WO2020046061A1 - Composition adhésive et son procédé de préparation - Google Patents

Composition adhésive et son procédé de préparation Download PDF

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Publication number
WO2020046061A1
WO2020046061A1 PCT/KR2019/011183 KR2019011183W WO2020046061A1 WO 2020046061 A1 WO2020046061 A1 WO 2020046061A1 KR 2019011183 W KR2019011183 W KR 2019011183W WO 2020046061 A1 WO2020046061 A1 WO 2020046061A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
lysine
malic acid
pressure
sensitive adhesive
Prior art date
Application number
PCT/KR2019/011183
Other languages
English (en)
Korean (ko)
Inventor
황지호
양영렬
오창엽
이창석
나경수
문준옥
Original Assignee
씨제이제일제당(주)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020190104998A external-priority patent/KR102190917B1/ko
Application filed by 씨제이제일제당(주) filed Critical 씨제이제일제당(주)
Priority to AU2019332549A priority Critical patent/AU2019332549B2/en
Priority to EP19854737.4A priority patent/EP3816249B1/fr
Priority to US17/254,018 priority patent/US20210189196A1/en
Priority to BR112020026540-3A priority patent/BR112020026540A2/pt
Priority to CN201980040000.5A priority patent/CN112313300B/zh
Priority to RU2020141621A priority patent/RU2768711C1/ru
Publication of WO2020046061A1 publication Critical patent/WO2020046061A1/fr

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Classifications

    • 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
    • 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

Definitions

  • the present application relates to a novel adhesive composition, and a method for preparing the same.
  • Adhesives generally use petroleum-based monomers and oily solvents as raw materials.
  • Monomers made from petroleum-derived raw materials and pressure-sensitive adhesives formed therefrom have problems of reduced production due to petroleum resource limitation, environmental hormones generated during manufacturing, and toxicity at disposal.
  • organic solvents derived from petroleum are used in the manufacturing process in order to improve the adhesive strength in the conventional adhesive manufacturing, which impairs the health of workers and has environmental problems in terms of environmental protection.
  • most adhesives are difficult to decompose naturally because the monomer units are made of covalent bonds, and environmental pollution problems are also raised by polymers that are not decomposed. For this reason, techniques of various water-separable pressure-sensitive adhesives for effectively removing the pressure-sensitive adhesive from the adherend have been developed.
  • An aspect of the present application is to provide an adhesive composition.
  • Another aspect of the present application is to provide a method for preparing the pressure-sensitive adhesive composition.
  • An adhesive composition which comprises lysine, malic acid and water, wherein the lysine and malic acid are in the form of a salt solution and do not form precipitates in the aqueous solution.
  • the term "adhesion” refers to a phenomenon in which two objects (but not gas) are in proximity and then require some force (or work) to pull them out.
  • some materials having adhesion may become solid after a certain time after the substrate is applied, and may be accompanied by irreversible physical breakdown if the adhesive is to be separated from the substrate.
  • the "adhesion” may include "viscoelasticity” which requires some force for viscoelastic deformation when the adhesive material is separated from the substrate.
  • the adhesive composition having a viscoelastic property is stored and distributed through a general processing form before being applied to a substrate, and its adhesion can be maintained even after a certain time.
  • Examples of the adhesive article obtained by applying and drying such an adhesive composition on a substrate include a label and an oriented polypropylene (OPP) tape.
  • OPP oriented polypropylene
  • Viscosity originates from internal friction between molecules and refers to the nature of trying to hinder the flow of a substance. At this time, friction is a force to prevent a difference in the distribution of flow velocity. Adhesiveness and viscosity are separate properties, and even a composition having high viscosity may have little adhesiveness, and even a composition having low viscosity may have high adhesiveness.
  • insoluble salt AB is obtained by chemical changes of the lysine aqueous solution A (aq) and malic acid aqueous solution B (aq) as shown in Scheme 1, the lysine aqueous solution as shown in Scheme 2 Insoluble state due to precipitation of lysine solid A (s) or malic acid solid B (s) from A (aq) or malic acid solution B (aq) or lysine solid A (s) or malic acid solid B (s) insoluble in the solvent It can include any that remain.
  • precipitation may be precipitation generated before the substrate or the adhesive to be applied, during storage and distribution.
  • lysine is one of basic ⁇ -amino acids, and the lysine may be biosynthesized from oxal acetic acid through a lysine biosynthetic pathway or chemically synthesized.
  • Lysine may comprise one lysine or a mixture of one or more lysines.
  • the lysine may be at least one selected from L-lysine represented by Formula 1, D-lysine represented by Formula 2, and salts thereof.
  • the lysine salts include, for example, lysine sulfate, lysine acetate, lysine monohydrochloride, lysine dihydrochloride, lysine monohydrate, lysine acetylsalicylate, lysine phosphate, lysine diphosphate, mixtures or combinations thereof. .
  • Such lysine salts can be converted to lysine preforms.
  • lysine may be obtained as a fermentation broth.
  • the conversion of lysine salts to lysine preforms is known to those skilled in the art. It is also possible to use commercially available lysine raw materials.
