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WO2025042084A1 - Composition adhésive sans solvant, film adhésif et son procédé de production - Google Patents

Composition adhésive sans solvant, film adhésif et son procédé de production Download PDF

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Publication number
WO2025042084A1
WO2025042084A1 PCT/KR2024/011375 KR2024011375W WO2025042084A1 WO 2025042084 A1 WO2025042084 A1 WO 2025042084A1 KR 2024011375 W KR2024011375 W KR 2024011375W WO 2025042084 A1 WO2025042084 A1 WO 2025042084A1
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WO
WIPO (PCT)
Prior art keywords
adhesive
acrylate
photoinitiator
film
solvent
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English (en)
Korean (ko)
Inventor
김태근
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Toray Advanced Materials Korea Inc
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Toray Advanced Materials Korea Inc
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Publication of WO2025042084A1 publication Critical patent/WO2025042084A1/fr
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C08K5/132—Phenols containing keto groups, e.g. benzophenones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • 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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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]
    • 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
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/312—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 parameters being the characterizing feature
    • 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
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation
    • 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
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502—Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents

Definitions

  • the present invention relates to a non-solvent type pressure-sensitive adhesive composition, an adhesive film, and a method for producing the same.
  • Optically transparent adhesive films are widely used in the display field because they have excellent workability and the advantage of being evenly adhered to the surface, and are also used for the windshields of automobiles.
  • the technical problem to be achieved by the present invention is to provide a solvent-free pressure-sensitive adhesive composition capable of implementing an adhesive layer having excellent durability and optical properties by increasing crosslinking density and gel fraction.
  • the technical problem to be achieved by the present invention is to provide an adhesive film including an adhesive layer having excellent durability and optical properties due to increased crosslinking density and gel fraction.
  • One embodiment of the present invention for achieving the above-described purpose provides a solvent-free pressure-sensitive adhesive composition comprising an acrylate-based prepolymer, an acrylate-based monomer, and a photoinitiator including two or more benzophenone-based functional groups.
  • One embodiment of the present invention provides an adhesive film including an adhesive layer including a photocured product of the non-solvent adhesive composition, wherein the adhesive layer has a gel fraction of 80 to 90% and a transmittance of the adhesive layer is 92.0 or higher.
  • One embodiment of the present invention provides a method for producing an adhesive film, comprising: a step of partially polymerizing an acrylate-based monomer mixture to obtain an acrylate-based prepolymer together with an unreacted acrylate-based monomer; and a step of mixing the acrylate-based prepolymer, the unreacted acrylate-based monomer, a urethane acrylate, and a photoinitiator including two or more benzophenone-based functional groups to produce a solvent-free pressure-sensitive adhesive composition; and a step of photocuring the solvent-free pressure-sensitive adhesive composition to produce an adhesive layer.
  • An adhesive film formed by photocuring the non-solvent adhesive composition according to one embodiment of the present invention can easily secure necessary durability while implementing excellent optical properties.
  • a and/or B means “A and B, or A or B.”
  • One embodiment of the present invention provides a solvent-free pressure-sensitive adhesive composition
  • a solvent-free pressure-sensitive adhesive composition comprising an acrylate-based prepolymer, an acrylate-based monomer, and a photoinitiator having two or more benzophenone-based functional groups.
  • the gel fraction is increased accordingly, thereby improving durability and oil resistance, and at the same time, an adhesive layer having excellent optical properties can be manufactured, and such an adhesive layer is useful for application to an adhesive film.
  • the above acrylate prepolymer can be manufactured by partially polymerizing an acrylate monomer, and can be additionally photocured by including a photocurable site.
  • the above acrylate monomer may be attributed to the unreacted acrylate monomer that did not participate in the production of the acrylate prepolymer.
  • the acrylate prepolymer is first synthesized by partially polymerizing the acrylate monomer, the unreacted acrylate monomer and the synthesized acrylate prepolymer can be obtained in a mixed state.
  • the solvent-free adhesive composition can be manufactured by including the result obtained in a mixed state of the unreacted acrylate monomer and the synthesized acrylate prepolymer. Accordingly, the acrylate monomer can be attributed to the unreacted acrylate monomer during the polymerization of the acrylate prepolymer.
  • the above acrylate monomer may include a mixture of at least one type.
