WO2014187692A1 - Preparation of pressure sensitive adhesive dispersions from multi-stage emulsion polymerization for applications of protective films - Google Patents
Preparation of pressure sensitive adhesive dispersions from multi-stage emulsion polymerization for applications of protective films Download PDFInfo
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- WO2014187692A1 WO2014187692A1 PCT/EP2014/059640 EP2014059640W WO2014187692A1 WO 2014187692 A1 WO2014187692 A1 WO 2014187692A1 EP 2014059640 W EP2014059640 W EP 2014059640W WO 2014187692 A1 WO2014187692 A1 WO 2014187692A1
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- sensitive adhesive
- dispersion
- ethylenically unsaturated
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- 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
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- 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
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
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- 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
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
- C09J133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C09J151/003—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 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
- C08G2170/40—Compositions for pressure-sensitive adhesives
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
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- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Definitions
- the present invention relates to a process for preparing a pressure sensitive adhesive dispersion.
- it relates to a process for preparing a pressure sensitive adhesive dispersion for protection of surfaces by a multi-stage emulsion polymerization, and the pressure sensitive adhesive dispersion prepared therefrom.
- Protective films are used to temporarily protect the surfaces of articles or products from scratches or pollutions, and they can find their applications in industrial processing and in surface protection of final products before the usage.
- adhesion strength e.g. tack and peel
- one common criterion is shared in most practices, i.e. when the protective film is removed, there should be no residue on the protected surface.
- the residual specimen from the adhesive on the protected surface can cause the "ghost shadow” that is commonly referred to as "ghosting" or "shadow”.
- Ghosting can happen with hot melt, solvent-borne, and polymer dispersion adhesives, which, though not quite clear, may be attributed to small molecules, oligomers, or low molecular weight short-chained polymers. In some special applications, a "ghost shadow" is problematic, in particular when a protective film is used on a glossy surface.
- WO2011/154920A1 discloses a process for preparing aqueous polymer dispersions for producing composite films by a multistage emulsion polymerization. The object thereof was to prepare aqueous polymer dispersions which can be used to produce composite films having very good instantaneous adhesion and very good heat stability. WO2011/154920A1 does not solve the "ghost shadow" problem for protective films.
- US2012/0077030A1 discloses the multistage emulsion polymerization preparation of aqueous pressure-sensitive adhesive dispersions for producing self-adhesive articles. The object was to provide aqueous PSA dispersions having as small an emulsifier content as possible, having good adhesion and cohesion, and forming as little coagulum as possible. US2012/0077030A1 does not have the effect of avoiding ghost shadow and adhesive residue on the metal surface.
- WO2012/038202A1 discloses a process for preparing an aqueous pressure-sensitive adhe- sive dispersion via multistage free-radical emulsion polymerization.
- the obtained aqueous pressure-sensitive adhesive dispersions can be used for producing self-adhesive articles, especially self-adhesive labels and adhesive tapes.
- WO2012/038202A1 does not aim at avoiding "ghost shadow" on protective films.
- CN200610077426.2 discloses a pressure sensitive adhesive that can be readily removed from sensitive surfaces without significant ghosting, exhibit good wet out and are easy and cheap to prepare. However, CN200610077426.2 does not relates to a process for preparing the pressure sensitive adhesive via multi-stages of emulsion polymerization, and the pressure sensitive adhesive of CN200610077426.2 is completely different from the pressure sensitive adhesive obtained in the present invention.
- An in-situ made protective colloid from a multi-stage emulsion polymerization is a promising solution for reducing or eliminating the ghost shadow, because 1) no emulsifier is used during the polymerization, and 2) the molecular weight and functionality of the protective colloid prepared therefrom can be easily controlled and adjusted for further treatments or modifications.
- Functional groups such as carboxylic acid groups and hydroxyl groups, that are incorporated into the dispersions through copolymerization of functional monomers, offer much flexibility to different crosslinking mechanisms as well as adjustable crosslinking degrees.
- These functional groups when coupled with multi-functional crosslinking agents, such as aziridine, isocya- nate, oxazoline and carbodiimide, can be utilized as a two-component crosslinking system.
- a pressure sensitive adhesive dispersion obtained from such an emulsifier- free multi-stage emulsion polymerization is provided to solve the "ghost shadow" problem for protective films.
- the present invention provides a preparation process of a pressure sensitive adhesive dis- persion via a multi-stage emulsion polymerization.
- a protective film coated with the pressure sensitive adhesive dispersion of the invention can avoid the "ghost shadow" on the protected surface when removed from the protected surface, through reduced - amount of low molecular weight species in the adhesive, particularly no emulsifiers engaged during the polymerization process.