  • the lysine may be D-lysine, L-lysine and / or DL-lysine, and since their physicochemical properties are the same or similar, the characteristics of the adhesive composition including them are also the same or similar, and thus, the present invention It can belong to the category of.
  • Malic acid is represented by the following general formula (3) as one of the organic acids.
  • Malic acid includes, for example, D-malic acid, L-malic acid, DL-malic acid, or a combination thereof.
  • Lysine and malic acid in the adhesive composition may be present in the form of a salt solution (salt solution). Specifically, even if lysine, malic acid and water are mixed, lysine and malic acid may be present in the form of aqueous salt solutions without forming covalent compounds or insoluble salts. Malic acid in the adhesive composition of the present application is not present in the form of an insoluble substance that is not dissolved in water.
  • the content of lysine, malic acid, and water may be controlled so that lysine and malic acid do not precipitate or crystallize.
  • the pressure-sensitive adhesive composition maintains a liquid state without forming crystals or precipitates, the pressure-sensitive adhesive is excellent in adhesion, and is easily applied to the substrate uniformly.
  • the mixed molar ratio of lysine and malic acid may be 1: 1.3 to 1: 3.
  • the mixed molar ratio of lysine and malic acid may be 1: 1.4 to 1: 2.5, 1: 2 to 1: 3, or 1: 1.5 to 1: 2.
  • precipitation in the composition may be formed, thereby lowering the adhesiveness or lowering the storage stability or storage stability of the adhesive composition.
  • the content of solids in the adhesive composition may be 70 parts by weight or less, for example, 0.1 to 70 parts by weight, 0.1 to 63 parts by weight, 1 to 63 parts by weight, or 10 to 63 parts by weight based on 100 parts by weight of the composition. .
  • the content of the solid content When the content of the solid content is within the above range, it is easy to apply the pressure-sensitive adhesive on the substrate, and when the content of the solid content is more than 70 parts by weight, precipitation may be formed, which may be difficult to use as the adhesive composition. Even if the content of the solid content decreases, the precipitate does not form or lose the cohesion in the composition. Therefore, the content of the solid content may be adjusted to a level of 0.1 to 10 parts by weight depending on the field of application.
  • the content range of the solid content is not formed.
  • the content of solids in the adhesive composition may be less than 64 parts by weight, for example, 0.1 to 63 parts by weight, 1 to 63 parts by weight, and 10 to 63 parts by weight. have.
  • the content of solids in the adhesive composition is 70 parts by weight or less, for example, 0.1 to 70 parts by weight, 1 to 70 parts by weight, or 10 To 70 parts by weight.
  • Malic acid and lysine may be included as active ingredients in the adhesive composition.
  • the sum of the malic acid and lysine content based on 100 parts by weight of the adhesive composition solid content may be 60 to 100 parts by weight, 70 to 99 parts by weight, 80 to 98 parts by weight, or 85 to 97 parts by weight.
  • the adhesive composition according to one embodiment may further include one organic acid selected from citric acid, itaconic acid, alpha ketoglutaric acid, and oxal acetic acid.
  • the content of the organic acid may be 0.1 to 10 parts by weight, for example 0.1 to 5 parts by weight based on 100 parts by weight of malic acid.
  • the adhesive force of the pressure-sensitive adhesive composition can be easily adjusted according to a desired use.
  • the malic acid and lysine of the present invention may be contained in the form of a condensate containing malic acid and lysine as a unit.
  • the condensate may be a dimer, trimer or oligomer, and the content of the condensate may be 20 parts by weight, 10 parts by weight or less, 1 part by weight or less based on 100 parts by weight of the sum of lysine and malic acid content. And may include zero.
  • the condensate is included in the above range, the adhesive strength of the pressure-sensitive adhesive composition may be reduced or the liquid state may not be maintained.
  • Lysine has two amino groups and malic acid has two carbonyl groups.
  • the unshared electron pair of oxygen of the carbonyl group of malic acid and the hydrogen of the amino group of lysine can interact through an ionic hydrogen bond.
  • lysine and malic acid can be confirmed as raw materials. From this it can be seen that the lysine and malic acid in the pressure-sensitive adhesive composition is bonded through an ionic hydrogen bond, they are present in the form of a salt solution (salt solution). Lysine and malic acid in the pressure-sensitive adhesive composition of the present invention can exhibit excellent adhesion properties while maintaining a liquid state without being precipitated in crystalline form (solid state) or precipitate form at room temperature (25 °C).
  • the adhesive composition of the present invention has water separation property. Therefore, when the pressure-sensitive adhesive composition of the present invention is used as the pressure-sensitive adhesive, it is easily removed because it is dissociated by water during separation and removal from the substrate or the adhesive to which the pressure-sensitive adhesive is applied. Specifically, the pressure-sensitive adhesive applied to the substrate or the adherend may be dissociated within 12 hours, specifically within 6 hours, and more specifically within 2 hours through stirring or washing with water at room temperature (25 ° C.). .
  • the adhesive composition of the present invention is easily dissociated with water, and the dissociated components are also environmentally friendly because they are harmless to life and the environment.
  • the adhesive composition of the present invention may further include one or more alcohol solvents selected from the group consisting of primary alcohols, polyhydric alcohols, diols and triols. Adding a solvent to the pressure-sensitive adhesive composition can increase the drying speed of the pressure-sensitive adhesive composition and increase the processability.
