfully grafted to polyacrylate molecules, and the rosin resin grafted polyacrylate with large molecular weight is prepared.
Polymer B
The acrylic pressure-sensitive adhesive composition further comprises a polymer B, wherein the polymer B is polyacrylate with the glass transition temperature of more than 60 ℃, and more preferably more than 80 ℃.
According to certain embodiments of the present invention, the above-mentioned polymer B is contained in the acrylic pressure-sensitive adhesive composition of the present invention in an amount of not less than 5 parts by weight, preferably not less than 10 parts by weight, based on 100 parts by weight of the acrylic pressure-sensitive adhesive composition; the content of polymer B is not more than 50 parts by weight, preferably not more than 30 parts by weight. When the content of the polymer B is within the above range, the pressure-sensitive adhesive composition can be prepared to have good high-temperature holding power and peeling force.
According to certain embodiments of the present invention, preferably, the polymer B is polymerized from polymerizable monomers, and the polymerizable monomers comprise 90 to 99 parts by weight of one or more of styrene or alpha-methylstyrene or (meth) acrylic cyclic ethylenically unsaturated monomer (B), 1 to 10 parts by weight of polymerizable acidic monomer (c) and optionally 0.1 to 10 parts by weight of rosin resin modified radical polymerizable monomer (d) based on 100 parts by weight of the polymerizable monomers.
According to certain embodiments of the present invention, preferably, the (meth) acrylic cyclic ethylenically unsaturated monomer (b) comprises one or more selected from the group consisting of: cyclic alkyl (meth) acrylates (such as cyclohexyl (meth) acrylate), isobornyl (meth) acrylate, aryl (meth) acrylates (such as phenyl acrylate), aryloxyalkyl (meth) acrylates, and arylalkyl (meth) acrylates, or mixtures thereof with styrene and/or alpha-methylstyrene.
According to certain embodiments of the present invention, the polymerizable acidic monomer (c) refers to a polymerizable monomer containing an acidic functional group (typically a carboxyl group), preferably comprising one or more selected from the group consisting of: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, citraconic acid, maleic acid, oleic acid, beta-carboxyethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and vinyl phosphonic acid.
According to certain embodiments of the present invention, the rosin resin-modified radical polymerizable monomer (d) refers to a monomer in which a rosin resin is attached to a radical polymerizable monomer by grafting. Preferably, it is typical that the rosin resin modifies the acrylic monomer by grafting the rosin resin to the acrylic monomer.
According to certain embodiments of the present invention, preferably, the polymerizable monomer of polymer B comprises 0.1 to 10 parts by weight of rosin resin-modified radical polymerizable monomer (d), and the weight average molecular weight of polymer B is 7,000 to 25,000 daltons.
According to certain embodiments of the present invention, the rosin resin-modified radical polymerizable monomer (d) is not included in the polymerizable monomers of the polymer B, and the polymer B has a weight average molecular weight of 7000 to 50,000 daltons.
In the present invention, according to certain embodiments, similarly to the above-mentioned polymer a, polymer B can also be synthesized by a two-step process, particularly when the polymerizable monomers of polymer B contain 0.1 to 10 parts by weight of the rosin resin-modified radical polymerizable monomer (d):
1) Prepolymerizing 75-95 parts by weight of monomer (b) and 0.75-9.0 parts by weight of monomer (c) in an organic solvent to synthesize prepolymer BB;
2) 4 to 15 parts by weight of the monomer (B), 0.25 to 1.0 part by weight of the polymerizable acidic monomer (c) and optionally 0.1 to 10 parts by weight of the monomer (d) are added to the obtained prepolymer BB to carry out polymerization reaction, thereby preparing a polymer B.
In the present invention, the polymerization method for obtaining the polymer a or B by means of monomer polymerization is not particularly limited, and may be prepared by any conventional polymerization or copolymerization method, for example, a photo-initiated radical polymerization may be employed to prepare a desired polymer. The photopolymerization method has the advantages that: (1) it is not necessary to heat the monomer solution; (2) photoinitiation stops completely when the activating light source is turned off. Monomer conversion in the system (the ratio of the weight of the monomer in which polymerization occurs to the weight of all monomers used to prepare the polymer) can be achieved by controlling the amount of photoinitiator, and the polymerization can be terminated by quenching the propagating radicals by removing the light source and passing air (oxygen) into the solution. The photoinitiators used may include: benzoin methyl ether, benzoin isopropyl ether, 2-dimethoxyacetophenone, 2-dimethoxy-2-phenyl-1-acetophenone, V-67 (available from DuPont corporation), and the like. Solution polymerization processes may also be used wherein the desired monomers and initiator may be polymerized together with a suitable inert organic solvent in a four-necked reaction vessel equipped with a stirrer, thermometer, condenser, addition funnel and temperature controller.
In the present invention, preferably, after the polymer a and the polymer B are obtained, the polymer B is added to the polymer a and then blended. Wherein a small amount of a solvent, for example, a mixed solvent of isopropyl alcohol/xylene (wherein xylene is less than 5 mass%), may be used to improve solubility, as required. After shaking for several minutes in a THINKY mixer, mix overnight on a three-roll machine. Preferably, the pressure sensitive adhesive composition obtained is homogeneous and transparent before the addition of the curing crosslinking agent.
Optional additives
According to some embodiments of the present invention, the acrylic pressure-sensitive adhesive composition may further comprise an additive selected from the group consisting of: tackifiers, crosslinkers, ultraviolet absorbers, antioxidants, light stabilizers, anti-aging agents, thickeners, plasticizers, softeners, fillers, colorants (e.g., pigments and dyes), surfactants, antistatic agents.
In the present invention, other additives may be added to the resulting adhesive composition, although not required, provided that such additives do not adversely affect the desired properties. For example, compatible tackifiers or crosslinkers can be added to help optimize the final tack and peel characteristics of the PSA. The use of such tack modifiers is common in the art, as described in Handbook of Pressure-Sensitive Adhesive Technology (1982), edited by Donatas Satas. Useful tackifiers include, but are not limited to, low molecular weight hydrocarbon polymers, hydrogenated rosin resins, rosin resins. Examples of useful tackifiers include, but are not limited to, escorez 1401 available from Exxon Mobil, GB-125 available from Arakawa Chemical Industries, GER-85/PER-90/PER-110F available from Wuzhou Sun Shine forest Forestry & Chemicals, and the like. Useful crosslinkers include aromatic aziridine compounds (e.g., RD1054, available from 3M company), polyfunctional aziridine crosslinkers (e.g., CX-100, available from DSM company), and the like.