  • the above acrylate monomer can be used without limitation as long as it is an acrylate monomer that can be used in an acrylic pressure-sensitive adhesive, and an appropriate mixed composition can be used considering the known properties, purpose of the adhesive, etc.
  • Examples of the above acrylate monomer may include 2-ethylhexyl acrylate (2-EHA), isooctyl acrylate (IOA), butyl acrylate (BA), isobornyl acrylate (IBOA), cyclohexyl acrylate (CHA), acrylamide (AAm), 2-hydroxyethyl acrylate (HEA), 4-hydroxybutyl acrylate (HBA), 2-hydroxyethyl methacrylate (HEMA), acrylic acid (AA), etc., but are not limited thereto, and may include at least one or more of these.
  • 2-EHA 2-ethylhexyl acrylate
  • IOA isooctyl acrylate
  • BA butyl acrylate
  • IBOA isoborn
  • the acrylate monomer may include at least one selected from the group consisting of soft monomers, hard monomers, functional monomers, and combinations thereof.
  • the above soft monomer may be an acrylic monomer having a glass transition temperature (Tg) of less than -50°C, and may be, for example, ethylhexyl acrylate (EHA), isooctyl acrylate (IOA), butyl acrylate (BA), and the like, but is not limited thereto, and may include one or more of these.
  • Tg glass transition temperature
  • EHA ethylhexyl acrylate
  • IOA isooctyl acrylate
  • BA butyl acrylate
  • the above hard monomer refers to an acrylic monomer having a glass transition temperature (Tg) that is relatively high compared to a soft monomer, from -10° C. to room temperature, and may be, for example, isobornyl (meth)acrylate (IBO(M)A), cyclohexyl (meth)acrylate (CH(M)A), acrylamide (Aam), etc., but is not limited thereto, and may include one or more of these.
  • Tg glass transition temperature
  • the above functional monomer means an acrylate monomer containing a functional functional group, such as an acrylate monomer containing a hydroxyl group or a carboxyl group, or a nitrogen-containing acrylate monomer, and may be, for example, hydroxyethyl acrylate (HEA), hydroxybutyl acrylate (HBA), hydroxyethyl acrylic acid (HEAA), hydroxyethyl methacrylic acid (HEMA), acrylic acid (AA), etc., but is not limited thereto, and may include one or more of these.
  • the photoinitiator containing two or more of the above benzophenone functional groups can initiate a polymerization reaction by generating radicals upon light irradiation. Since the photoinitiator containing two or more of the above benzophenone functional groups has two or more moieties capable of initiating a polymerization reaction by generating radicals upon light irradiation, a polymer structure can be formed densely through the polymerization reaction. Since the polymer structure is formed densely and the crosslinking density of the photocured product increases, the gel fraction increases, thereby improving durability and oil resistance, and at the same time, excellent optical properties can be implemented.
  • “functional group” may mean a common atomic group or bonding pattern of a group of organic compounds having common chemical properties.
  • photoirradiation means irradiation of electromagnetic waves capable of inducing a polymerization reaction by affecting a photoinitiator or a polymerizable compound
  • electromagnetic waves herein may be used to collectively refer to particle beams such as microwaves, infrared rays, ultraviolet rays, X-rays, and ⁇ -rays, as well as ⁇ -particle beams, proton beams, neutron beams, and electron beams.
  • the above-described solvent-free pressure-sensitive adhesive composition may contain the photoinitiator including two or more of the benzophenone-based functional groups in an amount of 0.01 to 5 parts by weight, specifically, 0.25 to 1 part by weight, relative to 100 parts by weight of the total of the acrylate-based prepolymer and the acrylate-based monomer.
  • the solvent-free pressure-sensitive adhesive composition may contain the photoinitiator including two or more of the benzophenone-based functional groups in an amount within the above-described numerical range, thereby improving the crosslinking density and gel fraction of the photocured product, while at the same time excellently implementing optical properties such as the transmittance, haze, and b* value in a colorimeter of the photocured product.
  • the above-mentioned non-solvent adhesive composition may further include urethane acrylate.
  • the urethane acrylate can improve the cohesion and adhesive properties of the photocured product together with the multifunctional crosslinking agent, and also make the molecular structure flexible.
  • the above urethane acrylate may contain 0.1 to 10 parts by weight, specifically, 0.5 to 3 parts by weight, based on 100 parts by weight of the total of the acrylate-based prepolymer and the acrylate-based monomer.