  • the mixed weight ratio of the deionized water and the alcohol in the pressure-sensitive adhesive composition may be 1: 1 to 10: 0. More specifically, the mixed weight ratio of deionized water and alcohol in the adhesive composition may be 1: 1 to 10: 1, 1: 1 to 5: 1, or 1: 1 to 3: 2. As the content of alcohol in the pressure-sensitive adhesive composition increases, the drying is better, the coating property is improved, the peel strength may increase. However, when the content of the alcohol in the adhesive composition is 1.5 times or more than the deionized water, phase separation may occur in the adhesive composition.
  • the alcohol solvent may be monohydric alcohol, polyhydric alcohols, unsaturated aliphatic alcohols, alicyclic alcohols, or mixtures thereof.
  • the monohydric alcohol may be at least one selected from methanol, ethanol, propan-2-ol, butan-1-ol, pentan-1-ol and hexadecane-1-ol.
  • the polyhydric alcohols include ethane-1,2-diol, propane-1,2-diol, propane-1,2,3-triol ( propane-1,2,3-triol, butane-1,3-diol, butane-1,2,3,4-tetraol butane-1,2,3,4 -tetraol), pentane-1,2,3,4,5-pentol (pentane-1,2,3,4,5-pentol), hexane-1,2,3,4,5,6-hexole (hexane -1,2,3,4,5,6-hexol), heptane-1,2,3,4,5,6,7-heptol (heptane-1,2,3,4,5,6,7- heptol).
  • Unsaturated aliphatic alcohols include, for example, Pro-2-ene-1-ol, 3,7-dimethylocta-2,6-diene-1-ol (3,7-Dimethylocta -2,6-dien-1-ol), pro-2-yn-1-ol (Prop-2-yn-1-ol) may be one or more selected.
  • the alicyclic alcohol is, for example, cyclohexane-1,2,3,4,5,6-hexol (cyclohexane-1,2,3,4,5,6-hexol), 2- (2-propyl)- 5-methylcyclohexane-1-ol (2- (2-propyl) -5-methyl-cyclohexane-1-ol) may be one or more selected from.
  • the pH of the pressure-sensitive adhesive composition is 2 to 11, specifically 2 to 9.5, more specifically 2 to 8.5.
  • the pressure-sensitive adhesive composition having a pH range is excellent in storage stability and storage stability, and even if stored for a long time, there may be no change in formulation or quality.
  • the pressure-sensitive adhesive composition is excellent in tackiness and does not form a precipitate even when used after being stored for a long time, as well as when used immediately.
  • the adhesive composition may be one in which no precipitation is formed after storage or distribution for 14 days or more.
  • 14 days or more for example, 12 months or more, even if stored, the composition is stable and the physical properties can be maintained as it is.
  • the temperature of the environment in which the adhesive composition is stored may be -18 °C to less than 80 °C, specifically -18 °C to 45 °C, 0 °C to 60 °C, or 20 °C to 40 °C. Even if stored in a low temperature or high temperature environment, if the temperature of the environment in which the pressure-sensitive adhesive composition is used at room temperature may have no effect on the formulation and quality. For example, when stored at low temperature, it can be used after leaving it to room temperature for a predetermined time before use.
  • a method of preparing the above-mentioned pressure-sensitive adhesive composition comprising mixing lysine, malic acid and water and stirring it below 80 ° C.
  • the stirring at below 80 ° C. may be performed at, for example, 0 ° C. or higher and less than 80 ° C. More specifically, the step may be carried out at 0 °C to 75 °C, 0 °C to 70 °C, 0 °C to 65 °C, or 0 °C to 60 °C.
  • the step of stirring below 80 ° C is, for example, i) 0 ° C. or higher but less than 80 ° C., 0 ° C. to 75 ° C., 0 ° C. to 70 ° C., or 0 ° C. to 60 ° C., and mixing step 1 and ii) room temperature It may include a second step of cooling to (20 to 30 °C).
  • the pressure-sensitive adhesive composition may further include the step of removing the water and the solvent by concentration under reduced pressure to control the solid content in a predetermined range.
  • an adhesive product comprising the above-mentioned adhesive composition on the substrate.
  • the adhesive product is a substrate; And a pressure-sensitive adhesive layer obtained by applying and drying the pressure-sensitive adhesive composition described above on the substrate. Through the drying, the solvent in the composition can be removed. Drying can be performed at 25 degreeC-45 degreeC.
  • the substrate can be used as long as the adherend to which the adhesive composition can be applied in the art.
  • the substrate may be, for example, glass, stainless steel (SUS), a polymer film, or the like.
  • the polymer membrane is mainly used for example polyolefin-based film or polyvinyl chloride film such as polyethylene, polypropylene, ethylene / propylene copolymer, polybutene-1, ethylene / vinyl acetate copolymer, a mixture of polyethylene / styrene butadiene rubber Can be.
  • plastics such as polyethylene terephthalate, polycarbonate, poly (methyl methacrylate), thermoplastic elastomers such as polyurethane, polyamide-polyol copolymer, and mixtures thereof can be used.
  • Unevenness may be formed on the surface of the substrate to increase adhesion between the substrate and the adhesive composition.