- the process of the invention comprises: a. preparing a protective colloid in a first stage of the emulsion polymerization, during which no extra emulsifier is used; b.
- the polymers obtained from the emulsion polymerization contain functional groups that can be crosslinked during the coating and drying processes when the pressure sensitive adhesives are formed; and preferably c. cross-linking the polymers obtained from the emulsion polymerization with a crosslinking agent.
- the pressure sensitive adhesive dispersion obtained from the process of the invention successfully avoids the "ghost shadow" on the protected surface.
- the pressure sensitive adhesive from the pressure sensitive adhesive dispersion of the invention or from the pressure sensitive adhesive formulation of the invention shows not only good anchorage on a polyethylene film but also good cohesion, and avoid occurrence of adhesives cohesive failure and adhesives transfer, thereby adhesive residues on the stainless steel surface are eliminated.
- no visible ghost shadow is present on a stainless steel surface after a protective film of the invention is removed, wherein the protective film of the invention is obtained from applying the pressure sensitive adhesive dispersion of the inven- tion or the pressure sensitive adhesive formulation of the invention onto a film.
- the present invention relates to a process for preparing a pressure sensitive adhesive dispersion via a multi-stage emulsion polymerization.
- ethylenically unsaturated monomers means mono-ethylenically unsaturated monomers.
- ethylenically unsaturated monomers in the present invention, when used, is independent from the term “carboxylic acid group containing-ethylenically unsaturated monomer” of the invention.
- the present invention relates to a process for preparing a pressure sensitive adhesive dispersion, comprising:
- aqueous medium in an aqueous medium, obtaining a first-stage polymer particle from a first-stage monomer composition consisting of ethylenically unsaturated monomers and at least one carboxylic acid group containing ethylenically unsaturated monomer, to form a first-stage dispersion, wherein the carboxylic acid group containing ethylenically unsaturated monomer is included in an amount of at least 1.0 wt% (preferably 10-30 wt%) of the first-stage monomer composition; ii) adding a chain transfer agent to the first-stage monomer composition, wherein the added amount of the chain transfer agent is in the range of 0.3-1.5 wt%, preferably 0.3-1.1 wt%, based on the weight of the first-stage monomer composition;
- a second stage of the emulsion polymerization wherein in the presence of the neutralized first-stage dispersion, a second-stage monomer composition consisting of ethylenically unsatu- rated monomers and optionally at least one multi-ethylenically unsaturated monomer, is polymerized into the first-stage polymer particles to form the second-stage polymer particles, thereby obtaining the pressure sensitive adhesive dispersion,
- weight ratio of the first-stage monomer composition to the total of the first- stage monomer composition and the second-stage monomer composition should be in the range of 5-50wt%, preferably 8-30 wt %, such as 10-20 wt %.
- the first-stage monomer composition forms the first-stage polymer particles, and then, in the second stage of emulsion polymerization, the second-stage monomer composition polymerizes into the first-stage polymer particles to form the pressure sensitive adhesive dispersion of the invention.
- the multi-stage emulsion polymerization of the invention takes place in an aqueous medium, and no emulsifier is used.
- the carboxylic acid group containing ethylenically unsaturated monomers are copolymerized with ethylenically unsaturated monomers of the first-stage monomer composition, to form the first-stage polymer particles with acid groups.
- the hydrophilicity of the first-stage polymer particles will increase so as to act as a protective colloid for the second stage emulsion polymerization and, toward the end of the polymerization, to be able to stabilize the polymer dispersion with high solids content.
- the number-average molecular weight of the obtained protective colloids should be above 2000 g/mol, and preferably within the range of 10,000-50,000 g/mol.
- seed particles may be contained in the initial charge to the first stage of the emulsion polymerization to precisely control the size of the polymer particles.
- seed dispersions e.g. polystyrene seed dispersion
- the weight ratio of the first- stage monomer composition to the total of the first-stage monomer composition and the second- stage monomer composition should be in the range of 5-50wt%, preferably 8-30 wt %, such as 10-20 wt %.
- the suitable ethylenically unsaturated monomers of the first-stage monomer composition can be one or a combination of, but not limited to, (meth)acrylates with/without functional groups (e.g. 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate, methyl acrylate, methyl methac- rylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, ureido methacrylate, glycidyl methac- rylate, acetoacetoxyethyl methacrylate, hydroxypropylcarbamate acrylate and SIPOMER® ⁇ - CEA (from Solvay Rhodia, Singapore)), vinyl and allyl monomers with/without functional groups (e.g.
