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WO2018092943A1 - Résine de polyuréthane respectueuse de l'environnement, procédé de préparation correspondant et composition de revêtement la comprenant - Google Patents

Résine de polyuréthane respectueuse de l'environnement, procédé de préparation correspondant et composition de revêtement la comprenant Download PDF

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Publication number
WO2018092943A1
WO2018092943A1 PCT/KR2016/013295 KR2016013295W WO2018092943A1 WO 2018092943 A1 WO2018092943 A1 WO 2018092943A1 KR 2016013295 W KR2016013295 W KR 2016013295W WO 2018092943 A1 WO2018092943 A1 WO 2018092943A1
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meth
water
polyurethane resin
resin
acrylic acid
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English (en)
Korean (ko)
Inventor
권동주
김용재
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JOHNS MEDIA Co Ltd
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JOHNS MEDIA Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes

Definitions

  • the present invention relates to an environment-friendly polyurethane resin, a method for preparing the same and a coating composition comprising the same.
  • the electrostatic printing process creates an image on the photoconductive surface, in order to print the image on the surface of the substrate, and then combines the image using ink with charged particles on the surface, and the charged particles in the form of an image to the substrate surface.
  • the charged particles used in the form of a powder or a liquid form is usually used an ink called the name "toner".
  • a stable printing quality can be maintained only by expressing an excellent adhesion with an image formed by applying an electric field due to the characteristics of electrostatic printing.
  • a water-dispersible resin provided with a carboxyl functional group to the polyolefin resin is used as a coating material.
  • the ethylene acrylic acid dispersion of this concept is described using Michem® Prime 4990R.E, commercially available from Michelman.
  • polyethylene acrylic acid resin used to prepare the ethylene acrylic acid dispersion is a resin sold under the trademark Primaco® 5980I by Dow-Chemical, which can be prepared by dissolving it in an alkaline aqueous solution while maintaining a proper solid content and viscosity.
  • one of the essential physical properties to be provided as the base film is to maintain excellent adhesion to the olefin-based film (PET, PE, PP, PO film, etc.) mainly used as the base film.
  • PET olefin-based film
  • a water-dispersed polyurethane resin is used for imparting adhesion with the base film.
  • NeoResins for increased adhesion to the ethylene acrylic acid dispersion of this concept. From Incorez 217 or Scott Bader Company Ltd.
  • the solution can be solved by adding a water-dispersed polyurethane resin such as TD7037 or TD 7038 supplied from the company.
  • the water-dispersed polyurethane resin includes the same components in the water-dispersed urethane resin because of the use of highly volatile toxic substances such as DMF and NMP when synthesizing the urethane resin before water dispersion.
  • the coating composition containing the toxic substance is classified as a toxic substance with only a very small amount of contents, which threatens the safety of the worker in the production process.
  • the highly volatile toxic organic solvent is difficult to completely volatilize at a low temperature drying process of 130 ° C. or lower, and deteriorates the coating properties when remaining in the film and causes blocking when winding up, and also has difficult management guidelines in the distribution and manufacturing process. There is a problem that must be followed.
  • high calorie energy is required to dry all of the high boiling point organic solvents. Excessive energy use not only increases production costs, but also relatively low glass transition temperature films (PE, PP, and PO). Etc.).
  • the water-dispersed polyurethane also corresponds to a material that is water-dispersed using alkali salt neutralization such as ammonia or amine, and the carboxyl functional group polymerized by radical polymerization in the synthesis method.
  • alkali salt neutralization such as ammonia or amine
  • carboxyl functional group polymerized by radical polymerization in the synthesis method.
  • the water-dispersed polyurethane synthesized by the hydroxy-isocyanate addition reaction compared to the polyolefin resin imparted has a significantly low weight average molecular weight.
  • polyolefin-based resins to which carboxyl functional groups are given are not only able to be used at a level of 75% of the acid value contained in the resin when neutralizing alkali salts due to their high molecular weight, but also increase the amount of alkali salts to increase the neutralization rate. It tends to increase in viscosity in terms of water supply, so it is generally used in the state of partial neutralization only.