  • the surface of the substrate may be hydrophilic. Using the hydrophilic substrate as described above, the coating composition of the pressure-sensitive adhesive composition can be more uniformly performed on the substrate having hydrophilicity, and thus the film formation property is excellent.
  • Bonding the adhesive composition to the first substrate by applying the adhesive composition to the first substrate according to another aspect of the present invention; And attaching the first substrate and the second substrate to each other by contacting the first substrate, to which the composition is bonded, with the second substrate, to provide a method for attaching the first substrate and the second substrate.
  • the first substrate and the second substrate may be independently selected from one or more selected from glass, stainless steel, polymer film, metal, plastic, paper, fiber, and soil, but is not limited thereto. .
  • the first substrate and the second substrate may be the same material, for example.
  • the adhesive composition or adhesive product according to one embodiment may be used as an adhesive tape, a label sheet, a spray adhesive, a dust remover, etc. as a water-separable adhesive, and may be easily removed without damaging the adherend by using water. Packaging materials can be easily recycled. And when the composition is applied to the pesticides and seeds field, it can be easily removed with water after using the pressure-sensitive adhesive-containing composition can be used in a wider range of applications.
  • the water-separable pressure-sensitive adhesive of the present specification as compared to the conventional organic solvent-type pressure-sensitive adhesives, as well as cost reduction and easy handling, workability is improved and the working environment can be cleaned.
  • the adhesive composition according to the present application may select a bio-derived monomer as a starting material to be used in the manufacture, and may be a monomer that can be utilized in vivo. Environmental pollution by an oligomer can be prevented beforehand. Structures such as an adhesive tape, a sheet for labels, and the like, wherein the composition of the present application is formed using a water-separable pressure-sensitive adhesive, have improved mechanical strength such as tensile shear strength and peel force.
  • the pressure-sensitive adhesive composition or adhesive material of the present application if necessary, reactive diluents, emulsifiers, tackifiers, plasticizers, fillers, antioxidants, curing accelerators, flame retardants, flocculants, surfactants, thickeners, Sunscreens, elastomers, pigments, dyes, fragrances, antistatic agents, antiblocking agents, slip agents, inorganic fillers, kneading agents, stabilizers, modifying resins, coupling agents, leveling agents, fluorescent brighteners, dispersants, thermal stabilizers, light stabilizers, ultraviolet rays It may comprise one or more additives selected from the group consisting of absorbents, waxes, wetting agents, antioxidants, preservatives and lubricants. The total content of such additives is not particularly limited and may include various additives in various weight ranges depending on the intended use. The content of each of the additives listed above may be used at levels conventionally used in the art.
  • the reactive diluent is a diluent which helps each component of the composition to be evenly applied to the object to which the composition is applied.
  • n-butylglycidyl ether aliphatic glycidyl ether, 2-ethylhexyl glycidyl Ether, phenylglycidyl ether, o-cresylglycidyl ether, nonylphenylglycidyl ether, p-tertbutylphenyl glycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, neopentylglycidyl ether, 1.4-cyclohexanedimethylol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether,
  • the emulsifying agent may be, for example, at least one selected from the group consisting of copolymers of polyoxyethylene and polyoxypropylene, copolymers of polyoxyethylene and polyoctylphenyl ether, and sodium dodecylbenzene sulfide.
  • the tackifiers are for example rosin and its modified products (eg rosin, hydrogenated rosin, polymerized rosin, maleated rosin, rosin glycerin, rosin modified phenolic resin, etc.), terpene-based resins ( Terpene-based resins (e.g. terpene resin, terpene-phenol resin, terpene-styrene resin, terpene-phenolic resin), Petroleum resin (e.g.
  • resin emulsions e.g. rosin emulsions, TPR water based resins, 2402 resin emulsions, petroleum resin emulsions
  • coumaroneindene resins coumaroneindene resins.
  • the plasticizer may be contained in the composition to serve to improve processing flow or drawing. And the plasticizer can improve the functions of the electrical insulation, adhesion, cold resistance, light resistance, oil resistance, non-leak resistance, flame retardant flame resistance, thermal stability, biprocessing (molecular activity), activity (intermolecular activity), nontoxicity of the composition.
  • Plasticizers for improving functions such as cold resistance may be dioctyl adipate (DOA), dioctyl azelate (DOZ), dioctyl sebacate (DOS), Flexol TOF (UCC), polyethylene glycol esters, and the like.
  • the plasticizer for improving the heat resistance (non-volatile) and non-performance can be a polymer blend such as polyester, NBR (nitrile butadiene rubber), trimellitic acid ester, pentaerythritol ester and the like.
  • Plasticizers for improving light resistance properties may be DOP, DOA, DOS, polyester, epoxidized soybean oil (ESBO) and the like.
  • the plasticizer for oil resistance improvement may be phosphplex aromatic phosphate ester (trade name: TPP, TCP, 112 (CDP), 179A (TXP)), polyester-based, NBR, etc., and plasticizers for soap resistance are TCP, ESBO. , Polyester-based, and the like.
  • the plasticizer for flame retardant flame retardant may be phosphate such as TCP, TXP, paraffin chloride, alkyl stearate, NBR, or the like, and the plasticizer for thermal stability may be ESBO, DOZ, DOS, DOP, polyethylene glycol ester, or the like.