  • the solvent-free pressure-sensitive adhesive composition contains the urethane acrylate in the content within the above numerical range, thereby improving the cohesiveness and adhesive properties of the photocured product, thereby maintaining the adhesiveness appropriately by controlling the degree of curing while maintaining a flexible molecular structure.
  • the above polyfunctional crosslinking agent may be a polyfunctional acrylate, and may include, for example, but is not limited to, at least one selected from the group consisting of hexanediol diacrylate, trimethylolpropanetrioxyethyl diacrylate, alkylene glycol diacrylate, dialkylene glycol diacrylate, trialkylene glycol diacrylate, dicyclopentenyl diacrylate, dicyclopentenyloxyethyl diacrylate, neopentyl glycol diacrylate, dipentaerythritol hexa diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and combinations thereof.
  • the above multifunctional cross-linking agent may be included in an amount of 0.01 to 10 parts by weight, specifically, 0.1 to 3 parts by weight, relative to 100 parts by weight of the total of the acrylate-based prepolymer and the acrylate-based monomer.
  • the solvent-free adhesive composition may include the multifunctional cross-linking agent in an amount within the above numerical range to improve the cohesion of the photocured product, thereby suppressing bubble generation under high temperature conditions, and may contribute to securing durability by appropriately controlling the degree of curing of the photocured product to improve adhesive strength and peeling strength while suppressing delamination or lifting between layers.
  • the coupling agent can be a silane coupling agent, and can include at least one selected from the group consisting of ⁇ -glycidoxypropyltrimethoxy silane, ⁇ -glycidoxypropylmethyldiethoxy silane, ⁇ -glycidoxypropyltriethoxy silane, 3-mercaptopropyltrimethoxy silane, vinyltrimethoxy silane, vinyltriethoxy silane, ⁇ -methacryloxypropyltrimethoxy silane, ⁇ -methacryloxypropyltriethoxy silane, ⁇ -aminopropyltrimethoxy silane, ⁇ -aminopropyltriethoxy silane, 3-isocyanatepropyltriethoxy silane, ⁇ -acetoacetatepropyltrimethoxy silane, and combinations thereof.
  • the coupling agent may be included in an amount of 0.005 to 5 parts by weight, specifically, 0.1 to 3 parts by weight, relative to 100 parts by weight of the total of the acrylate-based prepolymer and the acrylate-based monomer.
  • the solvent-free pressure-sensitive adhesive composition may include the coupling agent in an amount within the above numerical range, thereby contributing to securing durability and reliability by appropriately securing adhesive strength while suppressing the occurrence of bubbles or peeling.
  • the above-described non-solvent adhesive composition comprises a photoinitiator including two or more of the above-described benzophenone functional groups as the first photoinitiator, and may further comprise a second photoinitiator different from the first photoinitiator.
  • the second photoinitiator can control the degree of polymerization of the photocured product.
  • benzoin benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylamino acetophenone, a,a-methoxy-a-hydroxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone, 4,4'-diethylaminobenzophenone, It may include at least one selected from the group consisting of 2-chlorobenzophenone, 2-methylanthraquino
  • the second photoinitiator may be included in an amount of 0.01 to 10 parts by weight, specifically 0.1 to 5 parts by weight, relative to 100 parts by weight of the total of the acrylate-based prepolymer and the acrylate-based monomer.
  • the solvent-free adhesive composition may include the second photoinitiator in an amount within the above numerical range, thereby controlling the degree of polymerization of the photocured product to a desired level.
  • One embodiment of the present invention provides an adhesive film including an adhesive layer including a photocured product of the non-solvent adhesive composition, wherein the adhesive layer has a gel fraction of 80 to 90% and a transmittance of the adhesive layer is 92.0 or higher.
  • the adhesive layer can be produced from the solvent-free adhesive composition.
  • the above adhesive film may include an adhesive layer having a low swelling index, a high crosslinking density, an increased gel fraction, excellent durability, and high permeability.
  • the above adhesive layer can simultaneously implement excellent optical properties along with excellent durability, and is therefore suitable for application to adhesive films for automobiles.
  • the above-mentioned automotive adhesive film has excellent durability, and can be advantageous in ensuring safety when, for example, the windshield of a car is broken, and can suppress diffuse reflection of light due to its excellent optical properties.
  • the adhesive film may have a haze of the adhesive layer of 0.7 or less and a b* value of less than 0.45 in a colorimeter of the adhesive layer.