  • the inherent properties of the polyolefin-based resins imparted with the carboxyl functional groups described above are important characteristics to be considered when mixing with a water-dispersion resin using a relatively low molecular weight alkali salt, which is an aqueous dispersion using a low molecular weight alkali salt.
  • the alkali salts of the water-dispersed polyurethane resin toward the polyolefin-based resin endowed with a carboxyl functional group that is partially neutralized relative to the fully neutralized water-dispersed polyurethane resin It shows a characteristic of moving to achieve an equilibrium state, and as a result of this phenomenon, the water-dispersed polyurethane resin gradually loses alkali salts, which eventually breaks the dispersion stability of the water-dispersed polyurethane resin. Door to gel the entire dispersed phase There is a problem.
  • the inter-film blocking property is expressed, it causes serious defects not only in the film processing but also in the printing process, thereby losing the value as a product.
  • the polyolefin-based resin to which the carboxyl functional group is used to secure the print quality has a low glass transition temperature inherently, which makes it difficult to solve the blocking characteristics.
  • an object of the present invention is to provide an eco-friendly water-dispersible polyurethane resin and a method for producing the same, which are excellent in electrostatic printing properties and do not contain toxic substances.
  • an object of the present invention is to provide an eco-friendly coating composition and a coating film that can minimize the induction of blocking even without the toxic residual organic solvent in the coating film, including the eco-friendly water dispersion polyurethane resin.
  • an object of the present invention is to provide a coating composition and a coating film having a low storage stability and ensuring storage stability by utilizing a third water-dispersible resin as a buffer composition together with an eco-friendly water-dispersible polyurethane resin according to the present invention. do.
  • diisocyanate monomers having isocyanate functional groups at both ends; At least one polymerizable monomer selected from the group consisting of
  • the environment-friendly polyurethane resin according to the invention is characterized in that the compound represented by the following formula (3).
  • R 6 R 5 is to be represented by the formula (2), is an alkyl group having a carbon number of 3 to 20, n is an integer from 1 to 20;
  • X is an amine group having an alkyl group having 1 to 20 carbon atoms
  • R 1 , R 2 and R 4 are each independently an alkyl group having 6 to 20 carbon atoms
  • R 3 is an alkyl group having 2 to 20 carbon atoms
  • k is It is an integer of 1-20
  • l is an integer of 1-40
  • m is an integer of 1-20
  • n is an integer of 1-100.
  • Base film layer And a coating layer formed by applying and thermosetting the coating composition according to the invention on the top or both sides of the base film layer; It is characterized by being a laminated coating film.
  • the present invention (a) a dialcohol polyol monomer having a hydroxy functional group at both terminals; (b) a dialcohol monomer having a carboxyl functional group and a hydroxy functional group at both ends; And (c) diisocyanate monomers having isocyanate functional groups at both ends; It is an eco-friendly polyurethane resin composed of a main chain of at least one polymerizable monomer selected from the group consisting of:
  • the term 'coating' refers to forming a functional layer capable of imparting properties such as printability, substrate adhesion, and anti-blocking property to various substrate surfaces using resin, paper, nonwoven fabric, cloth, or composite materials. it means. In some cases, it may be used in the same sense as the protective layer.
  • a 2L glass reactor is prepared to be moisture free, and (a) a dialcohol polyol monomer having a hydroxy functional group at both ends and (c) a diisocyanate monomer having an isocyanate functional group at both ends is added with a monomer.
  • the total amount of the dimethyl carbonate solvent is designed to be about 300 g, and the reaction is carried out by stirring for about 30 minutes, and then (b) a dialcohol monomer having a carboxyl functional group and a hydroxy functional group at both terminals (for example, Dimethylol-propionic acid (DMPA) represented by the reaction is further reacted for 30 minutes while slowly adding a solution dissolved in a concentration of about 20% by weight in dimethyl carbonate (DMC) solvent.