- (meth)acrylates with/without functional groups e.g. 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate,
- monomers suitable for the first-stage monomer composition may be used in combination; and monomers suitable for the second-stage monomer composition may be used in combination.
- combinations of two or more monomers suitable for being used as ethylenically unsaturated monomers of the first-stage mon- omer composition may be applicable to the process of the invention.
- Combination of different ethylenically unsaturated monomers can not only control the glass transition temperature of the copolymers thus adjusting the performance of the adhesives, but also provide functional groups to improve the functionalities of the obtained dispersions.
- SIPOMER® COPS-I, SIPOMER® AAE-10, SIPOMER® AES-100, SIPOMER® ⁇ -CEA, LATEMUL PD-420, LATEMUL PD-450 and Golpanol® VS are applicable for better dispersion stability; glycidyl methacrylate, N-methylolacrylamide and diacetone acrylamide (paired with adipic dihydrazide) are applicable for crosslmking; and VeoVaTM 9, VeoVaTM 10, VeoVaTM EH, SIPOMER® PAM- 100 and ureido methacrylate are applicable for offering special properties such as good water whitening resistance and high polarity for physical "crosslinking" to the obtained adhesives thereafter.
- one or more of monomers selected from the group consisting of SIPOMER® COPS-I, SIPOMER® AAE-10, SIPOMER® AES-100, SIPOMER® ⁇ -CEA, LATEMUL PD-420, LATEMUL PD-450 and Golpanol® VS are used in combination with one or more of monomers selected from the group consisting of glycidyl methacrylate, N-methylolacrylamide, diacetone acrylamide (paired with adipic dihydrazide via addition of adipic dihydrazide to the final dispersion), VeoVaTM 9, VeoVaTM 10, VeoVaTM EH, SIPOMER® PAM-100 and ureido methacrylate.
- adipic dihydrazide should be added into the obtained pressure sensitive adhesive dispersion after the multi-stage emulsion polymerization of the invention, which means that di- acetone acrylamide, when used, should be paired with adipic dihydrazide, via addition of adipic dihydrazide to the dispersion, to obtain the final pressure sensitive adhesive dispersion.
- the suitable carboxylic acid group containing ethylenically unsaturated monomers in the first-stage monomer composition can be selected from ethylenically unsaturated acid monomers and the combination thereof, such as acrylic acid, methacrylic acid, itaconic acid and the combi- nation thereof. At least one carboxylic acid group containing ethylenically unsaturated monomers should be included at this stage of emulsion polymerization, and the amount should be preferably at least 1.0 wt% of the first-stage monomer composition in the first stage of polymerization to guarantee good dispersion stability and to provide enough functionality for the cross- linking step thereafter.
- the suitable bases for the neutralizing step in the first stage of emulsion polymerization can be one or a combination of aqueous inorganic bases, for example, but not limited to, sodium hydroxide, potassium hydroxide and ammonia water.
- a high pH value at this stage may affect the efficiency of the initiators, and a pH value of ⁇ 7.0 is preferable.
- a chain transfer agent is a must for the first stage of emulsion polymerization.
- the suitable chain transfer agent can be one or a combination of, but not limited to tertiary dodecyl mercaptan and 2-ethylhexyl thioglycolate, whose preferable amount should be in the range of 0.3-1.5 wt%, preferably 0.3-1.1 wt%, based on the weight of the first-stage monomer composition.
- the second-stage monomer composition is polymerized into the first-stage polymer particles formed from the first stage of emulsion polymerization.
- the suitable ethylenically unsaturated monomers in the second-stage monomer composition are one or a combination of, but not limited to (meth)acrylates with/without functional groups (e.g.2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, 2- hydroxyethyl acrylate, 2-hydroxypropyl acrylate, ureido methacrylate, glycidyl methacrylate, acetoacetoxyethyl methacrylate, hydroxypropylcarbamate acrylate and SIPOMER® ⁇ -CEA), vinyl and allyl monomers with/without functional groups (e.g.
- styrene vinyl acetate, VeoVaTM 9, VeoVaTM 10, VeoVaTM EH, Golpanol® VS, SIPOMER® COPS-I, SIPOMER® AAE-10 and SIPOMER® AES-100), and other functional ethylenically unsaturated monomers (e.g. SIPOMER® PAM-100, LATEMUL PD-420, LATEMUL PD-450, N-methylolacrylamide and diacetone acrylamide paired with adipic dihydrazide via addition of the adipic dihydrazide to the obtained pressure sensitive adhesive dispersion).
- SIPOMER® PAM-100 LATEMUL PD-420, LATEMUL PD-450, N-methylolacrylamide and diacetone acrylamide paired with adipic dihydrazide via addition of the adipic dihydrazide to the obtained pressure sensitive adhesive dispersion.