  • haze means the degree of opacity caused by light scattered from the surface of a transparent sample.
  • b* value in a colorimeter means a value that compares the degree of blue and yellow on one axis when measuring the color of a product using equipment that measures color differences, meaning that a larger b* value means closer to yellow, and a smaller b* value means closer to blue.
  • the adhesive layer may further include a release film laminated on at least one surface.
  • the above release film may be one having at least one surface selected from the group consisting of a polyethylene terephthalate film, a polytetrafluoroethylene film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a vinyl chloride copolymer film, a polyurethane film, an ethylene-vinyl acetate film, an ethylene-propylene copolymer film, an ethylene-ethyl acrylate copolymer film, an ethylene-methyl acrylate copolymer film, and a polyimide film, which has undergone an appropriate release treatment.
  • release agent used in the above release treatment examples include alkyd-based, silicone-based, fluorine-based, unsaturated ester-based, polyolefin-based or wax-based release agents, and among these, it is preferable to use an alkyd-based, silicone-based or fluorine-based release agent in terms of heat resistance, but is not limited thereto.
  • the adhesive layer may be interposed between the first release film and the second release film.
  • the first release film may be a light release film having a peel strength of 2 gf/inch or more and 2.5 gf/inch or less after attaching the TESA7475 tape at room temperature for 30 minutes
  • the second release film may be a heavy release film having a peel strength of 7 gf/inch or more and 7.5 gf/inch or less after attaching the TESA7475 tape at room temperature for 30 minutes.
  • One embodiment of the present invention provides a method for producing an adhesive film, comprising: a step of partially polymerizing an acrylate monomer mixture to obtain an acrylate prepolymer together with an unreacted acrylate monomer; and a step of mixing the acrylate prepolymer, the unreacted acrylate monomer, a urethane acrylate, and a photoinitiator including two or more benzophenone functional groups to produce a solvent-free pressure-sensitive adhesive composition; and a step of photocuring the solvent-free pressure-sensitive adhesive composition to produce an adhesive layer.
  • the above-described adhesive film can be manufactured according to the manufacturing method of the above-described adhesive film.
  • a detailed description of the acrylate-based prepolymer, the unreacted acrylate-based monomer, the urethane acrylate, and the photoinitiator including two or more benzophenone-based functional groups is as described above.
  • the acrylate-based prepolymer is partially polymerized, and can be obtained as a paste formulation having a viscosity of 1,500 to 5,500 cps, specifically, 2,000 to 4,500 cps, at 25°C by mixing with the unreacted acrylate-based monomer.
  • the viscosity can be controlled depending on the degree of partial polymerization of the acrylate-based prepolymer, and by controlling the viscosity within the above range and partially polymerizing the acrylate-based prepolymer, the gel fraction of the adhesive layer formed using the same is increased, thereby increasing the crosslinking density, and thereby implementing excellent durability and oil resistance, and at the same time implementing excellent optical properties.
  • the photoinitiator containing two or more benzophenone-based functional groups is referred to as a first photoinitiator, and the first photoinitiator, urethane acrylate, a multifunctional crosslinking agent, a coupling agent, and a second photoinitiator are further mixed into a mixture of the acrylate-based prepolymer and the unreacted acrylate-based monomer to manufacture the solvent-free adhesive composition.
  • the first photoinitiator and the second photoinitiator are as described above.
  • the paste-like mixture of the acrylate prepolymer obtained by partial polymerization and the unreacted acrylate monomer can be further mixed with a diluted monomer, etc., to prepare the solvent-free adhesive composition so as to be suitable for subsequent photocuring.
  • the solvent-free adhesive composition can be prepared with a viscosity of 1,500 to 2,500 cps at 25° C. By setting the viscosity of the solvent-free adhesive composition within the above numerical range, the solvent-free adhesive composition can be uniformly dispersed and coated on a release film, and workability can be improved.
  • the above diluted monomer can be any known substance without limitation as long as it does not impair the desired properties, and for example, an acrylate monomer can be used.
  • the solvent-free adhesive composition can be photocured by irradiation with an active energy ray.
  • photocuring by photopolymerization can additionally proceed.
  • active energy rays is a general term for particle beams such as microwaves, infrared rays, ultraviolet rays, X-rays, and ⁇ -rays, as well as ⁇ -particle beams, proton beams, neutron beams, and electron beams.
