WO2020046060A1 - Composition adhésive et son procédé de préparation - Google Patents

Composition adhésive et son procédé de préparation Download PDF

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Publication number
WO2020046060A1
WO2020046060A1 PCT/KR2019/011182 KR2019011182W WO2020046060A1 WO 2020046060 A1 WO2020046060 A1 WO 2020046060A1 KR 2019011182 W KR2019011182 W KR 2019011182W WO 2020046060 A1 WO2020046060 A1 WO 2020046060A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
lysine
pressure
sensitive adhesive
acid
Prior art date
Application number
PCT/KR2019/011182
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 KR1020190106134A external-priority patent/KR102190915B1/ko
Application filed by 씨제이제일제당(주) filed Critical 씨제이제일제당(주)
Priority to CN201980040599.2A priority Critical patent/CN112334557B/zh
Priority to EP19853503.1A priority patent/EP3816248A4/fr
Priority to RU2020142588A priority patent/RU2762134C1/ru
Priority to AU2019328988A priority patent/AU2019328988B2/en
Priority to BR112020026589-6A priority patent/BR112020026589A2/pt
Priority to US17/254,167 priority patent/US20210269683A1/en
Publication of WO2020046060A1 publication Critical patent/WO2020046060A1/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.
  • Lysine, alpha ketoglutaric acid and water wherein the lysine and alpha ketoglutaric acid are present in the form of a salt solution and do not form precipitates in the aqueous solution.
  • a composition is provided.
  • 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. In some cases, 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. In addition, 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 aqueous solution of lysine A (aq) and alpha ketoglutaric acid solution B (aq), as shown in Scheme 1 below, Scheme 2 Lysine solid A (s) or alpha ketoglutaric acid solid B (s) is precipitated from lysine aqueous solution A (aq) or alpha ketoglutaric acid aqueous solution B (aq) as described above, or lysine solid A (s) or alpha keto Glutaric acid solid B (s) may include all cases that are not dissolved in the solvent and remain in an insoluble state.
  • 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 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.
  • lysine may be obtained as a fermentation broth.
  • Alpha ketoglutaric acid is represented by the following general formula (3) as one of the organic acids.
  • Lysine and alpha ketoglutaric acid in the adhesive composition may be present in the form of a salt solution. Specifically, even if lysine, alpha ketoglutaric acid and water are mixed, lysine and alpha ketoglutaric acid may be present in the form of an aqueous salt solution without forming covalent compounds or insoluble salts. In the adhesive composition of the present application, alphaketoglutaric acid is not present in the form of an insoluble substance which is not dissolved in water.
  • the content of lysine, alpha ketoglutaric acid and water may be controlled so that lysine and alpha ketoglutaric acid do not precipitate or form crystals.
  • 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 alpha ketoglutaric acid may be 1.7: 1 to 1: 3.
  • the mixed molar ratio of lysine and alpha ketoglutaric acid may be 1.6: 1 to 1: 2, 1.5: 1 to 1: 2, 1.4: 1 to 1: 2, 1.3: 1 to 1: 1.5, or 1.2: 1 to 1: 1.5. If the content of lysine to alpha ketoglutaric acid is more or less than the above-mentioned range, precipitation in the composition may be formed, leading to deterioration in adhesiveness or deterioration in 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, 1 to 70 parts by weight, and 10 to 70 parts by weight based on 100 parts by weight of the composition.
  • 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.
  • Alphaketoglutaric acid and lysine may be included as active ingredients in the adhesive composition.
  • the sum of the alpha ketoglutaric acid and the lysine content based on 100 parts by weight of the adhesive composition 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, oxal acetic acid, and malic acid as a minor component.
  • 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 alpha ketoglutaric acid.
  • the adhesive force of the pressure-sensitive adhesive composition can be easily applied according to various applications.
  • the alpha ketoglutaric acid and lysine of the present invention may be contained in the form of a condensate containing alpha ketoglutaric 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 or less, 10 parts by weight or less, based on 100 parts by weight of the total content of lysine and alpha ketoglutaric acid, It may be 1 part by weight or less, and may include 0.
  • 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 alpha ketoglutaric acid has two carbonyl groups.
  • the non-covalent electron pair of oxygen of the carbonyl group of alpha ketoglutaric acid and the hydrogen of the amino group of lysine can interact through an ionic hydrogen bond.
  • lysine and alpha ketoglutaric acid can be identified as raw materials. From this, it can be seen that lysine and alpha ketoglutaric acid in the adhesive composition are bonded through an ionic hydrogen bond, and they exist in the form of a salt solution.
  • lysine and alpha ketoglutaric acid may exhibit excellent adhesion characteristics while maintaining a liquid state without precipitation in a crystalline form (solid state) or a 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.
  • alpha ketoglutaric acid may be added to the aqueous solution of lysine, or lysine, alpha ketoglutaric acid, and water may be mixed at the same time.
  • 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 40 °C, specifically -18 °C to 35 °C, 0 °C to 60 °C, or 20 °C to 35 °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 for preparing the above-mentioned pressure-sensitive adhesive composition comprising mixing lysine, alpha ketoglutaric acid and water and stirring it below 40 ° C.
  • the step of mixing the lysine, alpha ketoglutaric acid and water and stirring it at less than 40 °C is carried out outside the temperature range, side reaction substances, impurities, etc. may be formed, in some cases, the adhesive composition having the desired adhesiveness Can be difficult to obtain.