- the suitable multi-ethylenically unsaturated monomers in the second-stage monomer composition when necessary, are selected from the group consisting of divinylbenzene, allyl methacrylate, diethylene glycol dimethacrylate, Laromer® BDDA, trimethylolpropane trimethacry- lateand other multi-ethylenically unsaturated monomers.
- Water soluble initiators including thermal initiators and redox initiators, e.g. sodium persul- fate, potassium persulfate, ammonium persulfate, sodium acetone bisulfite/ tert-butyl hydroperoxide and sodium bisulfite / sodium persulfate, may be used during the multi-stage emulsion polymerization as well as the deodorization process after the polymerization.
- the emulsion polymerization of the present invention may take place at any temperature suitable for an emulsion polymerization, for example, at a temperature in a range of 65-95 °C, preferably 75-90 °C, and more preferably 80-85°C.
- the pressure sensitive adhesive dispersion prepared from the process of the invention has a solid content of 40-56%, and a pH value of 5.0-9.5.
- the average particle size of the polymer particles dispersed in the pressure sensitive adhesive dispersion is adjustable within the range of 140-350 nm.
- the glass transition temperature of the first-stage polymer is lower than 0°C; the glass transition temperature of the second-stage polymer is lower than - 20°C; and the glass transition temperature of the overall dispersion polymer is lower than -15°C.
- T n are the glass transition temperatures of the polymers synthesized in each case only from one of the monomers 1, 2, . . . n, in degrees Kelvin.
- the Tg values for the homopolymers of the majority of monomers are known and are listed in, for example, Ullmann's Ecyclopedia of Industrial Chemistry, Vol. 5, Vol. A21, page 169, VCH Weinheim, 1992; other sources of glass transition temperatures of homopolymers include, for example, J. Brandrup, E. H. Immergut, Polymer Handbook, 1st Edition, J. Wiley, New York 1966, 2nd Edition, J. Wiley, New York 1975, and 3rd Edition, J. Wiley, New York 1989.
- the present invention also relates to the pressure sensitive adhesive dispersion prepared by the process of the invention.
- the present invention relates to a process for preparing a pressure sensitive adhesive formulation, comprising steps of: adding a crosslinking agent to the pressure sensitive adhesive dispersion prepared from the process of the invention.
- one or more additional additives such as a wetting agent e. g. Lumiten® I-SC and a thickener may be added into the process of this aspect.
- a wetting agent e. g. Lumiten® I-SC and a thickener
- the process for preparing a pressure sensitive adhesive formulation of the invention when the pressure sensitive adhesive dispersion prepared from the process of the invention has a pH value of ⁇ 7.0, then preferably, before the step of adding a cross- linking agent to the pressure sensitive adhesive dispersion, the process for preparing a pressure sensitive adhesive formulation of the invention further comprises a step of neutralizing the pres- sure sensitive adhesive dispersion prepared from the process of the invention with a base to a pH value of > 7.0, preferably below 10.
- the base used for neutralization may be any base suitable for the purpose of the invention, e.g. ammonia water, potassium hydroxide and sodium hydroxide, preferably in form of aqueous solution.
- a crosslinking agent is added into the pressure sensitive adhesive dispersion of the invention and well mixed.
- the crosslinking agent suitable for the purpose of the invention is capable of reacting with carboxylic acid or carboxylate in polymers obtained by the multi-stage emulsion polymerization of the invention.
- the cross-linking agent is selected from the group consisting of multi-functional aziridine, isocyanate, oxazoline, carbodiimide and combinations thereof, e.g. Crosslinker® CX-100 (DSM NeoResins , Zwolle , The Netherlands), XAMA®7
- the amount of the crosslinking agent suitable for the process of the invention theoretically corresponds to the amount of carboxylic acid or carboxylate in polymers obtained by the multi-stage emulsion polymerization of the invention.
- the amount of the crosslinking agent is in the range of 0 to 10% by weight, preferably 0 to 8% by weight, more preferably 0.5 to 5% by weight, such as 1 to 3% by weight, based on the total weight of the pressure sensitive adhesive formulation of the invention.
- the present invention further relates to a pressure sensitive adhesive formulation obtained from the process for preparing a pressure sensitive adhesive formulation of the invention.
- the present invention relates to a substrate coated with the pressure sensitive adhesive dispersion of the invention or the pressure sensitive adhesive formulation of the invention.
- the substrate may be any substrate suitable for applying an adhesive, preferably the substrate is selected from the group consisting of tape, sheet, film, plate, and the like, more preferably the substrate is a protective film.