  • Plasticizers for processability include DOA. BBP, TOF, TCP, octyldiphenyl phosphate and the like, the plasticizer for the activity may be DOZ, DOS, dibasic lead phosphate (DLP), ESBO, polyethylene glycol ester and the like.
  • Plasticizers for non-toxicity may be BPBG, octyldiphenylphosphate, ESBO, citric acid esters, NBR and the like.
  • the plasticizer is specifically dibutyl phthalate (DBP), dihexyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate (DnOP), diisooctyl phthalate (DIOP), didecyl Phthalates (DDP), Diisodecylphthalate (DIDP), C8 ⁇ C10 mixed higher alcohol phthalates, Butylbenzylphthalate (BBP), Dioctyl adipate (DOA), Dioctyl azelate (DOZ), Dioctyl sebacate (DOS ), Tricresyl phosphate (TCP), trikisilenyl phosphate (TXP), monooctyl diphenyl phosphate (Santicizer 141), monobutyl- dikisylenyl phosphate, trioctyl phosphate (TOF), aromatic oils, polybro
  • Thickeners herein include, for example, alginine, alginic acid, sodium alginate, guar gum, xanthan gum, collagen, alginate ), Gelatin, furcellaran, agar, carrageenan, casein, locust bean gum, pectin, polyethylene oxide, polyethylene glycol, poly Vinyl alcohol, polyvinylpyrrolidone and the like can be used.
  • the surfactant may be used as long as it is commonly used in the art.
  • sodium dodecyl sulfate (SDS), sodium silicate (Na-silicate) and the like can be used.
  • the filler is added to improve the strength, durability, and workability of the composition, for example calcium carbonate, talc, ceramic, silica, dolomite, cray, titanium bag, zincation, carbon (anti-shrink, anti-blocking), potassium carbonate, Titanium oxide, liquid polysulfide polymer, volatile diluents, magnesium oxide, processing oil, and the like.
  • curing accelerators examples include dibutyltin dilaurate, JCS-50 (manufactured by Johoku Chemical Co., Ltd.), formate TK-1 (manufactured by Mitsui Chemical Co., Ltd.), and the like.
  • antioxidants are, for example, dibutylhydroxytoluene (BHT), Irganox (registered trademark) 1010, Irganox (registered trademark) 1035FF, Irganox (registered trademark) 565 (all, Chiba specialty chemicals) Product of the company.
  • the antistatic agent is not particularly limited, and specifically 1-hexyl-4-methylpyridinium hexafluorophosphate, dodecylpyridinium hexafluorophosphate, fluorinated organometallic compound (eg, 3M's HQ-115), alkali metal salt (Eg, NaPF 6 , NaSbF 6 , KPF 6 , KSbF 6, etc.), conductive polymers (eg, polythiophene (PEDOT from Bayer), polyaniline, polypyrrole, etc.), metal oxides (eg, indium doped tin oxide (ITO), Antimony-doped tin oxide (ATO), tin oxide, zinc oxide, antimony oxide, indium oxide, etc.), quaternary ammonium salts (e.g.
  • the elastomer refers to a polymer having rubber or elastomeric properties, for example, ethylene-vinyl acetate copolymer, acrylic rubber, natural rubber, isoprene rubber, styrenebutadiene rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, styrene-ethylene -Butylene-styrene copolymer, acrylonitrile-butadiene copolymer and the like can be used.
  • ethylene-vinyl acetate copolymer acrylic rubber, natural rubber, isoprene rubber, styrenebutadiene rubber, chloroprene rubber, butyl rubber, ethylene propylene rubber, styrene-ethylene -Butylene-styrene copolymer, acrylonitrile-butadiene copolymer and the like can be used.
  • the stabilizer serves to stabilize the adhesive strength of the composition, and examples thereof include polyhydric alcohol, polyvalent amine, and the like.
  • polyhydric alcohol polyvalent amine
  • the fluorescent brightener may be a benzooxazole compound, a benzothiazole compound, or a benzoimidazole compound.
  • the pigments may be natural or synthetic pigments, and these may be inorganic or organic pigments as another class. ,
  • the fragrance may be, for example, but not limited to, peppermint oil, spearmint oil, carbon or menthol, or the like.
  • the flame retardant may be melamine cyanurate, magnesium hydroxide, leadstone, zeolite, sodium silicate, aluminum hydroxide, antimony-based (antimony trioxide), or the like.
  • the water resistance improving additive may be glyoxal (glyoxal).
  • modified resins examples include polyol resins, phenol resins, acrylic resins, polyester resins, polyolefin resins, epoxy resins, epoxidized polybutadiene resins, and the like.
  • the coupling agent may improve adhesion and adhesion reliability between the adhesive composition and the packaging material.
  • the addition of such a coupling agent can improve adhesion reliability when the composition is left for a long time under high temperature and / or high humidity conditions.