  • DMPA Dimethylol-propionic acid
  • the molar ratio of (a) the dialcohol polyol monomer used for the reaction is 10 to 40 mol%, (b) the molar ratio of the dialcohol monomer having a carboxyl functional group and a hydroxyl functional group at both ends is 10 to 40 mol% and (c The molar ratio of diisocyanate is preferably 50 to 70 mol%.
  • the minimum molar ratio of the diisocyanate monomer must be 50 mol% or more, and when the molar ratio exceeds 70 mol%, the isocyanate functional group becomes excessive and unreacted diisocyanate monomer remains.
  • the molar ratio of diisocyanate may be 50 to 67 mol%.
  • the molar ratio of the dialcohol monomer having a carboxyl functional group and a hydroxy functional group at both ends is less than 10 mol%, it is difficult to disperse the polyurethane resin prepolymer, and when the molar ratio is more than 40 mol%, water resistance is deteriorated due to excessive acid value.
  • the dialcohol polyol monomer having a hydroxy functional group at both ends of (a) used in the reaction is, for example, 1,3-propanediol (1,3-PDO), 1,6-hexanediol (1,6- HDO), 1,5-pentanediol, 2-ethyl-1,6-hexanediol, 1,4-butanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-methyl-1 Aliphatic or 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,8-octanediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol , 4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol
  • 3-propanediol (1,3-PDO), 1,5-pentanediol, 1,6-hexanediol (1,6-HDO) 1,4-butanediol.
  • DMPA dimethylol-propionic acid
  • DEPA diethylol-propionic acid
  • DPPA di Propylol propionic acid
  • the (c) diisocyanate monomer used in the reaction is, for example, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and hydrogenated methylene diphenyl diisocyanate.
  • Aliphatic or cyclic isocyanate compounds such as HMDI, or aromatic isocyanates such as toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), and xylene diisocyanate (XDI).
  • HMDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • XDI xylene diisocyanate
  • Compounds can be used, but are not limited thereto. Among them, it is preferable to use non-yellowing isocyanate compounds such as HDI, IPDI, and HMDI from the viewpoint of weatherability.
  • R 1 , R 2 and R 4 are each independently an alkyl group having 6 to 20 carbon atoms
  • R 3 is an alkyl group having 2 to 20 carbon atoms
  • k is an integer of 1 to 20
  • l is 2 to 40 It is an integer of
  • m is an integer of 1-20
  • n is an integer of 1-100.
  • R ⁇ 1> , R ⁇ 2> and R ⁇ 4> are respectively independently C6-C15 alkyl groups.
  • R ⁇ 3> is a C2-C13 alkyl group.
  • k is an integer of 1-15
  • l is an integer of 2-20
  • m is an integer of 1-15
  • n is an integer of 1-60.
  • the non-toxic tertiary amine mixed with dimethyl carbonate (DMC) at 50% while maintaining the polyurethane resin prepolymer resin A represented by [Formula 1] at 40 was used in (b) both ends. Quantify as much as 95 mol% of the dialcohol monomer having a hydroxy functional group and a carboxyl functional group, and slowly ionize while stirring for 1 hour while slowly dropping.
  • DMC dimethyl carbonate
  • a water-dispersed polyurethane prepolymer resin B which may be represented by the following [Formula 2] in which the terminal group is terminated with an isocyanate functional group.
  • X is an amine group having an alkyl group having 1 to 20 carbon atoms
  • R 1 , R 2 and R 4 are each independently an alkyl group having 6 to 20 carbon atoms
  • R 3 is an alkyl group having 2 to 20 carbon atoms
  • k is It is an integer of 1-20
  • l is an integer of 2-40
  • m is an integer of 1-20
  • n is an integer of 1-100.
  • X may be an ethyl morpholine (n-ethylmorpholine), but this is only one example of a non-toxic tertiary amine, but is not necessarily limited thereto.