- the present invention relates to the use of the pressure sensitive adhesive dispersion of the invention or the pressure sensitive adhesive formulation of the invention for preparing a protective film.
- the pressure sensitive adhesive dispersion and the pressure sensitive adhesive formulation obtained from the present processes successfully eliminate the "ghost shadow". For example, when a protective film coated with the pressure sensitive adhesive dispersion obtained from the present process applied to the surface of a stainless steel test panel under the ambient and harsh ageing conditions, the protective film does not produce ghost shadow on the surface after being removed from the surface, and there exists no adhesive residue on the metal surface.
- the pressure sensitive adhesive formulation obtained from the present process produces the same result.
- the properties of the pressure sensitive adhesive dispersion and the pressure sensitive adhesive formulation of the invention such as tack and peel strength can be adjusted by changing the combination of monomers (to affect the glass transition temperature) and by adjusting the molecular weights and/or crosslinking degrees during the polymerization stages (with multi-ethylenically unsaturated monomers) and formulation/coating processes (with external crosslinking agents).
- the present invention relates to following embodiments:
- aqueous medium in an aqueous medium, obtaining a first-stage polymer particle from a first-stage monomer composition consisting of ethylenically unsaturated monomers and at least one carboxylic acid group containing ethylenically unsaturated monomer, to form a first-stage dispersion, wherein the carboxylic acid group containing ethylenically unsaturated monomer is included in an amount of at least 1.0 wt% (preferably 10-30 wt%) of the first-stage monomer composition; ii) adding a chain transfer agent to the first-stage monomer composition, wherein the added amount of the chain transfer agent is in the range of 0.3-1.5 wt%, preferably 0.3-1.1 wt%, based on the weight of the first-stage monomer composition;
- a second stage of the emulsion polymerization wherein in the presence of the neutralized first-stage dispersion, a second-stage monomer composition consisting of ethylenically unsaturated monomers and optionally at least one multi-ethylenically unsaturated monomer, is polymerized into the first-stage polymer particles to form the second-stage polymer particles, there- by obtaining the pressure sensitive adhesive dispersion,
- the weight ratio of the first-stage monomer composition to the total of the first- stage monomer composition and the second- stage monomer composition is in the range of 5- 50wt%, preferably 8-30 wt %, such as 10-20 wt %.
- a water soluble initiator is used in the emulsion polymerization
- the water soluble initiator is selected from the group consisting of thermal initiators and redox initiators, e.g. sodium persulfate, potassium persulfate, ammonium persulfate, sodium acetone bisulfite/ tert-butyl hydroperoxide and sodium bisulfite / sodium persulfate.
- the ethylenically unsaturated monomers of the first-stage monomer composition are selected from the group consisting of (meth)acrylates with/without functional groups, vinyl and allyl monomers with/without functional groups, other functional ethylenically unsaturated monomers and combinations thereof, preferably the ethylenically unsaturated monomers of the first-stage monomer composition other than the carboxylic acid group containing ethylenically unsaturated monomers are selected from the group consisting of 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, ureido methacrylate, glyc- idyl methacrylate, acetoacetoxyethyl methacrylate, hydroxypropylcarbamate acrylate, SIPOM
- ethylenically unsaturated monomers of the second-stage monomer composition are selected from the group consisting of 2-ethylhexyl acrylate, butyl acrylate, ethyl acrylate, methyl acrylate, methyl methacrylate, styrene, vinyl acetate, VeoVaTM 10, 2-hydroxyethyl acry- late, 2-hydroxypropyl acrylate, SIPOMER® COPS-I, LATEMUL PD-450, Golpanol® VS, ureido methacrylate, glycidyl methacrylate, diacetone acrylamide paired with adipic dihydrazide via addition of the adipic dihydrazide to the obtained dispersion, and carboxylic acid group containing ethylenically unsaturated monomers, such as acrylic acid, methacrylic acid and itaconic acid, and combinations thereof; and
- multi-ethylenically unsaturated monomers are selected from the group consisting of divinylbenzene, allyl methacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Laromer® BDDA and combinations thereof.
- the ethylenically unsaturated monomers of the first-stage monomer composition are combination of the ethylenically unsaturated monomer selected from the group consisting of VeoVaTM 10, 2-hydroxyethyl acrylate, 2- hydroxypropyl acrylate, SIPOMER® COPS-I, LATEMUL PD-450, Golpanol® VS, ureido methacrylate, glycidyl methacrylate, diacetone acrylamide paired with adipic dihydrazide via addition of the adipic dihydrazide to the obtained dispersion, with the ethylenically unsaturated monomer selected from the group consisting of 2-ethylhexyl acrylate, butyl acrylate, ethyl acry- late, methyl acrylate, methyl methacrylate, styrene, and vinyl acetate.