In the present invention, it is preferable that the resultant composition is subjected to curing crosslinking. The curing crosslinking may be carried out as follows: after the polymers A and B are mixed homogeneously, 0.1 to 0.2% of a crosslinking agent (for example RD1054, CX-100 or RD1054+ CX-100) is added to the transparent A + B system. Mixing is carried out on a three-roll machine and a THINKY machine, respectively, for about 1 hour.
In the present invention, preferably, UV stabilizers known in the art may also be added. The pressure-sensitive adhesive composition provided by the invention can further comprise pigment. The pressure-sensitive adhesive composition provided by the invention can further comprise expanded polymer particles or expanded polymer microspheres so as to improve the forward drop resistance of the prepared pressure-sensitive adhesive layer. These expanded polymeric particles or expanded polymeric microspheres typically have a particle size of 10 to 100 microns. For example, the metallized expanded polymer particles may be selected to impart a desired color appearance and additional foam-like characteristics to the pressure sensitive adhesive layer. The pressure-sensitive adhesive composition provided by the invention can further comprise a plasticizer, a dye, an antioxidant, a coupling agent, a dispersing agent, an anti-settling agent and the like, as long as the performance of the pressure-sensitive adhesive and the pressure-sensitive adhesive layer prepared by the pressure-sensitive adhesive composition is not influenced. In order to improve the die cutting performance of the pressure sensitive adhesive layer, some short synthetic fibers can be added into the pressure sensitive adhesive composition as long as the anti-falling performance of the pressure sensitive adhesive layer is not influenced.
In the present invention, although not particularly limited, preferably, the pressure-sensitive adhesive composition of the present invention is non-aqueous, and for example, it may be 100% solids (pressure-sensitive adhesive) or a blend with a non-aqueous solvent (pressure-sensitive adhesive glue). In addition, surfactants are generally not present in the adhesive composition.
The invention also provides a pressure-sensitive adhesive product. In the present invention, a pressure-sensitive adhesive article such as a pressure-sensitive adhesive sheet or tape can be produced by coating a pressure-sensitive adhesive composition on a suitable substrate or support and then exposing the coated pressure-sensitive adhesive composition to ultraviolet radiation to form a pressure-sensitive adhesive layer. The substrate or carrier may be rigid, flexible, transparent, or opaque, and may be made of any suitable material, such as a polymeric material, a glass or ceramic material, a metal, and the like. In some embodiments, the substrate or carrier may be a polymeric material, for example a flexible polymeric film which may be a flexible backing. Suitable polymeric materials may include: a polyolefin such as polyethylene, or polypropylene (including isotactic polypropylene), polystyrene, polyester (e.g., poly (ethylene terephthalate), poly (butylene terephthalate), polylactide, or poly (caprolactam)), nylon, polyvinyl alcohol, poly (vinylidene fluoride), or cellulose (e.g., cellulose acetate, or ethyl cellulose). The flexible substrate or carrier may have a particular microstructured surface, such as those described in U.S. Pat. Nos. 5141790 (Calhoun et al), 5296277 (Wilson et al), or 5362516 (Wilson et al). These microstructured surfaces can generally be obtained by microreplication techniques. The substrate or carrier may also be prepared from a fabric, such as a fabric formed from synthetic or natural fibers. The fabric may be woven or non-woven. The suitable fibers may include cotton, nylon, rayon, glass, or ceramic. In addition, other suitable substrates or supports may also include metal sheets, metal foils, metallized polymer films, ceramic sheets, or foams (such as acrylic, polyethylene, polyurethane, or neoprene foams).
In the present invention, the pressure-sensitive adhesive composition may be coated onto the substrate or carrier using any suitable method (e.g., roll coating, flow coating, dip coating, spin coating, spray coating, knife coating, or die coating). These different coating methods allow for the application of pressure sensitive adhesive compositions of various suitable thicknesses to a substrate or carrier. The coating thickness may vary, with typical thicknesses of the pressure sensitive adhesive layer ranging from 2 to 500 micrometers, and also from 25 to 250 micrometers. In the present invention, the standard sample for testing is 50um adhesive film +50um PET, and the surface of the adhesive film is protected by a release film of 10 g/inch.
In the present invention, preferably, the pressure-sensitive adhesive article may further include a release paper or a release film covering a surface of the acrylic pressure-sensitive adhesive composition, which is removed before use. Such articles can be made, for example, by extrusion coating the pressure-sensitive adhesive composition onto a substrate surface (preferably pre-cleaned) to form a flat pressure-sensitive adhesive composition layer, and then a release paper can be attached to the pressure-sensitive adhesive composition layer surface.
The present invention also provides a pressure-sensitive adhesive glue, comprising: the acrylic pressure-sensitive adhesive composition of any of the above embodiments and an organic solvent.
In the present invention, the organic solvent used in the pressure-sensitive adhesive glue is not particularly limited as long as the desired pressure-sensitive adhesive glue can be produced. Preferably, the organic solvent used in the present invention may be one or more selected from the group consisting of: ethyl acetate, butyl acetate, methyl formate, ethyl formate, methyl acetate, propyl acetate, isopropanol, acetone, butanone, toluene, xylene, petroleum ether, n-hexane, cyclohexane.
Because the polymer A in the acrylic pressure-sensitive adhesive composition provided by the invention is grafted with rosin resin and has higher molecular weight, the pressure-sensitive adhesive product or the pressure-sensitive adhesive glue obtained by the invention can be well used for bonding low-surface-energy substrates, and the low-surface-energy substrates include but are not limited to one or more of the following groups: polypropylene material, polyethylene material, polyurethane material, polycarbonate material. More particularly, the pressure-sensitive adhesive article or the pressure-sensitive adhesive glue of the present invention can be used for example for the adhesion of films on the surface of self-cleaning steel plates of automobile bodies, films on the surface of Thermo-Plastic vulcanizer, films on the surface of Plastic parts for automobile interiors, adhesion of polypropylene plates, adhesion of polyethylene films and/or adhesion of polypropylene overwraps.
In the present invention, when a range is referred to, both ends of the range and subranges thereof are understood to be included in the range unless otherwise indicated.
Various exemplary embodiments of the present invention are further illustrated by the following list of embodiments, which should not be construed as unduly limiting the invention:
embodiment 1 is an acrylic pressure-sensitive adhesive composition comprising, based on 100 parts by weight of the acrylic pressure-sensitive adhesive composition: 45-99.9 parts by weight of a polymer A, wherein the polymer A is rosin resin grafted polyacrylate and has a Tg of below 0 ℃, a weight average molecular weight of above 100,000 daltons and a polymer dispersibility index of above 7; and the rosin resin is 1 to 15 parts by weight based on 100 parts by weight of the polymer A.