  • a method for manufacturing an adhesive film may further include a step of coating the solvent-free adhesive composition on a release film, and a step of irradiating light onto an upper portion of the release film to photo-cure the solvent-free adhesive composition to form an adhesive layer.
  • the step of coating the above-mentioned non-solvent adhesive composition on a release film can be performed by applying the composition to the release film using a conventional means such as a bar coater, and photocuring the release film by irradiating light on the upper portion of the release film to produce an adhesive layer.
  • a conventional means such as a bar coater
  • the adhesive layer formed by the method for manufacturing the above adhesive film may have a gel fraction of 80 to 90%, a transmittance of 92.0 or more, a haze of 0.7 or less, and a b* value of less than 0.45 in a colorimeter.
  • the adhesive layer is formed transparently and has excellent optical properties such as transmittance, haze, and a b* value in a colorimeter, and has a high gel fraction, so that it is also excellent in durability.
  • a solution was prepared by dissolving 253 g of HDI Trimer (hexamethylene-1,6-diisocyanate) in 100 g of Butyl acetate, placed into a 2 L reactor, and stirred at room temperature. Next, a solution of 307 g of BPOH (4-hydroxybenzophenone) and 940 g of Butyl acetate was dropped into the 2 L reactor while being careful not to generate heat. Then, the temperature was increased to 100°C, stirred for 20 hours, and then cooled to room temperature.
  • HDI Trimer hexamethylene-1,6-diisocyanate
  • Manufacturing Example 1 Manufacturing of a paste-like mixture (A) of an acrylate prepolymer and an unreacted acrylate monomer
  • a paste-like mixture (A) of an acrylate prepolymer having a viscosity of 5,200 cps (at 25°C) and unreacted acrylate monomer was 2,320,000.
  • Manufacturing Example 2 Manufacturing of a paste-like mixture (B) of an acrylate prepolymer and an unreacted acrylate monomer
  • Manufacturing Example 3 Manufacturing of a paste-like mixture (C) of an acrylate prepolymer and an unreacted acrylate monomer
  • a paste mixture (A) of the acrylate prepolymer and unreacted acrylate monomer prepared in Manufacturing Example 1 0.2 parts by weight of hexanediol diacrylate (HDDA) as a curing agent, 0.2 parts by weight of a coupling agent (KBM 403, Shin-Etsu (manufactured)), 1.0 parts by weight of urethane acrylate, 0.3 parts by weight of a second photoinitiator (Irgacure 651, Ciba Specialty Chemicals (manufactured)) and 0.75 parts by weight of a first photoinitiator (Omnipol 2702) were mixed to prepare a solvent-free adhesive composition, from which a coating liquid having a viscosity of 2000 cps (at 25°C) was prepared.
  • HDDA hexanediol diacrylate
  • the manufactured coating solution was coated on a polyethylene terephthalate film (XD500P, Toray Advanced Materials, thickness: 75 ⁇ m) that had been subjected to release treatment using a bar coater so that the thickness after UV curing became 125 ⁇ m. After that, the film was cured by irradiating it with ultraviolet rays using a UV lamp for 5 minutes, thereby manufacturing an adhesive film.
  • XD500P polyethylene terephthalate film
  • An adhesive film was manufactured under the same conditions and method as in Example 1, except that a paste-like mixture (B) of the acrylate prepolymer manufactured in Manufacturing Example 2 and the unreacted acrylate monomer was used.
  • An adhesive film was manufactured under the same conditions and method as in Example 1, except that a paste-like mixture (C) of the acrylate prepolymer manufactured in Manufacturing Example 3 and the unreacted acrylate monomer was used.
  • An adhesive film was manufactured under the same conditions and method as Example 1, except that 0.5 part by weight of a photoinitiator having a structure represented by Chemical Formula 1 manufactured in Synthesis Example 1 was used as the first photoinitiator.
  • An adhesive film was manufactured under the same conditions and method as Example 1, except that 0.5 weight part of a photoinitiator having a structure represented by Chemical Formula 1 manufactured in Synthesis Example 1 was used as a first photoinitiator, and a paste-like mixture (B) of an acrylate-based prepolymer manufactured in Manufacturing Example 2 and an unreacted acrylate-based monomer was used.