- the ethylenically unsaturated monomer selected from the group consist
- the base is an aqueous inorganic base, preferably selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonia water.
- a process for preparing a pressure sensitive adhesive formulation comprising steps of: adding a crosslinking agent to the pressure sensitive adhesive dispersion obtained from the process of any one of embodiments 1-7;
- additives such as wetting agents and thickeners.
- the process further comprises, before the step of adding a crosslinking agent to the pressure sensitive adhesive dispersion, a step of neutralizing the pressure sensitive adhesive dispersion with a base to a pH value of > 7.0, preferably below 10.
- the base is an aqueous inorganic base, preferably selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonia water.
- cross-linking agent is selected from the group consisting of multi-functional aziridine, isocyanate, oxazoline, carbodiimide or combinations thereof, e.g. NEOCRYL® CX-100, XAMA®7, Basonat® DS 3582, Basonat® LR 9056, HYCASYLTM 510.
- the amount of the cross-linking agent is in the range of 0 to 10% by weight, preferably 0 to 8% by weight, more preferably 0.5 to 5% by weight, such as 1 to 3% by weight, based on the total weight of the pressure sensitive ad- hesive formulation.
- a polystyrene seed dispersion (4 g, solid content 33%) was introduced.
- the polystyrene seed dispersion was heated and Sodium persulfate (SPS, 7%, 71 g) was added when the temperature reached 80°C.
- SPS Sodium persulfate
- addition of the Mixture 1 (consisting of butyl acrylate 126 g, acrylic acid 22 g, tertiary dodecyl mercaptan 1.3 g) was started. 30 min after the start of addition of Mixture 1, ammonia water (25%, 10.5 g) was added within 45min.
- Mixture 2 consisting of butyl acrylate 716 g, styrene 42 g, methyl methacrylate 84 kg, Laromer® BDDA 7.7 g
- Mixture 2 consisting of butyl acrylate 716 g, styrene 42 g, methyl methacrylate 84 kg, Laromer® BDDA 7.7 g
- the dispersion P01 was formulated with 0.5% Lumiten® I-SC aqueous solution (50 wt.%, a wetting agent) to form the formulation FOla.
- the formulation FOla was further mixed with 2 and 3 wt.% Basonat® LR 9056 (a crosslinking agent) with vigorous stirring for 30 min, to form the formulations FOlb and FOlc, respectively.
- Each of the formulations was cast onto a corona treated polyethylene film respectively, and dried at 70°C for 3 min to form protective film Ola, protective film 01b and protective film 01c, respectively.
- the dry weights of the obtained adhesive layers on the film were ⁇ 5 g/m 2 .
- the dispersion P02 was prepared according to the same procedures as Example 1, except that no polystyrene seed dispersion was included as the initial charge of the polymerization vessel during the emulsion polymerization stages.
- the obtained dispersion P02 had a solid content of 44.6%, pH of 5.8 and particle size of ⁇ 212nm.
- the dispersion P02 was neutralized with NaOH solution (8 wt.%) to pH 7.4, and then formulated with 0.5% Lumiten® I-SC aqueous solution (50 wt.%), to form the formulation F02a.
- the formulation F02a was further mixed with 2 wt.% Basonat® LR 9056 with vigorous stirring for 30 min, to form the formulation F02b.
- Each of the formulations F02a and F02b was cast onto a corona treated polyethylene films respectively, and dried at 70°C for 3 min to form pro- tective film 02a and protective film 02b.
- the dry weights of the obtained adhesive layers on the film were ⁇ 5 g/m 2 .
- the dispersion P03 was prepared according to the same procedures as Example 1, except that the introduced polystyrene seed dispersion was 3.3 g, and the Mixture 1 consisted of 2- ethylhexyl acrylate 1 lg, butyl acrylate 82 g, acrylic acid 16 g, and tertiary dodecyl mercaptan 0.9 g-
- the obtained dispersion P03 had a solid content of 44.9%, pH of 6.7 and particle size of ⁇ 203nm.
- the dispersion P03 was neutralized with NaOH solution (8 wt.%) to pH 7.5, and then for- mulated with 0.5% Lumiten® I-SC aqueous solution (50 wt.%), to form the formulation F03.
- the formulation F03 was cast onto a corona treated polyethylene film, and dried at 70°C for 3 min to form a protective film 03.
- the dry weight of the obtained adhesive layer on the film was ⁇ 5 g/m 2 .