  • Tertiary amines that are not nontoxic accidental preparations used in the reaction are 2-amino-2methyl-1-propanol (2-amino-2-methyl-1-propanol, DMAMP-80), 2-dimethylamino 2-methyl-1-propanol (2-Dimethylamino-2-Methyl-1-Propanol, AMP-95), n-ethylmorpholine, dimethylaminopropanol, dimethylcyclohexylamine, Amines, such as dimethyl aza norbornene (2-methyl-2-azanorbornane), may be used, but are not necessarily limited thereto. Among them, the use of ethyl morpholine (n-ethylmorpholine) is preferable in terms of maintaining a stable aqueous phase.
  • ethyl morpholine n-ethylmorpholine
  • n-ethylmorpholine 10 to 50 mole percent of the hydroxy functional monomer at both ends thereof, including the carboxyl functional group and the dial alcohol monomer having a hydroxy functional group at the sock end. It is preferable in terms of maintaining a dispersed phase.
  • DMC Dimethyl carbonate
  • accident preparedness is one of the names according to the classification and labeling method of hazardous chemicals announced by the National Institute of Environmental Research. Looking at the classification and labeling methods announced by the National Institute of Environmental Research, hazardous chemicals are classified into toxic substances, licensed substances, restricted substances, prohibited substances, and accident preparations.
  • the prepared water-dispersed polyurethane prepolymer resin B of [Formula 2] has non-toxicity except toxic substances such as ethylenediamine and hydrazine, and an alkyldiamine monomer which is not an accident preparation material of the resin B 3 to 10 mol% of the amount of the diisocyanate used in the preparation is added to induce the urea reaction, and finally, an eco-friendly water-dispersible polyurethane resin C which can be represented by the following [Formula 3] having dispersion and storage stability Prepared.
  • the isocyanate functional groups remain to inhibit the stability of the water-dispersed polyurethane resin, and when it is 10 mol% or more, the number average molecular weight of the water-dispersed polyurethane resin is Excessively low problems such as poor weather resistance and elasticity of the physical properties as a urethane resin occurs.
  • Alkyldiamine-based monomers that are not a non-toxic accident-prevention material used in the reaction include alkyldiamine, 1,4-tetramethyldiamine, 1,4-tetramethyldiamine, 2-methyl-1,5- which are primary amines.
  • R 6 is represented by the formula (2), R 5 is an alkyldiamine monomer having an alkyldiamine monomer having 3 to 20 carbon atoms, which is not a non-toxic accident prepared material used in the third step reaction. n is an integer from 1 to 20.
  • the number-average molecular weight of the final eco-friendly water-dispersed polyurethane resin is about 5,000 to 200,000 g / mol, the glass transition temperature is 0 ⁇ 100 °C. It also has a water dispersion characteristic.
  • the water-dispersed polyurethane resin included in the coating composition of the present invention has a boiling point of 90 non-toxic, non-accidental non-hazardous general chemicals, dimethyl carbonate having a boiling point of 90 is used as a co-solvent, non-toxic as a neutralizing agent and prepared for accidents.
  • a tertiary amine, not a substance, is used as a neutralizing agent, has a non-toxic effect as a chain extender, and is an eco-friendly water-dispersible polyurethane resin that uses an alkyldiamine monomer, which is not an accident preparation material.
  • an eco-friendly, water-dispersible polyurethane resin that does not contain any toxic substances or accident preparation materials ensures safety from toxic substances in handling of coating compositions, manufacturing processes and film manufacturing processes, and facilitates accident preparation management. It is possible to provide, and to provide an environmentally friendly coating composition that can minimize the exposure of the film user from toxic substances.
  • a water-dispersible polyolefin type carboxyl (meth) acrylate copolymer contained in the coating composition of this invention a water-dispersion polyethylene (meth) acrylic acid copolymer, a water-dispersion polypropylene (meth) acrylic acid copolymer, and a water dispersion poly Butylene (meth) acrylic acid copolymer may be used.