Embodiment 2 is the acrylic pressure-sensitive adhesive composition of embodiment 1, further comprising, based on 100 parts by weight of the acrylic pressure-sensitive adhesive composition: 5 to 50 parts by weight of a polymer B, wherein the polymer B is a polyacrylate having a glass transition temperature of 60 ℃ or higher.
Embodiment 3 is the acrylic pressure-sensitive adhesive composition according to any one of embodiments 1 or 2, wherein the glass transition temperature of the polymer a is-50 ℃ or lower.
Embodiment 4 is the acrylic pressure-sensitive adhesive composition of any one of embodiments 1 to 3, wherein the polymer a has a weight average molecular weight Mw of 400,000 to 700,000 daltons.
Embodiment 5 is the acrylic pressure-sensitive adhesive composition according to any one of embodiments 1 to 4, characterized in that the acrylic pressure-sensitive adhesive composition comprises 80 to 90 parts by weight of the polymer a.
Embodiment 6 is the acrylic pressure-sensitive adhesive composition of any of embodiments 1-5, wherein the polymer a is polymerized from polymerizable monomers comprising 75 to 90 parts by weight of one or more of C4-C18 alkyl (meth) acrylate monomer (a), 5 to 12 parts by weight of styrene or alpha-methylstyrene or cyclic ethylenically unsaturated (meth) acrylate monomer (b), 1 to 10 parts by weight of polymerizable acidic monomer (C), and 1 to 10 parts by weight of rosin resin modified free radical polymerizable monomer (d).
Embodiment 7 is the acrylic pressure-sensitive adhesive composition of any one of embodiments 2 to 6, wherein the polymer B is polymerized from polymerizable monomers comprising 90 to 99 parts by weight of the (meth) acrylic cyclic ethylenically unsaturated monomer (B), 1 to 10 parts by weight of the polymerizable acidic monomer (c), and optionally 0.1 to 10 parts by weight of the rosin resin-modified radical polymerizable monomer (d).
Embodiment 8 is the acrylic pressure-sensitive adhesive composition of embodiment 6, wherein the C4-C18 alkyl (meth) acrylate monomer (a) comprises one or more selected from the group consisting of: n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, 2-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 4-methyl-2-pentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-methylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-octyl (meth) acrylate, isononyl (meth) acrylate, isoamyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, 2-propylheptyl (meth) acrylate, isotridecyl (meth) acrylate, isostearyl (meth) acrylate, octadecyl (meth) acrylate, 2-octadecyl (meth) acrylate, lauryl (meth) acrylate, and heptadecyl (meth) acrylate.
Embodiment 9 is the acrylic pressure-sensitive adhesive composition according to any one of embodiments 6 or 7, wherein the cyclic ethylenically unsaturated monomer (b) of (meth) acrylic acid includes one or more selected from the group consisting of a cyclic alkyl (meth) acrylate such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, an aryl (meth) acrylate such as phenyl acrylate, an aryloxyalkyl (meth) acrylate, and an arylalkyl (meth) acrylate.
Embodiment 10 is the acrylic pressure-sensitive adhesive composition according to any one of embodiment 6 or 7, characterized in that the polymerizable acidic monomer (c) includes one or more selected from the group consisting of: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, citraconic acid, maleic acid, oleic acid, beta-carboxyethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and vinyl phosphonic acid.
Embodiment 11 is the acrylic pressure-sensitive adhesive composition of embodiment 7, wherein the polymerizable monomer of the polymer B comprises 0.1 to 10 parts by weight of the rosin resin-modified radical polymerizable monomer (d), and the weight average molecular weight Mw of the polymer B is 7,000 to 25,000 daltons.
Embodiment 12 is the acrylic pressure-sensitive adhesive composition of embodiment 7, wherein the polymerizable monomer of polymer B does not comprise the rosin resin-modified radical polymerizable monomer (d), and the weight average molecular weight of polymer B is 7,000 to 50,000 daltons.
Embodiment 13 is a pressure-sensitive adhesive article comprising:
a substrate; and
a coating of the acrylic pressure sensitive adhesive composition of any one of claims 1-12 coated on at least one surface of the substrate.
Embodiment 14 is the pressure-sensitive adhesive article of embodiment 13, further comprising a release paper or a release film covering the coated surface of the acrylic pressure-sensitive adhesive composition.
Embodiment 15 is an acrylic pressure-sensitive adhesive water comprising the acrylic pressure-sensitive adhesive composition according to any one of embodiments 1 to 12 and an organic solvent.
Embodiment 16 is the acrylic pressure-sensitive glue of embodiment 15, wherein the acrylic pressure-sensitive glue has a solid content of 20 to 70 wt.%.
Embodiment 7 is the acrylic pressure-sensitive glue of any of embodiments 15 or 16, wherein the organic solvent is selected from one or more of the following: ethyl acetate, butyl acetate, methyl formate, ethyl formate, methyl acetate, propyl acetate, isopropyl alcohol, acetone, butanone, toluene, xylene, petroleum ether, n-hexane, and cyclohexane.
Embodiment 18 is a method of preparing a rosin resin grafted polyacrylate having a weight average molecular weight of 100,000 daltons or more and a polymer dispersibility index of 7 or more, the method comprising:
1) Pre-polymerizing 50-89 parts by weight of one or more of a C4-C18 alkyl (meth) acrylate monomer (a), 5-12 parts by weight of one or more of styrene or alpha-methylstyrene or a cyclic ethylenically unsaturated (meth) acrylate monomer (b), 0.85-9.5 parts by weight of a polymerizable acidic monomer (C) in an organic solvent to obtain a prepolymer AA having an intrinsic viscosity in the range of 0.6-1.0 dl/g;
2) 1-10 parts by weight of rosin resin modified free radical polymerizable monomer (d), 1-25 parts by weight of (methyl) acrylic acid C4-C18 alkyl ester monomer (a) and 0.15-0.5 part by weight of polymerizable acidic monomer (C) are added into the obtained prepolymer AA for polymerization, and the rosin resin grafted polyacrylate A with the weight average molecular weight Mw of more than 100,000 daltons and the polymer dispersibility index of more than 7 is obtained.