- Example 4 Preparation and application of dispersion P04
- the dispersion P04 was prepared according to the same procedures as Example 1, except the reaction temperature was 90°C.
- the obtained dispersion P04 had a solid content of 41.9%, pH of 6.2 and particle size of ⁇ 217nm.
- the dispersion P04 was neutralized with NaOH solution (8 wt.%) to pH 7.8, and then formulated with 0.5%) Lumiten® I-SC aqueous solution (50 wt.%), to form the formulation F04, after which the formulation F04 was cast onto a corona treated polyethylene film, and dried at 70°C for 3 min to form a protective film 04.
- the dry weight of the obtained adhesive layer on the film was ⁇ 5 g/m 2 .
- the dispersion P05 was prepared according to the same procedures as Example 1, except that the introduced polystyrene seed dispersion was 3.1 g, the Mixture 1 consisted of butyl acry- late 69 g, acrylic acid 19 g, diacetone acrylamide 9.9 g and tertiary dodecyl mercaptan 0.9 g, and after the chemical deodorization, adipic dihydrazide 10.2 g was added into the dispersion before cooling and filtration.
- the obtained dispersion P05 has a solid content of 44 wt.%, the particle size of -189 nm and pH of 6.5.
- the dispersion P05 was neutralized with NaOH solution (8 wt.%) to pH 8.0, and then for- mulated with 0.5% Lumiten® I-SC aqueous solution (50 wt.%), to form the formulation F05a.
- the formulation F05a was further mixed with 2 wt.% Basonat® LR 9056 with vigorous stirring for 30 min, to form the formulation F05b.
- the formulation F05a and formulation F05b were respectively cast onto a corona treated polyethylene film, and dried at 70°C for 3 min to form a protective film 05 a and a protective film 05b.
- the dry weight of the obtained adhesive layer on the film was ⁇ 5 g/m 2 .
- the dispersion P06 was prepared according to the same procedures as Example 1, except that the initial charge of the polystyrene seed dispersion was 3.3 g, the Mixture 1 consisted of butyl acrylate 90 g, acrylic acid 18.5 g and 2-ethylhexyl thioglycolate 0.9 g, and the Mixture 2 consisted of butyl acrylate 820 g, styrene 48 g, methyl methacrylate 95 kg, Laromer® BDDA 8.5 g and Sipomer COPS-1 (40 wt.% in water) 11.5g.
- the obtained dispersion P06 has a solid content of 45.7 wt.%, the particle size of -195 nm and pH of 6.8.
- the dispersion P05 was neutralized with NaOH solution (8 wt.%) to pH 8.0, and then for- mulated with 0.5% Lumiten® I-SC aqueous solution (50 wt.%), to form the formulation F06a.
- the formulation F06a was further mixed with 1 wt.% Basonat® LR 9056, 2 wt.% Basonat® LR 9056, 3 wt.% Basonat® LR 9056, 5 wt.% Basonat® LR 9056, 10 wt.% Basonat® LR 9056 respectively, with vigorous stirring for 30 min, to form the formulation F06b, formulation F06c, formulation F06d, formulation F06e and formulation F06f.
- the formulation F06a, formulation F06b, formulation F06c, formulation F06d, formulation F06e and formulation F06f were cast onto a corona treated polyethylene film respectively, and dried at 70°C for 3 min to form a protective film 06a, a protective film 06b, a protective film 06c, a protective film 06d, a protective film 06e and a protective film 06f, respectively.
- the dry weight of the obtained adhesive layer on the film was -5 g/m 2 .
- the dispersion P07 was prepared according to the same procedures as Example 1, except that the introduced polystyrene seed dispersion was 3.3 g, the Mixture 1 consisted of butyl acrylate 93 g, acrylic acid 6.5 g, 2-ethylhexyl thioglycolate 0.9 g and Latemul PD450 l lg, and the Mixture 2 consisted of butyl acrylate 830 g, styrene 50 g, methyl methacrylate 98 kg and Laromer® BDDA 9g.
- the obtained dispersion P07 has a solid content of 45.2 wt.%, the particle size of -270 nm and pH of 6.3.
- the dispersion P07 was neutralized with NaOH solution (8 wt.%) to pH 8.0, and then for- mulated with 0.5%> Lumiten® I-SC aqueous solution (50 wt.%), and further mixed with 2 wt.% Basonat® LR 9056 with vigorous stirring for 30 min to form the formulation F07, after which the formulation F07 was cast onto a corona treated polyethylene film, and dried at 70°C for 3 min to form a protective film 07.
- the dry weight of the obtained adhesive layer on the film was -5 g/m 2 .