  • a polyethyleneacrylic acid copolymer Primacor 5980I and 5990I resins provided by Dow Chemical may be used. In general, it may be represented by the following formula.
  • R 1 is an alkyl group having a carbon number of 2 ⁇ 12
  • R 2 is hydrogen (H) or a methyl group.
  • l is 1-20
  • m is 1-10
  • n is 10-3000.
  • the Primacor 5980I resin has a copolymerization ratio of ethylene and acrylic acid of 79.5: 20.5 weight ratio, and a neutralization factor of 0.75 is introduced.
  • a 2L three-necked glass reactor may be prepared to disperse the Primacor 5980I resin, add 750 g of deionized water and 250 g of Primacor 5980I resin, and reflux by installing a condenser while raising the temperature to 95 ° C. .
  • Dispersed polyolefin-based carboxyl (meth) acrylate copolymer by adding non-toxic tertiary amine as a neutralizing agent to 50 to 90 mol% of the number of moles of acrylic acid in Primacor 5980I resin and reacting for 8 hours while stirring at 150 rpm Prepare a resin solution.
  • the amount of the tertiary amine used is 50 mol% or less, it is difficult to dissolve the Primacor 5980I resin, and when 90 mol% or more, the viscosity increases exponentially due to excessive neutralization.
  • Tertiary amines that are not nontoxic accidental preparations used in the reaction are 2-amino-2methyl-1-propanol (2-amino-2-methyl-1-propanol, DMAMP-80), 2-dimethylamino 2-methyl-1-propanol (2-Dimethylamino-2-Methyl-1-Propanol, AMP-95), n-ethylmorpholine, dimethylaminopropanol, dimethylcyclohexylamine, Amines, such as dimethyl aza norbornene (2-methyl-2-azanorbornane), may be used, but are not necessarily limited thereto.
  • ethyl morpholine (n-ethylmorpholine), 2-amino-2methyl-1-propanol (2-amino-2-methyl-1-propanol, DMAMP-80), 2-dimethylamino-2-methyl-1- Propanol (2-Dimethylamino-2-Methyl-1-Propanol, AMP-95) is preferably used in terms of cost competitiveness as a commercialized material.
  • the water-dispersed polyolefin carboxyl (meth) acrylate copolymer contained in the coating composition of the present invention is (a) polyethylene acrylic acid copolymer resin, the copolymerization ratio of acrylic acid is 18 to 30% by weight, ethylene monomer is 70 to 82 weight%; And (b) 30 to 75 mol% of the neutralizing agent used for water dispersion of the polyethylene acrylic acid copolymer resin, which is not an accident-preparing substance having non-toxicity, compared with acrylic acid used for copolymerization; Characterized in that prepared using. When used less than 30 mol% may not be dispersed in water, even if used in excess of 75 mol% is ineffective.
  • the water-dispersible polyacrylate copolymer having a glass transition temperature of 50 to 120 ° C. prepared using a nonionic surfactant included in the coating composition of the present invention is a resin that can be prepared by a conventional emulsion polymerization method, and specifically, Polymethyl methacrylate (meth) acrylic acid copolymer, polymethyl methacrylate butyl (meth) acrylate (meth) acrylic acid copolymer, polymethyl methacrylate ethyl (meth) acrylate (meth) acrylic acid copolymer, polystyrene ( Meta) acrylic acid copolymer, polystyrenemethyl (meth) acrylate (meth) acrylic acid copolymer, polystyrene butyl (meth) acrylate (meth) acrylic acid copolymer, polystyreneethyl (meth) acrylate (meth) acrylic acid copolymer, polystyrenemethyl Methacrylate (meth)
  • the glass transition temperature of the NP-960 resin was 105 ° C., the weight average molecular weight was about 1,200,000 g / mol, and the solid content was 50%.