Examples
The following examples and comparative examples are provided to aid in the understanding of the present invention, and should not be construed as limiting the scope of the invention. Unless otherwise indicated, all parts, percentages, ratios, concentrations, and the like in the examples and the remainder of the specification are by weight, and all reagents used in the examples are obtained or obtainable from general chemical suppliers or may be synthesized by conventional methods.
The raw materials used in the examples of the present invention and the comparative examples are shown in table 1 below.
TABLE 1
Test methods and standards:
glass transition temperature (Tg) measurement
The glass transition temperature (Tg) was determined using a Differential Scanning Calorimeter (DSC) (Q100, commercially available from TA instruments, TA co. Each sample was lowered to-80 ℃ and held at-80 ℃ for 2 minutes, and then heated to 40 ℃ at a rate of 10 ℃/minute (or to 100 ℃). Tg corresponds to the peak temperature at which the glass transitions to a liquid state.
Intrinsic Viscosity (IV) measurement
The viscosity is mainly used to characterize the molecular weight of the polymer (blend) and is measured as follows: a0.5 g/dl dilute solution sample of the pressure sensitive adhesive composition was prepared in ethyl acetate. 25.00ml of this dilute solution was pipetted into a 70ml aluminum dish and dried in a forced air oven at 105 ℃ for 30 minutes and the weight of the dried polymer was recorded as w. 9g of ethyl acetate were pipetted into a Cannon-Fenske viscometer and passed through
AVS 400 electronic timer measures flow time (t) 0 ) While the flow time (t) of the same weight of the dilute solution sample was also measured s ). Base ofAt the measured w, t 0 And t s The intrinsic viscosity IV is calculated using the following formula:
RV＝t 0 /t s
IV 0 ＝(LnRV)/4w
IV＝0.2[(RV-1)/4w-IV 0 )](1-0.5/4w)+IV 0
where Ln represents the natural logarithm.
n w Polymer molecular weight (including number average molecular weight M and weight average molecular weight M) test:
sample preparation and experimental methods: the sample was dissolved in tetrahydrofuran standard solution at a concentration of 20mg/4 ml. After the sample underwent gentle shaking to accelerate dissolution, it was left overnight to ensure dissolution.
Test conditions-equipment: waters 2695-MALS, column: jordi-DVB 30cm x 7.8mm, column temperature: 40 ℃, solvent: tetrahydrofuran standard, flow rate: 1.0ml/min, sample injection amount: 40 microliter, test: reflective Index, standard: polystyrene.
Polymer Dispersion Index (PDI)Defined as PDI = M w /M n 。
180 degree peel force test
The 180 ° peel force of the pressure sensitive adhesive prepared was measured according to the ASTM D3330/D3330M standard on the surface of polypropylene (PP), self-cleaning coated paint plate (urethane) and standard stainless steel plate, respectively.
70 ℃ static shear holding time measurement
The static shear holding time at 70 ℃ is used to characterize the cohesion of the polymer, the longer this time, the better the cohesion, and the test procedure is as described in ASTM international standard D3654. Specifically, test samples were prepared as follows: the 25.4mm by 25.4mm pressure sensitive tape was rolled back and forth once with a 1kg rubber roller to adhere the adhesive film to the surface of the alumina plate cleaned with IPA. Then, a 1kg load was loaded under the test sample, and then vertically suspended in a 70 ℃ dry box. The time recorded during the test is the duration of time that the test sample did not fall off the alumina plate surface under load. If the duration is greater than 10000min, then the mark is good; if the duration is 1000min to 10000min, marking as qualified; if the duration is less than 1000min, it is flagged as failed. Comparisons between specific times can also be made to determine relative goodness.
Permanent adhesion test at 70 ℃ for 304 steel plate/PP/low surface energy paint plate
The 1inch # 1inch standard was attached to the surface of PP/paint board/steel plate and suspended vertically at 70 ℃ with a 1kg weight. If the duration is greater than 10000min, then the mark is good; if the duration is 1000min to 10000min, marking as qualified; if the duration is less than 1000min, it is flagged as being rejected.
85 ℃/85% RH aging test
The tape adhered to the paint/steel panels was placed in an oven at 85 ℃/85% relative humidity along with the substrate, and the aged samples were subjected to one or more of the above experimental tests to determine the relative superiority and inferiority of the aging resistance by comparing the performance differences before and after aging.
Long time aging test at 80 deg.C
The tape with release paper protection is put into an oven at 80 ℃ for aging for 4 weeks, and then the aged sample is used for one or more experimental tests, and the relative superiority and inferiority of the aging resistance are determined by comparing the performance difference before and after aging.
120 ℃ high temperature aging test
And (3) putting the adhesive tape with the release paper protection into an oven at 120 ℃ for aging for 5 days, then using the aged sample for one or more experimental tests, and determining the relative superiority and inferiority of the aging resistance by comparing the performance difference before and after aging.
In all performance tests (tables 7 to 11), the results were averaged over 3 measurements.
Preparation of Polymer A
Synthesis example 1:
1) 1098.2g (75.2 parts by weight) of isooctyl acrylate monomer (a), 169g (11.6 parts by weight) of isobornyl acrylate monomer (b) and 34.9g (2.4 parts by weight) of acrylic acid monomer (c) are added into an organic solvent (ethyl acetate 848.6g, butyl acetate 565.8 g), and the mixture is reacted for 8 hours at 58 ℃ under the protection of nitrogen in the presence of an initiator benzoin methyl ether to obtain a prepolymer AA with the intrinsic viscosity of 0.6-1.0 dl/g;
2) After the temperature of the reaction vessel was raised to 80 ℃ in a nitrogen atmosphere, 76.8g (5.3 parts by weight) of TSR-0065 monomer (d), 153.6g (10.5 parts by weight) of isooctyl acrylate monomer (a), and 3.5g (0.2 part by weight) of acrylic acid monomer (c) were added to the reaction vessel and mixed with the prepolymer AA obtained in step 1), and the solid content was adjusted to 45% by weight using solvents (149.8 g of ethyl acetate and 99.8g of butyl acetate). Oxygen was removed with nitrogen and reacted in the presence of benzoin methyl ether as a polymerization initiator for 24 hours to obtain the final product a. Denoted A1.
Samples A2-A3 of rosin resin grafted polyacrylate Polymer A were prepared as in A1, with the specific formulations and process parameters shown in Table 2:
synthesis example 2:
in 1569g of ethyl acetate as an organic solvent, 1245.6g (86.6 parts by weight) of isooctyl acrylate monomer (a), 158.4g (11.0 parts by weight) of isobornyl acrylate monomer (b), and 34.6g (2.4 parts by weight) of acrylic acid monomer (c) were reacted in the presence of benzoin methyl ether as an initiator at 58 ℃ for 24 hours under nitrogen protection to obtain a polyacrylate polymer, which was designated as CA1.