  • Stirring at less than 40 °C may be performed at less than 40 °C 0 for example. More specifically, the step may be carried out at 0 ° C or more and less than 40 ° C, 0 ° C to 30 ° C, or 0 ° C to 25 ° C.
  • the step of stirring below 40 ° C is i) the first step of mixing and stirring at 0 ° C or above 40 ° C, 0 ° C to 30 ° C, or 0 ° C to 25 ° C and ii) room temperature (20 to 30 ° C) It may include a second step of cooling to).
  • alpha ketoglutaric acid may be added to the aqueous solution of lysine, or lysine, alpha ketoglutaric acid, and water may be mixed at the same time.
  • 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 25-45 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 film is mainly a polyolefin film such as a mixture of polyethylene, polypropylene, ethylene / propylene copolymer, polybutene-1, ethylene / vinyl acetate copolymer, polyethylene / styrene butadiene rubber, or polyvinyl chloride film.
  • 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. r By using a hydrophilic substrate as described above, the coating composition of the pressure-sensitive adhesive composition can be more uniformly carried out on the substrate having hydrophilicity, so that the film forming 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.
  • SDS sodium dodecyl sulfate
  • Na-silicate sodium silicate
  • 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.
  • 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., 60 ⁇ 10% relative humidity), the surface change of the pressure-sensitive adhesive composition present on the OPP film was confirmed to evaluate the shape change. 2 is shown.
  • the composition containing lysine and alpha ketoglutaric acid did not form a precipitate, while the composition containing other organic acids and lysine could form a precipitate to evaluate the adhesiveness. 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.
  • an adhesive composition comprising lysine and alpha ketoglutaric acid was prepared.
  • Molar ratio of lysine and alpha ketoglutaric acid 1: 1, 50 parts by weight of solids content
  • To the prepared 50 g of the pressure-sensitive adhesive composition 25 g of the additional solvent of Table 3 were added and stirred for 1 hour. After stirring, the solubility in each solvent of the pressure-sensitive adhesive composition was confirmed.
  • 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 comprising lysine and alpha ketoglutaric acid was prepared.
  • the molar ratio of lysine and alpha ketoglutaric acid was 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)
  • Viscosity was measured using a rotary viscometer (manufacturer: LAMYRHEOLOGY) under conditions of 25 rpm, 1 ° C LV-1 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 contacted with the adhesive composition for 1 minute to maintain a 0.01 mm gap, and then the force generated by peeling the probe at the same speed was measured. Quantitative evaluation was performed.
  • room temperature indicates drying condition 1 and oven indicates drying condition 2.
  • the adhesive composition was prepared by subdividing the molar ratio of lysine and alpha ketoglutaric acid into 2.0: 1, 1.9: 1, 1.8: 1, 1.7: 1, 1.6: 1, 1.5: 1. Then (50 parts by weight of solid content), the stability, viscosity, and initial adhesion were evaluated in the same manner.
  • an adhesive composition comprising lysine and alpha ketoglutaric 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.
  • the molar ratio of lysine and alpha ketoglutaric acid is 1: 1.
  • the solid content was adjusted to the content of water.
  • the solids content in the composition may be 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%,
  • an adhesive composition (molar ratio of lysine and alpha ketoglutaric acid is 1: 1)
  • the same method was used to evaluate the stability, viscosity, and initial adhesion. It was. The evaluation results are shown in Table 7 below.
  • the content of the solid content in the adhesive composition was maintained from 65% to 70% by weight, but when the solid content in the adhesive composition is 71% by weight or more, it is confirmed that a precipitate is formed within 2 weeks.
  • a precipitate is formed within 2 weeks.
  • an adhesive composition comprising lysine and alpha ketoglutaric acid was prepared.
  • lysine and alpha ketoglutaric acid were mixed so that the molar ratio of lysine and alpha ketoglutaric 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 determined to have the greatest effect according to the molar ratio of lysine and alpha ketoglutaric acid. It was confirmed that it is large.
  • an adhesive composition comprising lysine and alpha ketoglutaric acid was prepared.
  • Control 1 After preparing a commercially available polyvinyl alcohol based adhesive (PVA 088-50, Qingdao Sanhuan Colorchem CO., LTD), by adjusting the content of water so that the solid content is 10% by weight of the adhesive composition (hereinafter, Control 1) was prepared.
  • the adhesive composition of the present application was applied to a thickness of 50 ⁇ 60 ⁇ m on the PET film and then dried for 30 minutes at 40 °C.
  • 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.
  • a pressure-sensitive adhesive composition containing lysine and alpha ketoglutaric acid was prepared (following 6-1 to 6-3).
  • an adhesive composition was prepared using a molar ratio of lysine and alpha ketoglutaric acid as 1.5: 1, 1: 1, and 1: 1.5, respectively. (50 parts by weight of solid content)
  • an adhesive composition containing lysine and alpha ketoglutaric acid was prepared (6-4 to 6-6 below).
  • the pressure-sensitive adhesive composition was prepared with a molar ratio of lysine and alpha ketoglutaric acid of 1.5: 1, 1: 1, and 1: 1.5, respectively. Used. (50 parts by weight of solid content)
  • control 2 a commercially available acrylic pressure-sensitive adhesive (K901, Hansung P & I) (hereinafter referred to as control 2) (solid content 59 wt%) was prepared. Peel strength and water separability of each of the adhesive compositions were evaluated according to the following methods, 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 into a size of 25 mm ⁇ 25 mm, attached to stainless steel (SUS304), and pressed and bonded five 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
  • 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.
  • HPLC high performance liquid chromatography