  • the water-dispersed polyacrylate copolymer resin having a glass transition temperature of 50 to 120 ° C. includes: (a) an aqueous dispersion polyacrylate copolymer resin prepared by emulsion polymerization using a nonionic surfactant as a main emulsifier; And (b) a water-dispersible polyacrylate copolymer resin having a glass transition temperature in the range of 50 to 120 ° C.
  • the water-dispersible polyacrylate copolymer may cause shock of an ionic emulsifier to prevent gelation of the water-dispersed polyolefin-based resin to which the partially neutralized carboxyl functional group is imparted and the fully neutralized water-dispersed polyurethane resin. It can prevent the blocking between films after coating with the effect of the high glass transition temperature while effectively improving the storage stability by inhibiting the water in advance, while acting as a buffer between the water-dispersible resin.
  • the water-dispersible polyacrylate copolymer resin included in the coating composition of the present invention includes (a) an emulsion-polymerized water-dispersible polyacrylate copolymer resin using a nonionic surfactant as a main emulsifier; And (b) a water dispersion polyacrylate copolymer resin having a glass transition temperature of 50 to 120 ° C.
  • the hard coating composition of the present invention comprises 1) an environment-friendly water dispersion polyurethane resin, 2) water dispersion polyolefin carboxyl (meth) acrylate copolymer resin, and 3) water dispersion polyacrylate copolymer described above.
  • the coating composition of the present invention 1) 100 parts by weight based on 1) environmentally friendly water-dispersed polyurethane resin solids, 2) 60 to 150 parts by weight based on water-dispersed polyolefin carboxyl (meth) acrylate copolymer solids And 3) 60 to 150 parts by weight of the water-dispersed polyacrylate copolymer solids based resin.
  • the coating composition of the present invention is 1) 100 parts by weight based on eco-friendly water-dispersed polyurethane resin solids, 2) 80 to 120 parts by weight based on water-dispersed polyolefin-based carboxyl (meth) acrylate copolymer, and 3 ) May comprise 80 to 120 parts by weight based on the water-dispersed polyacrylate copolymer solids.
  • the coating composition of the present invention may include other conventional additives in addition to the eco-friendly water-dispersible polyurethane resin, the water-dispersed polyolefin-based carboxyl (meth) acrylate copolymer resin, and the water-dispersible polyacrylate copolymer resin.
  • the additives include slip additives and surfactants.
  • the slip additive may include a silicone slip additive, an acrylic slip additive, a fluorine slip additive, and the like, but is not limited thereto.
  • slip additives that are commercially available in the art include, for example, BYK-348, BYK-348, BYK-330, BYK-310, BYK-307, etc. There is a kind of slip additive.
  • the slip additive may be used in the range of 0.02 to 2 parts by weight, preferably 0.1 to 1 parts by weight, relative to 100 parts by weight of the resin solids contained in the entire coating composition. If the content of the slip additive is less than 0.02 parts by weight, it is difficult to expect the effect of adding the slip additive in the coating film, and if it exceeds 2 parts by weight, the ink adhesion performance may be deteriorated due to the excessive amount of the slip additive.
  • nonionic surfactant in which the hydrophilic group is adjusted to the number of moles of ethylene oxide added and the aliphatic oil component is contained as a hydrophobic group, but is not limited thereto.
  • the nonionic surfactant may be selected from, for example, a family of Tween 20, 40, 60, 80, and the like, or a nonionic surfactant family of Surfynol-104 and Surfynol-440 series of Air Products.
  • the surfactant may be used in the range of 0.05 to 3 parts by weight, preferably 0.1 to 2 parts by weight, relative to 100 parts by weight of the resin solids contained in the total coating composition. If the content of the surfactant is less than 0.05 parts by weight, it is difficult to expect the improvement of wettability during coating, and if it exceeds 3 parts by weight, the water resistance is impaired due to excessive surfactant effects.
  • the film of the present invention is a film prepared by coating a coating composition having a composition defined above on a substrate surface.
  • the film of the present invention More specifically, the film of the present invention; And a coating layer formed by applying a coating composition on or above the base film layer. It can be made into a laminated film.