In the same manner as in CA1, 76.8g (5.3 parts by weight) of TSR-0065 monomer (d) was added to the polymerization monomers for the synthesis of CA 2.
TABLE 2
Note: TSR-0065 or TSR-6000 as monomer (d) is first dissolved in another monomer or solvent. The total reaction time for all samples was 24 hours.
Comparative sample CA1 contained no rosin resin.
The formula of the comparative sample CA2 is completely the same as that of the sample A1, all monomers are polymerized together through one-step reaction to directly obtain the comparative sample CA2, and a prepolymer with the intrinsic viscosity of 0.6-1.0dl/g is not prepared through a two-step method, and then the prepolymer is polymerized with the rest monomers.
The molecular weight measurements carried out on the samples A1 to A3 of the polymer A described above and on the comparative samples CA1 to CA2 are shown in Table 3 below:
TABLE 3
As can be seen from Table 3, the rosin resin-grafted polyacrylate polymers A1 to A3 prepared according to the invention have number average molecular weights (Mn) in the range from 50,000 to 80,000 Dalton and weight average molecular weights (Mw) of more than 100,000 Dalton, in the range from 400,000 to 700,000 Dalton, and PDI (M) w /M n ) Are all larger than 7 and are in the range of 7-11.
Preparation of Polymer B
According to the following table 4, 90wt.% of the monomer (b) and 80wt.% of the monomer (c) were polymerized in a reaction kettle at 65 ℃ for 8 hours under nitrogen protection in a solvent in the presence of a polymerization initiator to obtain a prepolymer; the rosin resin-modified monomer (d) obtained by grafting to an acrylate monomer is dissolved in the remaining monomers (b) and (c), and the final solid content and molecular weight are adjusted using a solvent. After raising the temperature to 85 ℃ in a nitrogen atmosphere, the remaining monomers (B) and (c) and the monomer (d) (i.e., TSR-0065 or TSR-6000, commercially available from Tongxuan Ixin chemical Co., ltd.) were added to the obtained prepolymer, oxygen was removed with nitrogen after the addition, and polymerization was carried out in the presence of a polymerization initiator for 8 hours, thereby obtaining polymer B.
Samples B1 and B2 of Polymer B were prepared according to the reaction procedure described above, wherein B2 contained no rosin resin.
The formulation and process parameters are shown in table 4:
TABLE 4
Remarking: the solids content of all samples was 25wt%.
The results of molecular weight measurements on samples B1-B2 of polymer B are shown in Table 5 below:
TABLE 5
Preparation of pressure-sensitive adhesive compositions (examples E1 to E5, E11 to E14 and comparative examples C1 to C3, C11 to C16)
After adding the polymer B or the crosslinking agent/tackifier to the polymer A, mixing is carried out on a three-roll machine for 12 hours, and the required pressure-sensitive adhesive composition can be obtained. If necessary, a small amount of a mixed solvent such as isopropanol/xylene (wherein xylene is less than 5 mass%) may be used to improve solubility. The formulations of the specific pressure-sensitive adhesive compositions are shown in tables 6-1 and 6-2.
TABLE 6-1 sample composition combination Table of pressure sensitive adhesive compositions (Polymer A + Polymer B)
| A1 | A2 | A3 | CA1 | CA2 | B2 | RD1054 | CX-100 | 0065 | 1401 | |
| E1 | 90.9 | 9.1 | 0.1 | 0.1 | ||||||
| E2 | 90.9 | 9.1 | 0.2 | |||||||
| E3 | 45.45 | 45.45 | 9.1 | 0.2 | ||||||
| E4 | 90.9 | 9.1 | 0.2 | 12 | ||||||
| E5 | 90.9 | 9.1 | 0.2 | |||||||
| C1 | 90.9 | 9.1 | 0.2 | |||||||
| C2 | 90.9 | 9.1 | 0.2 | 12 | ||||||
| C3 | 90.9 | 9.1 | 0.2 |
TABLE 6-2 sample composition combination Table of pressure sensitive adhesive compositions (Polymer A + crosslinker/tackifier)
| A1 | A2 | A3 | CA1 | CA2 | B2 | RD1054 | CX-100 | 0065 | 1401 | GB-125 | |
| E11 | 100 | 0.2 | |||||||||
| E12 | 100 | 0.2 | |||||||||
| E13 | 100 | 0.2 | |||||||||
| E14 | 100 | 0.2 | |||||||||
| C11 | 100 | 0.2 | |||||||||
| C12 | 100 | 0.2 | 12 | ||||||||
| C13 | 100 | 12 | |||||||||
| C14 | 100 | 12 | |||||||||
| C15 | 95 | 0.2 | 5 | ||||||||
| C16 | 100 | 0.2 |
Performance testing of pressure sensitive adhesive compositions
The obtained pressure-sensitive adhesive compositions were subjected to 180 ° peel force test and 180 ° peel force after aging, and basic property comparison, and the results are shown in tables 7 to 9 below.
In which Table 7-1 is the 180 ℃ peel force on the painted surface and on the white standard paint plates for examples E1, E2 and E5 and comparative examples C1, C3.
TABLE 7-1
In Table 7-1, it is acceptable to use a 180 degree peel force on the LSE finish greater than 0.7 and a 180 degree peel force on the standard white finish greater than 0.8. Considering that the pressure-sensitive adhesive needs to simultaneously meet the high-temperature permanent-adhesion performance, the preferred sequence of the failure modes is as follows: separation from the substrate > vibration > separation from the backing > cohesive failure.
Comparative examples C1 and C3 use polymer CA1 without rosin or polymer CA2 prepared by the conventional one-shot process, while examples E1, E2 and E5 use large molecular weight polymers A3 or A1 grafted with rosin. As shown in Table 7-1, the use of the rosin-grafted large molecular weight polymer in the pressure-sensitive adhesive composition can improve the 180 ℃ peel force.
TABLE 7-2
In Table 7-2, it is acceptable to use a 180 degree peel force on the LSE finish greater than 0.50 and a 180 degree peel force on the standard white finish greater than 0.7. Considering that the pressure-sensitive adhesive needs to simultaneously satisfy the high-temperature holding property, the preferred sequence of the failure modes is as follows: separation from the substrate > vibration > separation from the backing > cohesive failure.