  • the coupling agent include ⁇ -glycidoxypropyl triethoxy silane, ⁇ -glycidoxy propyl trimethoxy silane, ⁇ -glycidoxy propyl methyldiethoxy silane, ⁇ -glycidoxy propyl triethoxy silane , 3-mercaptopropyl trimethoxy silane, vinyltrimethoxysilane, vinyltriethoxy silane, ⁇ -methacryloxypropyl trimethoxy silane, ⁇ -methacryloxy propyl triethoxy silane, ⁇ -aminopropyl tri Methoxy silane, ⁇ -aminopropyl triethoxy silane, 3-isocyanato propyl triethoxy silane, ⁇ -
  • the kneading agent may be an aromatic hydrocarbon resin.
  • the anti-aging agent may be N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.
  • the humectant may be, for example, a mixture of saccharides, glycerin, sorbitol aqueous solution or amorphous sorbitol aqueous solution alone or mixed.
  • the ultraviolet absorber is ethylhexyl methoxycinnamate (eg 2-Ethylhexyl 4-methoxycinnamate), ethylhexyl salicylate, 4-methylbenzylidene camphor, isoamyl p-methoxycinnamate, octocrylene, phenyl Benzimidazolesulphonic acid, homosalate, synoxate, ethylhexyltrizone, polysilicone-15, tie-salicylate, popba (PABA), ethylhexyldimethylpava, glycerylpava and the like. These may be used alone or in combination of two or more.
  • ethylhexyl methoxycinnamate eg 2-Ethylhexyl 4-methoxycinnamate
  • ethylhexyl salicylate 4-methylbenzylidene camphor
  • the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application is, in addition to the above-mentioned additives, US Pat.
  • the additives disclosed in Japanese Patent Laid-Open No. 5959867 and Korean Patent No. 989942 are incorporated by reference in their entirety.
  • the adhesive composition or adhesive product according to one embodiment may be used to attach a label or the like to various packaging materials including metal, glass and plastic.
  • the packaging materials may for example be containers for food, drinks or household goods and these containers may be made of glass, metal or plastic.
  • the adhesive composition or adhesive product may be used for an adhesive, a coating agent, a carrier, a food additive, and the like according to its composition and properties.
  • the adhesive composition or adhesive product of the present application is used as an adhesive, for labeling, sealing, papering, cigarette paper, adhesive block toys, sand sculpture, food, bathroom / kitchen cleaner, animal ointment spray , Exfoliation, hair fixation, hair gel. It can be applied to soil stabilizers, water pools and intensifiers, corrugated cardboard, and zone adhesives. Soil stabilizer is used to remove fine dust such as yellow sand or dust generated in plant.
  • the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application may be used as a coating agent, it may be used for forest fire control, fruit vegetables, cut flower stem cut surfaces, and the like, and may be used for dyes, antifouling pretreatment coating agents and the like.
  • the antifouling pretreatment coating agent may be used in the process of coating the composition on a medium contaminated easily, and then simply washing with water when the composition is contaminated.
  • the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application is used as a carrier, it is applicable to forest protection, forest fire control, toilet fragrance, disinfectant, agricultural materials, household goods, toys and the like.
  • Forest protection may include, for example, forest protection such as pine tree nematodes
  • disinfectants may include, for example, bird flu disinfectants and foot and mouth disease disinfectants.
  • agricultural materials include fertilizers, taping, seed coating and the like.
  • the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application When the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application is applied to agricultural materials, it may be used for seed coating agents, plant taping agents, insecticide additives, fertilizer excipients, natural insecticides and the like. And when the composition of the present application is applied to household goods, it is added to the paint does not flow down to stick to paper or food coloring can be used in the manufacture of edible paints used by infants. As another example that the composition of the present application is applied to household goods, it may be used as a decontamination pretreatment agent, which will be described in more detail when the composition of the present application is sprayed on contaminated media such as insect screens, window frames, automobiles, etc. Decontamination can be quickly removed.
  • the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application When the pressure-sensitive adhesive composition or pressure-sensitive adhesive product of the present application performs a carrier function, it is possible to implement oxygen barrier properties, water barrier properties, oil resistance, and heat sealing functions, and when used in an eco-friendly food packaging coating layer, it prevents moisture from penetrating the outside. It has the effect of preventing and delaying food rot and oxidation.
  • the adhesive composition or the adhesive product of the present application when used as a food additive, it refers to a case where it is used for flour gluten substitute material, jelly, starch syrup, medicine, pigment, ice cream, anti-icing agent and the like.
  • the adhesive composition according to one embodiment has water-separable adhesion, coating and carrier functions.
  • the pressure-sensitive adhesive composition is used as a water-separable pressure-sensitive adhesive can be dissociated by water from the adherend or the substrate according to one embodiment can be easily removed from the adherend or the substrate. Therefore, such a pressure-sensitive adhesive is environmentally friendly as a water separation material.
  • compositions were prepared by mixing lysine, which is a basic amino acid, with various organic acids, the stability (precipitation formation) of each composition was evaluated.
  • the composition was prepared by varying only the type of organic acid. Except that each of the organic acids shown in Table 1 was used, the composition was prepared in the same manner as in Example 1.
  • each composition was applied to a thickness of about 50 ⁇ m using a bar coater on a 50 ⁇ m thick OPP film (Samyoung Chemical). After the film to which the composition was applied was left for 14 days at room temperature (25 ° C.) and a relative humidity of 60 ⁇ 10%, the surface change of the pressure-sensitive adhesive composition present on the OPP film was checked to evaluate the shape change.