  • the film of the present invention A coating layer formed by applying a coating composition on or above the base film layer; This laminated electrostatic printing film can be produced.
  • the base film layer may be made of polypropylene resin, polyethylene resin, polyamide resin, polyester resin, polyacrylic resin, polyvinyl chloride resin, polycarbonate resin, urethane resin, paper, cloth, nonwoven fabric, and inorganic
  • a material such as a composite material can be used, and in the present invention, one formed of various materials can be used without particular limitation on the selection of the base material.
  • the base film layer may have a thickness in a range of about 12 to 400 ⁇ m, preferably in a range of 20 to 300 ⁇ m. If the thickness of the base film layer is less than 12 ⁇ m it may be difficult to control the coating tension due to the thickness of the substrate is too thin, if the thickness is thicker than 400 ⁇ m it may be difficult to use the electrostatic-type printing printer is not smooth.
  • the coating layer may be formed by coating the coating composition of the present invention.
  • the coating composition may be coated on one surface of the base film layer, and then heated at a temperature of about 80 to 150 ° C. for about 30 seconds to 2 minutes to form a coating film.
  • the thickness of the coating layer may be in the range of about 0.5 ⁇ 40 ⁇ m.
  • the thickness of the coating layer is less than 0.5 ⁇ m there may be a risk of lowering the ink adhesion, if the thickness exceeds 40 ⁇ m may decrease the substrate adhesion performance.
  • DMAMP-80 2-dimethylamino-2-methylpropanol
  • DMC dimethyl carbonate
  • the reactant was dispersed while being slowly added 500 g of deionized water for 1 hour while stirring at high speed at about 700 rpm.
  • the water dispersion polyurethane resin had a number average molecular weight of 52,000 g / mol, a glass transition temperature of 42 ° C., and a solid content of 25.3%.
  • the water-dispersed polyurethane resin intermediate A prepared by the reaction of Preparation Example 1-2) has the following chemical formula.
  • R 1 is an alkyl group having 6 carbon atoms
  • R 2 is an alkyl group having 3 carbon atoms
  • R 3 is an alkyl group having 6 carbon atoms.
  • the number average molecular weight of the prepared resin was about 1,000 g / mol.
  • the water-dispersed polyurethane resin finally prepared by the reaction of Preparation Example 1-5) has the following chemical formula.
  • R 6 is the main chain of intermediate A prepared by the reaction of Preparation Example 1-2), R 5 is an alkyl group having 6 carbon atoms, and the number average molecular weight of the prepared resin was about 2,000 g / mol.
  • Solid content of the prepared water-dispersed polyolefin-based carboxyl (meth) acrylate copolymer resin solution was 25.2%.
  • the production process is the same as in Preparation Example 2, except that Primacor 5990I was used in preparing the aqueous polyolefin carboxyl (meth) acrylate copolymer resin solution.
  • DMSO dimethyl sulfoxide
  • DMF dimethylformamide
  • NMP ethylene-2-pyrrolidone
  • DMF dimethylformamide
  • NMP ethylene-2-pyrrolidone
  • DMF dimethylformamide
  • Each coating composition prepared above was coated on both sides of the base film of a polypropylene (PP) material without a primer treatment having a thickness of 100 ⁇ m and a width of 1,080 mm so as to have a dry coating thickness of 1 ⁇ m by a bar coating method, followed by a convection oven. It was put in to dry for 1 minute at 120 °C temperature to prepare a coating film specimen for evaluation of each coating composition.
  • PP polypropylene
  • each coating film prepared above was cut to A3 standard, and then each coating produced in Experimental Example 1 using an Indigo 5500 printer device manufactured by HP.
  • a printed specimen for evaluation was produced by printing on one side of the film specimen.
  • Each test film prepared for each coating film prepared in Experimental Example 2 was prepared in 200 mm X 100 mm, and then laminated on the surface of the coating layer by 100 mm using a roller of 1 kg load on the surface of the coating layer for 30 minutes. Liver left.