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

Abstract

La présente invention permet de fournir une composition adhésive, la composition adhésive comprenant de la lysine, de l'acide alpha-cétoglutarique et de l'eau, la lysine et l'acide alpha-cétoglutarique étant sous la forme d'une solution saline aqueuse et ne formant pas de précipités dans la solution aqueuse.
PCT/KR2019/011182 2018-08-31 2019-08-30 Composition adhésive et son procédé de préparation WO2020046060A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN201980040599.2A CN112334557B (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
EP19853503.1A EP3816248A4 (fr) 2018-08-31 2019-08-30 Composition adhésive et son procédé de préparation
RU2020142588A RU2762134C1 (ru) 2018-08-31 2019-08-30 Клеевая композиция и способ ее получения
AU2019328988A AU2019328988B2 (en) 2018-08-31 2019-08-30 Adhesive composition and preparation method thereof
BR112020026589-6A BR112020026589A2 (pt) 2018-08-31 2019-08-30 Composição adesiva, método para preparar uma composição adesiva, e produto adesivo
US17/254,167 US20210269683A1 (en) 2018-08-31 2019-08-30 Adhesive composition and preparation method thereof

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KR10-2018-0104016 2018-08-31
KR20180104016 2018-08-31
KR10-2019-0106134 2019-08-28
KR1020190106134A KR102190915B1 (ko) 2018-08-31 2019-08-28 점착 조성물, 및 이의 제조방법

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US4959412A (en) 1989-02-27 1990-09-25 Arizona Chemical Company High shear tackifier resins
US7939145B2 (en) 2000-01-10 2011-05-10 Process Resources Corporation Techniques for labeling of plastic, glass or metal containers or surfaces with polymeric labels
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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
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