  • An adhesive film was manufactured under the same conditions and method as Example 1, except that 0.5 weight part of a photoinitiator having a structure represented by Chemical Formula 1 manufactured in Synthesis Example 1 was used as a first photoinitiator, and a paste-like mixture (C) of an acrylate-based prepolymer manufactured in Manufacturing Example 3 and an unreacted acrylate-based monomer was used.
  • An adhesive film was manufactured under the same conditions and method as in Example 1, except that the first photoinitiator was not used in Example 1.
  • An adhesive film was manufactured under the same conditions and method as in Example 1, except that a paste-like mixture (B) of the acrylate prepolymer manufactured in Example 2 and the unreacted acrylate monomer was used and the first photoinitiator was not used .
  • An adhesive film was manufactured under the same conditions and method as in Example 1, except that a paste-like mixture (C) of the acrylate prepolymer manufactured in Example 3 and the unreacted acrylate monomer was used and the first photoinitiator was not used.
  • the adhesive films manufactured in the examples and comparative examples were cut to a size of 1 in ⁇ 1 in ⁇ 125 ⁇ m (width ⁇ length ⁇ thickness), the release film was peeled off, and one side of the adhesive film was attached to a polyethylene terephthalate (XG7PH8, 75 ⁇ m) film having a urethane side formed thereon, and the opposite side of the adhesive film was attached to the SUS side.
  • the attachment of the adhesive film was performed by reciprocating a 5 kg roller 5 times based on ASTM D1002. Thereafter, the film was maintained at a temperature of 90 ° C. for 30 minutes, and then the shear strength was measured at a crosshead speed of 1 mm/min under high temperature conditions using a UTM (Universal Testing Machine, Zwick).
  • the adhesive films manufactured in the examples and comparative examples were cut to a size of 25 mm x 20 cm (width x height), the release film was peeled off, and a 2 kg roller was attached to stainless steel (SUS 304) by reciprocating 5 times. After 20 minutes, the peeling force was measured using a tensile tester under the conditions of a peeling speed of 300 mm/min and a peeling angle of 180°.
  • the adhesive layer of the adhesive film manufactured in the examples and comparative examples was cut to a size of 5 cm ⁇ 5 cm, placed in a polyethylene bottle, and the weight (a) was measured. Then, ethyl acetate was put into the polyethylene bottle so that the adhesive layer was sufficiently submerged, and left at room temperature for 24 hours. Next, the adhesive layer and ethyl acetate in the polyethylene bottle were poured and filtered through a wire mesh (weight: b) cut to a size of 14 cm ⁇ 14 cm. Thereafter, the wire mesh from which the adhesive layer was filtered was dried in an oven at 110° C. for 2 hours, and then the weight (c) was measured. Then, the measured weights a, b, and c were substituted into the following general formula 1 to measure the gel fraction (unit: %).
  • the release film of the adhesive film manufactured in the examples and comparative examples After peeling off the release film of the adhesive film manufactured in the examples and comparative examples, it was attached to a glass substrate having a thickness of 1.1 T using a 2 kg roller, and a glass substrate having a thickness of 0.55 T was laminated on the other side of the adhesive film to which the glass substrate was not attached, so that the glass substrate was attached to both sides of the adhesive film. Then, after leaving it in an autoclave at 40° C. and 4 bar conditions for 20 minutes, it was irradiated with 3 J of ultraviolet rays. Furthermore, the specimen after the ultraviolet irradiation was placed in an oven at a temperature of 85° C. and a relative humidity of 85 RH%, and the occurrence of white turbidity was visually confirmed after 3 days.
  • the performance of preventing white turbidity was evaluated as ⁇ if no white turbidity was generated, and X if white turbidity was generated.
  • the release film of the adhesive film manufactured in the examples and comparative examples After peeling off the release film of the adhesive film manufactured in the examples and comparative examples, it was attached to glass and then cut into a size of 1 in ⁇ 1 in (width ⁇ height) to manufacture a specimen. Thereafter, the specimen was immersed in artificial sebum (ESTASAN 3580, Koshr (manufactured)) for 10 minutes, and the penetration distance of the artificial sebum that penetrated through the side surface of the specimen, i.e., the adhesive interface between the adhesive layer and the glass, was measured using a vernier caliper.
  • artificial sebum ESASAN 3580, Koshr (manufactured)
  • the chemical resistance was evaluated according to the following criteria.