  • Table 2 The evaluation results are shown in Table 2 below.
  • the composition containing lysine and malic acid did not form a precipitate, while the composition containing other organic acids and lysine could form a precipitate to evaluate the adhesion. That is, when the composition is prepared by mixing lysine and various organic acids, it was confirmed that not all compositions exhibit stickiness without forming a precipitate.
  • the solubility evaluation results of the pressure-sensitive adhesive composition according to the type of solvent and each solvent added are shown in Table 3 below.
  • the pressure-sensitive adhesive composition of the present application was dissolved when an alcohol such as methanol was used as a solvent, but was not dissolved in other organic solvents.
  • an adhesive composition containing lysine and malic acid was prepared.
  • the molar ratio of lysine and malic acid is 3: 1.
  • An adhesive composition was prepared at 2.5: 1, 2: 1, 1.5: 1, 1: 1, 1: 1.5, 1: 2, 1: 2.5 and 1: 3. (50 parts by weight of solid content)
  • the viscosity was measured using a rotary viscometer (manufacturer: LAMYRHEOLOGY) at 25 ⁇ 1 ° C., LV-1 form spindle, 60 rpm.
  • Initial adhesion was evaluated for the composition in which no precipitation was formed in the stability evaluation.
  • Initial adhesive force was used by Anton Paar's Rheometer measuring equipment, through which the initial adhesive strength of the adhesive composition was compared.
  • a probe made of SUS material having a diameter of 25 mm was brought into contact with the adhesive composition for 1 minute to maintain a gap of 0.01 mm. Quantitative assessments were made.
  • room temperature represents drying condition 1
  • oven represents drying condition 2.
  • Precipitation was formed when the molar ratio of lysine and malic acid was 1: 1, whereas no precipitation was formed when the molar ratio of lysine and malic acid was 1: 1.5.
  • the molar ratio of lysine and malic acid was subdivided into 1: 1, 1: 1.1, 1: 1.2, 1: 1.3, 1: 1.4, 1: 1.5 to prepare an adhesive composition (solid content). 50 parts by weight), the stability, viscosity and initial adhesive strength were evaluated in the same manner.
  • an adhesive composition containing lysine and malic acid was prepared.
  • the adhesive composition was prepared so that the solids content in the adhesive composition was 10% by weight, 20% by weight, 30% by weight, 40% by weight, 50% by weight, 60% by weight, 70% by weight, and 75% by weight, respectively.
  • Molar ratio of lysine and malic acid is 1: 1.5
  • the solid content was adjusted to the content of water.
  • the solids content in the composition may be 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, After further subdividing to 69 wt% and 70 wt% to prepare a pressure-sensitive adhesive composition, the molar ratio of lysine and malic acid was 1: 1.5), and stability, viscosity, and initial adhesion were evaluated in the same manner.
  • an adhesive composition containing lysine and malic acid was prepared.
  • lysine and malic acid were mixed so that the molar ratio of lysine and malic acid was 1: 2, 1: 3, and 2: 1, respectively.
  • the water content was adjusted so that the solids content in the composition was 10%, 20%, 30%, 40%, 50%, 60%, 70% by weight, respectively.
  • the stability of the composition was evaluated in the same manner as described in Example 1. The evaluation results are shown in Table 8.
  • the stability and adhesion of the pressure-sensitive adhesive composition of the present application is judged to have the largest influence according to the molar ratio of lysine and malic acid, and when the molar ratio of lysine and malic acid is the same, it was confirmed that the content of solids is affected.
  • Control 1 After preparing a commercially available polyvinyl alcohol based adhesive (PVA 088-50, Qingdao Sanhuan Colorchem CO., LTD), by adjusting the water content so that the solid content is 10% by weight, the adhesive composition (hereinafter, Control 1) was prepared.
  • the water separability of the pressure-sensitive adhesive composition (solid content of 10% by weight) of the present application and the control 1 was evaluated.
  • the method for evaluating the water separability is as follows: The pressure-sensitive adhesive composition of the present application was applied on the PET film with a thickness of 50-60 ⁇ m and then dried at 40 ° C. for 30 minutes. The dried resultant was cut to a size of 25 mm ⁇ 25 mm, attached to stainless steel (SUS304), and pressed by bonding 5 times at a pressure of 2 kgf using a hand roller to prepare a specimen.
  • PVA pressure-sensitive adhesive was applied on the PET film with a thickness of 50 ⁇ 60 ⁇ m, cut into 25mmX25mm size and attached to stainless steel (SUS304), and pressed by 5 times at a pressure of 2kgf using a hand roller to prepare a specimen. .
  • the specimens were completely immersed in distilled water (DIW) at room temperature, atmospheric pressure and pH neutral conditions, the specimens were checked after i) one hour or ii) 24 hours at 200 rpm using a stirrer. Thereafter, the time from the specimen until the adhesive composition or the adhesive was completely removed from the substrate was measured to evaluate the water separability of the specimen.
  • DIW distilled water
  • the pressure-sensitive adhesive composition according to the present application exhibited an equivalent level of initial adhesive force as compared to the polyvinyl alcohol-based pressure-sensitive adhesive composition (Control 1), and was separated in water in a short time.