Comparative examples C11 and C12 use a polymer CA1 containing no rosin. Comparative example C15 uses a rosin-free polymer CA1 and a rosin-modified monomer TSR-0065. Comparative example C16 used a one-shot preparation of polymer CA2, with cohesive failure mode.
The pressure-sensitive adhesive compositions prepared by mixing the polymers A3, A2 and A1 in examples E11, E13 and E14, respectively, with a crosslinking agent have better 180 DEG peel strength for the LSE finish and the standard white finish.
TABLE 8-1
TABLE 8-2
The aging of tables 8-1 and 8-2 was carried out by applying the pressure sensitive adhesive to a substrate and testing the 180 DEG peel force on the painted surface and the standard board after aging the pressure sensitive adhesive composition for 600 hours at 85 ℃/85% RH. The peel force is further increased due to the wetting promoted by the high temperature. After aging at 85 ℃/85% RH for 600h, the LSE surface 180 degree peel force of greater than 1.00 is qualified, and the standard white paint surface 180 degree peel force of greater than 1.20 is qualified.
The large molecular weight polymer A3 grafted with rosin was used in examples E1, E2 and E11, and the polymer CA1 without rosin was used in comparative examples C11 and C12. Therefore, the embodiment using the high molecular weight polymer containing the grafted rosin shows obvious bonding advantages before and after aging, and has good high-temperature, high-humidity and anti-aging performance. The lack of a high Tg polymer for E11 increases cohesion and the failure mode shifts to cohesive failure.
TABLE 9-1
| Sample (I) | 180 degree peel force (N/mm) on polypropylene sheet | Sticking time (min) at 70 ℃ on polypropylene plate |
| E1 | 0.87/CP | 10000+ |
| E4 | 0.90/CP | 10000+ |
| C1 | 0.61/CP | 10000+ |
| C2 | 0.75/CP | 9400/CF |
| C3 | 1.00/S | 788/CF |
TABLE 9-2
| Sample (I) | 180 degree peel force (N/mm) on polypropylene sheet | Sticking time (min) at 70 ℃ on polypropylene plate |
| E12 | 0.67/CP | 213/CF |
| C11 | 0.52/CP | 77/PO |
| C12 | 0.57/CP | 517/PO |
| C16 | 1.01/CF | 67/CF |
* PO represents interface detachment; CF represents cohesive failure; CP represents separation from the substrate.
Tables 9-1 and 9-2 show the basic property comparisons (180 ℃ peel force, 70 ℃ static tack) for examples E1, E4 and E12 and comparative examples C1, C2, C3 and C11, C12, C16.
In examples E1 and E4, the high molecular weight polymer A3 and the polymer B2 of the grafted rosin were used. In example E12, the high molecular weight polymer A3 grafted with rosin was used. It can be seen that when the pressure-sensitive adhesive composition contains the combination of polymer a and polymer B, both good peel force and good holding power can be obtained. The reason is that after adding the polymer B, effective crosslinking and curing are formed, and the permanent adhesion at high temperature is also improved.
Comparative example C3 it can be seen that, due to the use of the one-shot polymer A, the pressure-sensitive adhesive, although containing rosin resin in the formulation, suffered severe cohesive failure and poor permanent tack in the high temperature static shear test due to migration of the rosin resin.
TABLE 10-1
Note: CP indicates separation from the substrate and CF indicates cohesive failure.
TABLE 10-2
Note: CP indicates separation from the substrate and CF indicates cohesive failure.
Tables 10-1 and 10-2 show the results of the 180 DEG peel force test performed again after the pressure-sensitive adhesive prepared was coated on a 50 mu m PET film and directly placed in an oven at 80 ℃ for four weeks. A percent reduction of less than 20% compared to the peel force before aging was acceptable.
In the case where the macromolecular polymer A1 of grafted rosin and the polymer CA1 synthesized by the one-shot method were used in example E5 and comparative example C3, respectively, it can be seen that the 180 ° peel force before and after aging of E5 was less decreased.
In examples E12, E13 and E14, the rosin-grafted macromolecular polymers A3, A2 and A1 were used, respectively, and although no polymer B was added, the 180 ℃ peel force reduction before and after aging of the corresponding pressure-sensitive adhesive compositions was less than 20%.
Table 11-1: 180 DEG Peel force Change after 5 days of aging at 120 DEG C
Note: CP indicates separation from the substrate and CF indicates cohesive failure.
Table 11-2: 180 DEG Peel force Change after 5 days of aging at 120 DEG C
Note: CP indicates separation from the substrate and CF indicates cohesive failure.
Tables 11-1 and 11-2 show that the pressure-sensitive adhesive prepared was coated on a 50 μm PET film, directly put into an oven at 120 ℃ and aged for five days, and the 180 ℃ peel force before and after the aging was measured.
In the case where the macromolecular polymer A1 of grafted rosin and the polymer CA1 synthesized by the one-shot method were used in example E5 and comparative example C3, respectively, it can be seen that the 180 ° peel force before and after aging of E5 was less decreased.
In examples E12, E13 and E14, the rosin-grafted macromolecular polymers A3, A2 and A1 were used, respectively, and although no polymer B was added, the 180 ℃ peel force reduction before and after 120 ℃ aging of the corresponding pressure-sensitive adhesive compositions was less than 20%.
While not being bound by a particular theory, the inventors of the present invention believe that the possible reasons why the present invention can have the above-described advantageous effects are: in a common blending system, rosin resin is blended and dispersed in polymer molecules in an initial mixture, a mixture after polymerization and crosslinking and a mixture after aging, and only plays a role in swelling and increasing the adhesive force. In the long-term aging process, the rosin resin with small molecular weight migrates to the surface and is enriched under the surface energy and the entanglement of polymer chains, so that the adhesive property and the stability are reduced. In the invention, the rosin resin is grafted on the acrylate long chain to prepare a high molecular weight polymer, and in the initial mixture, the mixture after polymerization and crosslinking and the mixture after aging, the rosin resin is fixed on the acrylate long chain through chemical bonds and is difficult to freely migrate; even after the aging process, the stability can still be kept, and the aging stability is enhanced.
Although the foregoing detailed description contains many specific details for purposes of illustration, it will be appreciated by those of ordinary skill in the art that numerous variations, modifications, substitutions and alterations to these details are within the scope of the invention as claimed. Therefore, the disclosure described in the detailed description does not impose any limitations on the invention claimed. The proper scope of the invention should be determined by the appended claims and their proper legal equivalents. All cited references are incorporated herein by reference in their entirety.