  • Each coating composition prepared in the above Examples and Comparative Examples was placed in a 50ml vial and then left in an 80 convection oven for 7 hours, and then gelled every 1 days to visually check whether the change in viscosity occurred by date.
  • the coating film specimens for each coating composition prepared in Experimental Example 1 were prepared in 100 mm X 100 mm and then remained in the coating film using the Emission test chamber method (Small), (EN / ISO 16000-9). The content of TVOC was compared by GC-MS analysis.
  • the specimen prepared by using the coating composition of Examples 1 to 4 proposed by the present invention is a coating film capable of electrostatic printing with good substrate adhesion and ink adhesion as compared with Comparative Examples 1 to 3. Confirmed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacturing & Machinery (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une résine de polyuréthane respectueuse de l'environnement, un procédé pour sa préparation et une composition de revêtement la comprenant. La présente invention concerne une résine aqueuse de polyuréthane respectueuse de l'environnement qui est exempte de substances toxiques en plus de présenter d'excellentes propriétés d'impression, telles que l'adhérence, la propriété antiblocage, l'étanchéité à l'eau et analogues, une composition de revêtement et un film, tous deux contenant la même résine.
PCT/KR2016/013295 2016-11-17 2016-11-17 Résine de polyuréthane respectueuse de l'environnement, procédé de préparation correspondant et composition de revêtement la comprenant Ceased WO2018092943A1 (fr)

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KR102695123B1 (ko) 2021-07-05 2024-08-16 주식회사 삼성그라테크 폴리아미드 접착층을 포함하는 열가소성 공압출 다층필름
KR102520534B1 (ko) * 2022-11-07 2023-04-14 주식회사 아이큐브글로벌 종이용 코팅 조성물 및 이를 포함하는 종이 성형물

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090069695A (ko) * 2007-12-26 2009-07-01 (주)디피아이 홀딩스 수분산 폴리우레탄 수지
KR20090085805A (ko) * 2008-02-05 2009-08-10 현대자동차주식회사 낮은 이온 함량 및 높은 고형분 함량을 갖는 수분산폴리우레탄 수지의 제조방법
KR20110081699A (ko) * 2010-01-08 2011-07-14 풍원정밀(주) 폴리우레탄 고분자, 이의 제조 방법 및 이를 포함하는 에칭 레지스트 인쇄용 잉크 조성물
KR20110082572A (ko) * 2008-10-17 2011-07-19 인비스타 테크놀러지스 에스.에이.알.엘. 분산액을 포함하는 수성 폴리우레탄우레아 조성물 및 필름
KR20120115027A (ko) * 2011-04-08 2012-10-17 주식회사 케이씨씨 폴리우레탄 수분산 수지, 그 제조방법 및 이를 포함하는 ｐｃｍ용 도료 조성물

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4122265A1 (de) 1991-07-05 1993-01-07 Hoechst Ag Polyurethan-dispersionen

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20090069695A (ko) * 2007-12-26 2009-07-01 (주)디피아이 홀딩스 수분산 폴리우레탄 수지
KR20090085805A (ko) * 2008-02-05 2009-08-10 현대자동차주식회사 낮은 이온 함량 및 높은 고형분 함량을 갖는 수분산폴리우레탄 수지의 제조방법
KR20110082572A (ko) * 2008-10-17 2011-07-19 인비스타 테크놀러지스 에스.에이.알.엘. 분산액을 포함하는 수성 폴리우레탄우레아 조성물 및 필름
KR20110081699A (ko) * 2010-01-08 2011-07-14 풍원정밀(주) 폴리우레탄 고분자, 이의 제조 방법 및 이를 포함하는 에칭 레지스트 인쇄용 잉크 조성물
KR20120115027A (ko) * 2011-04-08 2012-10-17 주식회사 케이씨씨 폴리우레탄 수분산 수지, 그 제조방법 및 이를 포함하는 ｐｃｍ용 도료 조성물

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