  • the manufactured adhesive layer was attached to a 1.1 T glass surface in the form of glass/adhesive layer/glass, and then the transmittance/haze was measured using NDH 5000 (Nippon Denshoku).
  • CM-3600A Konica Minolta
  • Example 1 Swelling index (Swelling index) High temperature Flyer too (Kgf/in 2 ) write Peeling power (gf/in) White turbidity Chemical resistance Haze Transmittance b* value
  • Example 1 84.8 8.77 3.0 1000 ⁇ ⁇ 0.52 92.46 0.40
  • Example 2 84.6 9.77 2.9 990 ⁇ ⁇ 0.38 92.57 0.39
  • Example 3 80.1 18.55 3.0 1250 ⁇ ⁇ 0.61 92.40 0.30
  • Example 4 88.5 8.56 3.2 1050 ⁇ ⁇ 0.54 92.40 0.42
  • Example 5 86.8 9.68 3.1 1000 ⁇ ⁇ 0.39 92.48 0.41
  • Example 6 81.2 18.92 3.1 1240 ⁇ ⁇ 0.62 92.42 0.31
  • Comparative Example 1 79.7 10.44 1.8 1060 ⁇ ⁇ 0.54 92.61 0.19
  • Comparative Example 2 78.9 11.65 2.2 1200 ⁇ ⁇ 0.45 92.86 0.18 Compar
  • the adhesive films manufactured in Examples 1 to 6 according to the present invention have a gel fraction of 80 to 90%, and thus, it can be confirmed that white turbidity does not occur and that chemical resistance is excellent. In addition, it can be confirmed that the haze and optical properties of the adhesive layer are excellent, so that there is no problem in using it as an optical adhesive film.

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  • 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

L'invention concerne : une composition adhésive sans solvant comprenant un prépolymère à base d'acrylate, un monomère à base d'acrylate et un photo-initiateur contenant au moins deux groupes fonctionnels à base de benzophénone ; un film adhésif ; et son procédé de production.
PCT/KR2024/011375 2023-08-22 2024-08-02 Composition adhésive sans solvant, film adhésif et son procédé de production Pending WO2025042084A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020230109620A KR20250029323A (ko) 2023-08-22 2023-08-22 무용제형 점착제 조성물, 점착필름 및 이의 제조 방법
KR10-2023-0109620 2023-08-22

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WO2025042084A1 true WO2025042084A1 (fr) 2025-02-27

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100210530B1 (ko) * 1991-02-28 1999-07-15 스프레이그 로버트 월터 아크릴을 주성분으로 하는 조성물을 제조하기 위한 다단계 조사 방법 및 이로써 제조된 조성물
KR20030080712A (ko) * 2002-04-10 2003-10-17 주식회사 큐시스 자외선 흡수제(ｕｖａ)가 도입된 반응형 우레탄아크릴레이트, 이의 제조방법 및 이를 함유한 광경화형수지조성물
US20180273782A1 (en) * 2015-09-28 2018-09-27 MGI Digital Technology Varnish composition with low levels of migration for inkjet-printed substrate
KR20190037936A (ko) * 2017-09-29 2019-04-08 주식회사 엘지화학 점착 조성물 및 점착 필름
KR20200129552A (ko) * 2019-05-09 2020-11-18 주식회사 테이팩스 광 경화형 광학용 점착제 조성물, 상기 조성물로부터 제조된 점착제, 및 상기 점착제의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100210530B1 (ko) * 1991-02-28 1999-07-15 스프레이그 로버트 월터 아크릴을 주성분으로 하는 조성물을 제조하기 위한 다단계 조사 방법 및 이로써 제조된 조성물
KR20030080712A (ko) * 2002-04-10 2003-10-17 주식회사 큐시스 자외선 흡수제(ｕｖａ)가 도입된 반응형 우레탄아크릴레이트, 이의 제조방법 및 이를 함유한 광경화형수지조성물
US20180273782A1 (en) * 2015-09-28 2018-09-27 MGI Digital Technology Varnish composition with low levels of migration for inkjet-printed substrate
KR20190037936A (ko) * 2017-09-29 2019-04-08 주식회사 엘지화학 점착 조성물 및 점착 필름
KR20200129552A (ko) * 2019-05-09 2020-11-18 주식회사 테이팩스 광 경화형 광학용 점착제 조성물, 상기 조성물로부터 제조된 점착제, 및 상기 점착제의 제조 방법

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