  • the polyvinyl alcohol-based adhesive composition was dissolved in water after 24 hours after immersion in water, but only partially dissolved in water after 1 hour.
  • the pressure-sensitive adhesive composition according to the present invention is compared to the conventional pressure-sensitive adhesive strength or more than the equivalent level or water separation is very excellent, it is expected that it can be utilized in various fields.
  • an adhesive composition containing lysine and malic acid was prepared (6-1 to 6-3 below).
  • the pressure-sensitive adhesive composition was prepared by setting the molar ratio of lysine and malic acid to 1: 1, 1: 1.5, and 1: 2, respectively. (50 parts by weight of solid content)
  • the adhesive composition containing lysine and malic acid was produced (following 6-4 to 6-6).
  • the pressure-sensitive adhesive composition was prepared with a molar ratio of lysine and malic acid of 1.5: 1, 1: 1, and 1: 1.5, respectively, and a mixture of deionized water and methanol in a 1: 1 weight ratio was used as a solvent. (50 parts by weight of solid content)
  • control 2 a commercially available acrylic adhesive (K901, Hansung P & I) (hereinafter referred to as control 2) was prepared. (59 wt% of solids content) The water separability of each of the adhesive compositions was evaluated according to the following method, and the evaluation results are shown in Table 10 below.
  • the prepared pressure-sensitive adhesive composition, and the composition of the control 2 were each applied to a thickness of 50 ⁇ 60 ⁇ m on the PET film and then dried at 40 °C for 30 minutes.
  • the dried resultant was cut to a size of 25 mm ⁇ 25 mm, attached to stainless steel (SUS304), and pressed by bonding 5 times at a pressure of 2 kgf using a hand roller to prepare a specimen.
  • the specimens were completely immersed in distilled water (DIW) at room temperature, atmospheric pressure and pH neutral conditions, the specimens were checked after i) one hour or ii) 24 hours at 200 rpm using a stirrer.
  • DIW distilled water
  • Liquid maintenance 6-4 1 1 DIW and Methanol (1: 1 wt ratio) 47.0 - Sedimentation 6-5 1: 1.5 40.4 1.205
  • the adhesive product obtained using the adhesive composition according to the present application was separated from water within 1 hour after being immersed in water.
  • the initial adhesion is further improved.
  • the pressure-sensitive adhesive composition according to the present application was confirmed that the initial adhesive strength is comparable level, although the solid content is lower than that of the conventional acrylic pressure-sensitive adhesive (Control 2).
  • the acrylic adhesive did not dissolve in water even after 24 hours.
  • the composition in the adhesive composition was analyzed according to the reaction time.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

La présente invention peut fournir une composition adhésive contenant de la lysine, de l'acide malique et de l'eau, la lysine et l'acide malique se présentant sous la forme d'une solution saline et ne formant pas de précipités en solution.
PCT/KR2019/011183 2018-08-31 2019-08-30 Composition adhésive et son procédé de préparation WO2020046061A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU2019332549A AU2019332549B2 (en) 2018-08-31 2019-08-30 Adhesive composition and preparation method therefor
EP19854737.4A EP3816249B1 (fr) 2018-08-31 2019-08-30 Composition adhésive et son procédé de préparation
US17/254,018 US20210189196A1 (en) 2018-08-31 2019-08-30 Adhesive composition and preparation method therefor
BR112020026540-3A BR112020026540A2 (pt) 2018-08-31 2019-08-30 Composição adesiva, método para preparar uma composição adesiva e produto adesivo
CN201980040000.5A CN112313300B (zh) 2018-08-31 2019-08-30 粘着组成物及其制备方法以及包括其的粘着产品
RU2020141621A RU2768711C1 (ru) 2018-08-31 2019-08-30 Клеевой состав и способ его получения

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KR10-2018-0104015 2018-08-31
KR20180104015 2018-08-31
KR1020190104998A KR102190917B1 (ko) 2018-08-31 2019-08-27 점착 조성물, 및 이의 제조방법
KR10-2019-0104998 2019-08-27

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US4959412A (en) 1989-02-27 1990-09-25 Arizona Chemical Company High shear tackifier resins
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JP2002138161A (ja) * 2000-11-02 2002-05-14 Chisso Corp 組成物、および樹脂組成物
US6777465B2 (en) 2001-06-11 2004-08-17 Michael L. Haile Tackifier composition
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JP2005021454A (ja) * 2003-07-03 2005-01-27 Hiroshi Nishida 高分子ミセルを有効成分とする組織接着剤
US7306844B2 (en) 2004-03-10 2007-12-11 Avery Dennison Corporation Labels and labeling process
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WO2007120653A1 (fr) 2006-04-14 2007-10-25 National Starch And Chemical Investment Holding Corporation Adhésif aqueux contenant un biopolymère, destiné à des applications d'étiquetage
KR20090083484A (ko) * 2006-11-30 2009-08-03 가부시끼가이샤 비엠지 자기 분해성을 갖는 분체­액체 및 분체­분체의 2 반응제형 의료용 접착제
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KR20160095132A (ko) 2013-12-09 2016-08-10 헨켈 아게 운트 코. 카게아아 수성 접착제 조성물

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