Claims (17)
1. An acrylic pressure-sensitive adhesive composition comprising, based on 100 parts by weight of the acrylic pressure-sensitive adhesive composition: 45 to 99.9 parts by weight of polymer A and 5 to 50 parts by weight of polymer B,
wherein the polymer A is polyacrylate grafted by rosin resin, and has Tg below 0 ℃, a weight average molecular weight above 100,000 daltons and a polymer dispersibility index above 7; and said rosin resin is 1 to 15 parts by weight based on 100 parts by weight of said polymer A,
the polymer B is polyacrylate with a glass transition temperature of more than 60 ℃ and is polymerized by polymerizable monomers, wherein the polymerizable monomers comprise 90-99 parts by weight of (methyl) acrylic acid cyclic ethylenic unsaturated monomer (B), 1-10 parts by weight of polymerizable acidic monomer (c) and optional 0.1-10 parts by weight of rosin resin modified free radical polymerizable monomer (d).
2. The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the glass transition temperature of the polymer a is-40 ℃ or lower.
3. The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the weight-average molecular weight M of the polymer A w Is 400,000 to 700,000 daltons.
4. The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the acrylic pressure-sensitive adhesive composition comprises 80 to 90 parts by weight of the polymer a.
5. The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the polymer a is polymerized from polymerizable monomers comprising 75 to 90 parts by weight of one or more of C4-C18 alkyl (meth) acrylate monomer (a), 5 to 12 parts by weight of styrene or α -methylstyrene or cyclic ethylenically unsaturated (meth) acrylate monomer (b), 1 to 10 parts by weight of polymerizable acidic monomer (C) and 1 to 10 parts by weight of rosin resin-modified free radical polymerizable monomer (d).
6. The acrylic pressure-sensitive adhesive composition according to claim 5, wherein the C4-C18 alkyl (meth) acrylate monomer (a) comprises one or more selected from the group consisting of: n-butyl (meth) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, 2-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 4-methyl-2-pentyl (meth) acrylate, 2-methylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-octyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, 2-propylheptyl (meth) acrylate, isotridecyl (meth) acrylate, isostearyl (meth) acrylate, octadecyl (meth) acrylate, 2-octadecyl (meth) acrylate, lauryl (meth) acrylate, and heptadecyl (meth) acrylate.
7. The acrylic pressure-sensitive adhesive composition according to claim 1 or 5, wherein the cyclic ethylenically unsaturated monomer (b) of (meth) acrylic acid comprises one or more selected from the group consisting of a cyclic alkyl (meth) acrylate, isobornyl (meth) acrylate, aryl (meth) acrylate, aryloxyalkyl (meth) acrylate, and arylalkyl (meth) acrylate.
8. The acrylic pressure-sensitive adhesive composition according to claim 7, wherein the (meth) acrylic cyclic ethylenically unsaturated monomer (b) comprises one or more selected from the group consisting of cyclohexyl (meth) acrylate and phenyl acrylate.
9. The acrylic pressure-sensitive adhesive composition according to claim 1 or 5, wherein the polymerizable acidic monomer (c) comprises one or more selected from the group consisting of: acrylic acid, methacrylic acid, itaconic acid, crotonic acid, citraconic acid, maleic acid, oleic acid, beta-carboxyethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and vinyl phosphonic acid.
10. The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the polymerizable monomer of the polymer B comprises 0.1 to 10 parts by weight of the rosin resin-modified radical polymerizable monomer (d), and the weight average molecular weight Mw of the polymer B is 7,000 to 25,000 daltons.
11. The acrylic pressure-sensitive adhesive composition according to claim 1, wherein the polymerizable monomer of polymer B does not contain the rosin resin-modified radical polymerizable monomer (d), and the weight average molecular weight of polymer B is 7000 to 50,000 daltons.
12. A pressure-sensitive adhesive article, comprising:
a substrate; and
a coating of the acrylic pressure sensitive adhesive composition of any one of claims 1-11 coated on at least one surface of the substrate.
13. The pressure-sensitive adhesive article according to claim 12, further comprising a release paper or a release film covering the coated surface of the acrylic pressure-sensitive adhesive composition.
14. An acrylic pressure-sensitive adhesive water comprising the acrylic pressure-sensitive adhesive composition according to any one of claims 1 to 11 and an organic solvent.
15. The acrylic pressure-sensitive glue of claim 14, wherein the acrylic pressure-sensitive glue has a solid content of 20-70 wt%.
16. The acrylic pressure-sensitive glue of claim 14 or 15, characterized in that the organic solvent is selected from one or more of the following: ethyl acetate, butyl acetate, methyl formate, ethyl formate, methyl acetate, propyl acetate, isopropyl alcohol, acetone, methyl ethyl ketone, toluene, xylene, petroleum ether, n-hexane, and cyclohexane.