- the dispersion P08 was prepared according to the same procedures as Example 1, except that the introduced polystyrene seed dispersion was 3.3 g, the Mixture 1 consisted of butyl acrylate 93 g, methacrylic acid 16 g, tertiary dodecyl mercaptan 0.9 g and Latemul PD450 l lg, the Mixture 2 consisted of butyl acrylate 883 g, methyl methacrylate 98 kg and Laromer® BDDA 8.6 g, and ammonia water (25%, 8.6 g) was used for the two additions of ammonia water respectively.
- the obtained dispersion P08 has a solid content of 44.6 wt.%, the particle size of -272 nm and pH of 9.1.
- the dispersion P08 was formulated with 0.5% Lumiten® I-SC aqueous solution (50 wt.%), and further mixed with 2 wt.% Basonat® LR 9056 with vigorous stirring for 30 min to form the formulation F08, after which the formulation F08 was cast onto a corona treated polyethylene film, and dried at 70°C for 3 min to form a protective film 08.
- the dry weight of the obtained adhesive layer on the film was ⁇ 5 g/m 2 .
- Example 9 Adhesive performance tests and results of the protective film application
- the protective film Ola obtained from example 1 was applied on a steel panel to form a covered steel panel. Then the covered steel panel was aged for 7 days at 70°C, 85% relative humidity. After that, the protective film Ola was peeled off from the steel panel. Then the appearance of the obtained naked steel panel was observed and the result was reported in following tables.
- Series 1 of the test corresponds to protective films 01 a, 01b, 01c
- Series 2 of the test corresponds to protective films 02a, 02b
- Series 3 of the test corresponds to protective film 03
- Series 4 of the test corresponds to protective film 04
- Series 5 of the test corresponds to protective films 05a, 05b
- Series 6 of the test corresponds to protective films 06a, 06b, 06c, 06d, 06e, 06f
- Series 7 of the test corresponds to protective film 07
- Series 8 of the test corresponds to protective film 08.
- Rank 1 Clean, no residue, no visible shadow when observed vertically to the surface of the steel panel under regular indoor daylight, however when observed from a direction having an angle to vertical direction to the observed surface, very slight shadow was observed;
- Rank 3 Clean, no residue, no visible shadow when observed under regular indoor daylight, however when observed under illumination of a close light source and from a direction having an angle to vertical direction to the observed surface, very slight shadow was observed;
- the percentage of the crosslinking agent was provided on the basis of the total weight of the formulation.
- All the protective films obtained from the invention can result in a surface having a clean, no residue, no visible shadow appearance when observed vertically to the surface of the steel panel under regular illumination;
- crosslinker will make the appearance of the surface better, as can be seen from series No. 1, 2, 5 and 6.
- Example 5 for preparing protective film 05 series used monomer combination of
- Example 6 for preparing protective film 06 series further used a functional monomer, the results of this test series 6 are generally better than that of the test series 2.
Abstract
Description
Claims
Priority Applications (6)
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EP14724068.3A EP2999758A1 (en) | 2013-05-21 | 2014-05-12 | Preparation of pressure sensitive adhesive dispersions from multi-stage emulsion polymerization for applications of protective films |
KR1020157035718A KR20160010568A (en) | 2013-05-21 | 2014-05-12 | Preparation of pressure sensitive adhesive dispersions from multi-stage emulsion polymerization for applications of protective films |
BR112015029093A BR112015029093A2 (en) | 2013-05-21 | 2014-05-12 | processes for preparing a dispersion and pressure sensitive adhesive formulation, dispersion and pressure sensitive adhesive formulation, coated substrate, and dispersion and pressure sensitive adhesive formulation uses |
CN201480041160.9A CN105408437B (en) | 2013-05-21 | 2014-05-12 | Pressure-sensitive adhesive agent dispersion for protective film is prepared by multistage emulsion polymerization |
JP2016514327A JP6463737B2 (en) | 2013-05-21 | 2014-05-12 | Production of pressure-sensitive adhesive dispersions by multi-stage emulsion polymerization for the application of protective films |
US14/892,898 US20160122597A1 (en) | 2013-05-21 | 2014-05-12 | Preparation of pressure sensitive adhesive dispersions from multi-stage emulsion polymerization for applications of protective films |
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CNPCT/CN2013/075984 | 2013-05-21 |
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US (1) | US20160122597A1 (en) |
EP (1) | EP2999758A1 (en) |
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US20160122597A1 (en) | 2016-05-05 |
JP2016521771A (en) | 2016-07-25 |
EP2999758A1 (en) | 2016-03-30 |
JP6463737B2 (en) | 2019-02-06 |
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