17. A method of preparing a rosin resin-grafted polyacrylate having a weight average molecular weight of 100,000 daltons or more and a polymer dispersibility index of 7 or more, the method comprising:
1) Pre-polymerizing 50-89 parts by weight of one or more of a C4-C18 alkyl (meth) acrylate monomer (a), 5-12 parts by weight of one or more of styrene or alpha-methylstyrene or a cyclic ethylenically unsaturated (meth) acrylate monomer (b), 0.85-9.5 parts by weight of a polymerizable acidic monomer (C) in an organic solvent to obtain a prepolymer AA having an intrinsic viscosity in the range of 0.6-1.0 dl/g;
2) 1 to 10 weight portions of rosin resin modified free radical polymerizable monomer (d), 1 to 25 weight portions of (methyl) acrylic acid C4-C18 alkyl ester monomer (a) and 0.15 to 0.5 weight portion of polymerizable acid monomer (C) are added into the obtained prepolymer AA for polymerization to obtain the weight average molecular weight M w Rosin resin-grafted polyacrylate A having a polymer dispersibility index of 7 or more and a molecular weight of 100,000 Dalton or more.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010314227.9A CN113528065B (en) | 2020-04-16 | 2020-04-16 | Acrylic pressure-sensitive adhesive composition, product thereof and related preparation method |
| PCT/IB2021/052860 WO2021209861A1 (en) | 2020-04-16 | 2021-04-06 | Acrylic pressure-sensitive adhesive composition, product thereof, and related preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010314227.9A CN113528065B (en) | 2020-04-16 | 2020-04-16 | Acrylic pressure-sensitive adhesive composition, product thereof and related preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113528065A CN113528065A (en) | 2021-10-22 |
| CN113528065B true CN113528065B (en) | 2023-02-17 |
Family
ID=75690636
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010314227.9A Active CN113528065B (en) | 2020-04-16 | 2020-04-16 | Acrylic pressure-sensitive adhesive composition, product thereof and related preparation method |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113528065B (en) |
| WO (1) | WO2021209861A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114958209B (en) * | 2022-05-25 | 2024-06-14 | 烟台德邦科技股份有限公司 | Ultraviolet light curing adhesive with delayed curing function and preparation method thereof |
| CN115232580A (en) * | 2022-06-14 | 2022-10-25 | 惠州市浩明科技股份有限公司 | Pressure sensitive adhesive and protective film |
| CN115286735B (en) * | 2022-07-07 | 2023-08-11 | 艾利丹尼森(昆山)材料有限公司 | High-performance flame-retardant pressure-sensitive adhesive for phosphorus-containing monomer and cyclic monomer grafted modified acrylate pressure-sensitive adhesive and power battery |
| CN115595077A (en) * | 2022-10-18 | 2023-01-13 | 苏州世华新材料科技股份有限公司（Cn） | Bio-based ultrathin double-sided adhesive |
| CN116376465A (en) * | 2023-04-27 | 2023-07-04 | 世晨材料技术(上海)有限公司 | Environment-friendly low-resistance Wen Wanshe pressure-sensitive adhesive tape and preparation method thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5141790A (en) | 1989-11-20 | 1992-08-25 | Minnesota Mining And Manufacturing Company | Repositionable pressure-sensitive adhesive tape |
| JPH04114079A (en) * | 1990-09-03 | 1992-04-15 | Nitto Denko Corp | Pressure-sensitive adhesive composition |
| US5296277A (en) | 1992-06-26 | 1994-03-22 | Minnesota Mining And Manufacturing Company | Positionable and repositionable adhesive articles |
| CA2370498A1 (en) * | 1999-05-07 | 2000-11-16 | Avery Dennison Corporation | Adhesives and method for making same |
| JP5095279B2 (en) * | 2007-07-06 | 2012-12-12 | 日東電工株式会社 | Adhesive sheet for vehicle surface adhesion |
| JP4813509B2 (en) * | 2008-03-13 | 2011-11-09 | 日東電工株式会社 | Double-sided pressure-sensitive adhesive sheet, method for producing the same, and method for fixing plastic film |
| KR101432886B1 (en) * | 2012-05-11 | 2014-08-21 | (주)엘지하우시스 | Adhesive composition having improved rework properties in high temperature |
| CN103059212B (en) | 2012-12-25 | 2014-11-05 | 中科院广州化学有限公司 | Hydrogenated rosin modified acrylic ester hybridization emulsion and preparation method and application thereof |
| KR20140120490A (en) * | 2013-04-03 | 2014-10-14 | 동우 화인켐 주식회사 | Acrylic copolmer, adhesive composition containing threrof and polarizing plate |
| DE102015217131A1 (en) * | 2015-09-08 | 2017-03-09 | Tesa Se | Adhesive resin-modified pressure-sensitive adhesive |
| CN106479367A (en) | 2016-08-25 | 2017-03-08 | 李先兰 | Acrylic acid modified rosin preparation method |
| CN107236496A (en) | 2017-06-21 | 2017-10-10 | 东莞市联洲知识产权运营管理有限公司 | It is a kind of based on Abietyl modified polyurethane acroleic acid lower shrinkage liquid optical cement and preparation method thereof |
| CN107254023B (en) | 2017-06-26 | 2018-06-29 | 四会市邦得利化工有限公司 | Preparation method and application of graft modified tackifying resin |
| CN110699019A (en) * | 2019-11-26 | 2020-01-17 | 深圳市益达兴科技股份有限公司 | High-temperature-resistant acrylate pressure-sensitive adhesive and double-sided adhesive without base material |
-
2020
- 2020-04-16 CN CN202010314227.9A patent/CN113528065B/en active Active
-
2021
- 2021-04-06 WO PCT/IB2021/052860 patent/WO2021209861A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2021209861A1 (en) | 2021-10-21 |
| CN113528065A (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113528065B (en) | Acrylic pressure-sensitive adhesive composition, product thereof and related preparation method | |
| JP3058346B2 (en) | Radiation-curable acrylate / silicone pressure-sensitive adhesive-coated tape that can be adhered to paint-coated substrates | |
| CN110283549B (en) | Multilayer pressure sensitive adhesive assembly | |
| US5308887A (en) | Pressure-sensitive adhesives | |
| TWI461497B (en) | Adhesive composition and optical member using the same | |
| JP4753196B2 (en) | Optical member pressure-sensitive adhesive composition and optical member-use pressure-sensitive adhesive sheet using the pressure-sensitive adhesive composition | |
| CA1341126C (en) | Pressure-sensitive adhesive | |
| JP3921017B2 (en) | Pressure sensitive adhesive sheet | |
| WO2007061242A1 (en) | Acrylic pressure-sensitive adhesive composition | |
| KR20100051079A (en) | Adhesive film, production method of shaped body | |
| JP2013514445A (en) | Pressure sensitive adhesive for low surface energy substrates | |
| JP6023538B2 (en) | Water-dispersible acrylic pressure-sensitive adhesive composition for re-peeling and pressure-sensitive adhesive sheet | |
| KR20120116874A (en) | Removable water-dispersible acrylic pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet | |
| EP2475715B1 (en) | Dual crosslinked tackified pressure sensitive adhesive | |
| WO2008088115A1 (en) | Acrylic pressure sensitive adhesive compositions | |
| JP2014503640A (en) | Pressure sensitive adhesive for low surface energy substrates | |
| KR20020011341A (en) | Pressure-sensitive adhesive sheets and method of fixing functional film | |
| KR100678795B1 (en) | Pressure-sensitive adhesive compositions and adhesive films | |
| JP2020516741A (en) | Pressure sensitive adhesive composition | |
| JPH10330722A (en) | Pressure-sensitive acrylic adhesive composition | |
| JP6709103B2 (en) | Adhesive composition and adhesive sheet using the same | |
| EP3492542A1 (en) | Pressure-sensitive adhesive sheet | |
| KR20030067278A (en) | Acrylic pressure sensitive adhesive composition | |
| EP3492543A1 (en) | Pressure-sensitive adhesive sheet | |
| JP2003049129A (en) | Method for producing acrylic adhesive tape and acrylic adhesive tape |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |