Classifications

• • 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
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
• • 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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • 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
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters
• • 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
  • C09D175/06—Polyurethanes from polyesters
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • 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
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• the present invention relates to an aqueous dispersion of a polyurethane resin and a coating agent for a plastic film using the same.
• a primer is required to improve adhesion.
• the primer used here is required to have sufficient adhesion to various plastic films, strong resistance, suitability for post-processing, and the like. Since the performance of these coating agents depends on the performance of the resin constituting the coating agent, solvent-based coating agents mainly composed of a polyurethane resin have been frequently used in the past because of adhesion to a plastic film.
• solvent-based primer compositions containing chlorinated polyolefin as a main component are often used for polyolefin-based films.
• aqueous polyurethane resin is disclosed (Patent Document 1).
• the present inventors also have a polyester glycol composed of a mixed dicarboxylic acid of aromatic and aliphatic and a branched glycol, a polyol having 3 or more hydroxyl groups, a free carboxyl group or a tertiary amino group.
• Patent Document 2 Water-based polyurethane with excellent adhesion to a wide variety of films, leaving a carboxyl group or a tertiary amino group without completely neutralizing a urethane prepolymer having an isocyanate group at the end, which has a chain extender as a constituent component A resin composition has been disclosed (Patent Document 2).
• Patent Documents 1 and 2 may not be sufficient.
• the present invention has been made in view of the above problems, and provides an aqueous dispersion of a polyurethane resin that is excellent in adhesion to a wide variety of films and that provides a coating film free from cissing and uneven coating. Is an issue.
• the inventors of the present invention have intensively studied to solve the above problems, and as a result, have a specific structure and type of polyester glycol (A), polyol (B), organic diisocyanate (C), chain extender (A polyurethane resin obtained by cross-linking a urethane prepolymer having an isocyanate group at the terminal with D) or (D ′) as a constituent component with water in the presence of a specific amount of a neutralizing agent (E) and water of a specific structural compound It has been found that the above problems can be solved by using a dispersion, and the present invention has been completed.
• a polyurethane resin obtained by cross-linking a urethane prepolymer having an isocyanate group at the terminal with D) or (D ′) as a constituent component with water in the presence of a specific amount of a neutralizing agent (E) and water of a specific structural compound
• Polyurethane resin is a polyol (B) having 35 or more and less than 70% by weight of a polyester glycol (A) containing aromatic dicarboxylic acid or aliphatic dicarboxylic acid and a branched glycol, and an organic compound having 3 or more hydroxyl groups.
• a urethane prepolymer having an isocyanate group at the terminal comprising a diisocyanate (C) and a chain extender (D) having a free carboxyl group as a constituent component, with respect to the chain extender (D) having a free carboxyl group
• An aqueous dispersion which is a polyurethane resin having an acid value of 12.5 to 81.0 (KOHmg / g) crosslinked with water in the presence of a neutralizing agent (E) in an amount of 0.4 to 0.8 mol,
• R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.
• Y 1 and Y 2 each independently represents an alkylene group having 2 to 6 carbon atoms.
• x and y represent an average added mole number and satisfy 1 ⁇ x + y ⁇ 30.
• Polyurethane resin is a polyol (B) having 35 or more and less than 70% by weight of a polyester glycol (A) containing aromatic dicarboxylic acid or aliphatic dicarboxylic acid and a branched glycol, and an organic compound having 3 or more hydroxyl groups.
• a urethane prepolymer having an isocyanate group at the terminal comprising a diisocyanate (C) and a chain extender (D ′) having a tertiary amino group as a constituent component, and a chain extender (D ′) having the tertiary amino group.
• Water dispersion which is a polyurethane resin having an amine value of 12.5 to 81.0 (KOHmg / g) crosslinked with water in the presence of 0.4 to 0.8 mol of a neutralizing agent (E) body, [In General Formula (1), R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.
• Y 1 and Y 2 each independently represents an alkylene group having 2 to 6 carbon atoms.
• x and y represent an average added mole number and satisfy 1 ⁇ x + y ⁇ 30.
• [3] The aqueous dispersion of polyurethane resin according to [1] or [2], wherein the content of the acetylene compound is 0.05 to 2% by mass of the aqueous dispersion.
• [4] The polyurethane resin aqueous dispersion according to any one of [1] to [3], wherein the polyurethane resin has a glass transition temperature of 40 ° C. or higher.
• a plastic film coating agent comprising the polyurethane resin aqueous dispersion according to any one of [1] to [4].
• aqueous dispersion of the polyurethane resin of the present invention it is possible to obtain a coating film having excellent adhesion to a wide variety of films and free from repelling and uneven coating.
• an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid are used as the acid component, at least a branched glycol is used as the polyol component, and the polyester glycol (A) obtained by reacting the acid component with the polyol component, and the number of hydroxyl groups Is obtained by reacting an organic diisocyanate (C) with a chain extender (D) having at least a free carboxyl group or a chain extender (D ') having a tertiary amino group.
• the urethane prepolymer having an isocyanate group at the terminal is added with water in the presence of a neutralizing agent (E) in an amount of 0.4 to 0.8 mol relative to the chain extender (D) having a free carboxyl group.
• a neutralizing agent E
• an aqueous dispersion of a polyurethane resin having a crosslinked acid value or amine value of 12.5 to 81.0 KOHmg / g
• the aromatic dicarboxylic acid as an acid component constituting the polyester glycol (A) used in the present invention is not particularly limited, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5 -Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, tetrahydrophthalic acid, etc., or reactive derivatives such as acid anhydrides, alkyl esters, acid halides, and the like. These aromatic dicarboxylic acids can be used alone or in combination of two or more.
• the aliphatic dicarboxylic acid is not particularly limited, but for example, malonic acid, succinic acid, tartaric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, alkyl succinic acid, linolenic acid, maleic acid , Fumaric acid, mesaconic acid, citraconic acid, itaconic acid and the like, or reactive derivatives thereof such as acid anhydrides, alkyl esters and acid halides.
• These aliphatic dicarboxylic acids can be used alone or in combination of two or more.
• the ratio of the aromatic dicarboxylic acid to the aliphatic dicarboxylic acid in the acid component is preferably a mass ratio of aromatic dicarboxylic acid: aliphatic dicarboxylic acid of 9.5: 0.5 to 5: 5, and 9: It is more preferably 1 to 6: 4, and further preferably 9: 1 to 7: 3. If the aromatic dicarboxylic acid content is 95% by mass or less, the adhesiveness to the plastic film is good, and if it is 50% by mass or more, water resistance, blocking resistance and transparency are good.
• the branched glycol as the glycol component constituting the polyester glycol (A) used in the present invention is not particularly limited, and examples thereof include 1,2-propylene glycol, 1-methyl-1,3-butylene glycol, 2-methyl- 1,3-butylene glycol, neopentyl glycol, 1-methyl-1,4-pentylene glycol, 2-methyl-1,4-pentylene glycol, 1,2-dimethyl-neopentyl glycol, 2,3-dimethyl -Neopentyl glycol, 1-methyl-1,5-pentylene glycol, 2-methyl-1,5-pentylene glycol, 3-methyl-1,5-pentylene glycol, 1,2-dimethylbutylene glycol, 1 , 3-dimethylbutylene glycol, 2,3-dimethylbutylene glycol, 1, - and dimethyl butylene glycol.
• These branched glycols can be used alone or in combination of two or more.
• a linear glycol may be used as an additional component as long as the target performance is not deteriorated as required.
• Such linear glycol is not particularly limited, and examples thereof include ethylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,5-pentylene glycol, 1,6-hexamethylene glycol, diethylene glycol and the like. be able to.
• These linear glycols can be used alone or in combination of two or more.
• the polyester glycol (A) may be contained in a polyester segment of 35 or more and less than 70% by mass, more preferably 40 to less than 60% by mass with respect to the urethane prepolymer having an isocyanate group at the terminal. When it is 35% by mass or more, the coating film hardness is improved and the blocking resistance is good, and when it is less than 70% by mass, the adhesion is good.
• the number average molecular weight of the polyester glycol (A) is preferably 500 to 10000, more preferably 1000 to 5000, and still more preferably 1200 to 3000.
• the number average molecular weight is less than 500, the obtained polyurethane resin is hard and brittle, and the adhesion is also lowered.
• the number average molecular weight exceeds 10,000, the resulting polyurethane resin becomes soft, and the blocking resistance also decreases.
• the polyester glycol (A) in the present invention is obtained by a method similar to a known polyester production method in which an acid component and a glycol component are dehydrated and condensed.
• the polyol (B) having 3 or more hydroxyl groups used in the present invention is not particularly limited.
• trimethylolpropane is preferable from the viewpoint of adhesion.
• These polyols (B) having 3 or more hydroxyl groups can be used alone or in combination of two or more. By using the polyol (B) having 3 or more hydroxyl groups within a range that does not impair the water dispersibility of the resulting polyurethane resin, the adhesion to the plastic film can be improved.
• the organic diisocyanate (C) used in the present invention is not particularly limited, and examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and araliphatic diisocyanates.
• the aliphatic diisocyanate is not particularly limited.
• tetramethylene diisocyanate dodecamemethylene diisocyanate, 1,4-butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- Examples thereof include trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.
• the alicyclic diisocyanate is not particularly limited.
• isophorone diisocyanate hydrogenated xylylene diisocyanate, 4,4′-cyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (Isocyanate methyl) cyclohexane and the like can be mentioned.
• the aromatic diisocyanate is not particularly limited.
• tolylene diisocyanate 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and the like.
• the aromatic aliphatic diisocyanate is not particularly limited, and examples thereof include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, ⁇ , ⁇ , ⁇ , ⁇ -tetramethylxylylene diisocyanate.
• dialkyldiphenylmethane diisocyanate tetraalkyldiphenylmethane diisocyanate
• ⁇ , ⁇ , ⁇ -tetramethylxylylene diisocyanate alicyclic diisocyanates are preferable from the viewpoint of hardness, and isophorone diisocyanate and 4,4′-cyclohexylmethane diisocyanate are more preferable.
• These organic diisocyanates can be used alone or in combination of two or more.
• the chain extender (D) having a free carboxyl group used in the present invention is not particularly limited, and examples thereof include dihydroxy carboxylic acids such as dialkylol alkanoic acids, particularly dimethylol alkanoic acids (for example, dimethylol acetic acid, dialkyl And methylolbutanoic acid, dimethylolpropionic acid, dimethylolbutyric acid, dimethylolpentanoic acid, etc.) and dihydroxysuccinic acid. Among these, dimethylolpropionic acid and dimethylolbutanoic acid are preferable from the viewpoint of adhesion.
• These chain extenders (D) having a free carboxyl group can be used alone or in combination of two or more.
• the chain extender (D ′) having a tertiary amino group used in the present invention is not particularly limited, and examples thereof include N-alkyl dialkanolamines and N-alkyldiaminoalkylamines.
• the N-alkyl dialkanolamine is not particularly limited, and examples thereof include N-methyldiethanolamine and N-ethyldiethanolamine.
• the N-alkyldiaminoalkylamine is not particularly limited, and examples thereof include N-methyldiaminoethylamine and N-ethyldiaminoethylamine. Among these, N-methyldiethanolamine is preferable from the viewpoint of adhesion.
• These chain extenders (D ′) having a tertiary amino group can be used alone or in combination of two or more.
• other usable chain extenders are not particularly limited, and examples thereof include glycols, aliphatic diamines, alicyclic diamines, and aromatic diamines.
• the glycols are not particularly limited.
• the aliphatic diamine is not particularly limited, and examples thereof include ethylene diamine, propylene diamine, hexamethylene diamine, 1,4-butane diamine, and aminoethyl ethanol amine.
• the alicyclic diamine is not particularly limited, and examples thereof include isophorone diamine and 4,4′-dicyclohexylmethane diamine. Although it does not specifically limit as said aromatic diamine, For example, xylylenediamine, tolylenediamine, etc. can be mentioned. These other usable chain extenders can be used alone or in combination of two or more.
• the polyurethane resin aqueous dispersion of the present invention can be produced by any conventionally known method, and (1) a one-shot method in which each component is reacted at once, or (2) a multi-stage method in which the components are reacted in stages.
• any method such as a method in which an organic polyisocyanate and a part of an active hydrogen compound are reacted to form a prepolymer having an isocyanate group at the end, and then the remainder of the active hydrogen compound is added and further reacted.
• the multi-stage method is preferred because it is easy to introduce a carboxyl group or a tertiary amino group into the polyurethane molecular chain.
• a method of adding water and then removing the organic solvent can be preferably used.
• the organic diisocyanate (C), the polyester glycol (A), and the number of hydroxyl groups are 3 or more in an organic solvent that is inert to isocyanate and compatible with water.
• a polyol (B) is reacted to form a prepolymer having an isocyanate group at its end, and then a chain extender (D) having a free carboxyl group or a chain extender (D ') having a tertiary amino group;
• the urethane prepolymer having an isocyanate group at the terminal obtained by reacting with the above is obtained by subjecting it to chain extension with water in the presence of the neutralizing agent (E) and at the same time making it aqueous.
• the term “hydration” as used herein refers to stably dispersing or emulsifying a resin in water.
• isocyanate is synthesized in an excess system, and the content of free isocyanate groups is preferably 0.2 to 3.0% by mass, more preferably 0.5 to 2.0% by mass. It is. If it is 3.0 mass% or less, it is preferable at the point of blocking resistance, and if it is 0.2 mass% or more, adhesiveness will improve.
• the neutralizing agent (E) is not particularly limited, and examples thereof include ammonia, N-methylmorpholine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine, morpholine, tripropylamine, ethanolamine, triisopropanolamine, 2 -Amino-2-methyl-1-propanol and the like.
• the neutralizing agent for neutralizing the tertiary amino group as a quaternary ammonium salt is not particularly limited, and examples thereof include alkyl halides and sulfuric acid esters.
• the alkyl halide is not particularly limited, and examples thereof include benzyl chloride and methyl chloride.
• the sulfate ester is not particularly limited, and examples thereof include dimethyl sulfate and diethyl sulfate.
• the content of the neutralizing agent (E) with respect to the chain extender (D) having a free carboxyl group or the chain extender (D ′) having a tertiary amino group is 0.4 to 0.8 mol.
• the amount is preferably 0.40 to 0.75 mol.
• the aqueous dispersion of the polyurethane resin is usually produced at a temperature of 20 to 140 ° C., preferably 40 to 120 ° C.
• a urethane reaction catalyst for example, an amine catalyst, a tin-type catalyst, a titanium-type catalyst etc. can be mentioned.
• the amine catalyst is not particularly limited, and examples thereof include triethylamine, N-ethylmorpholine, and triethylenediamine.
• the tin-based catalyst is not particularly limited, and examples thereof include dibutyltin dilaurate, dioctyltin dilaurate, and tin octylate. Although it does not specifically limit as said titanium type catalyst, For example, tetrabutyl titanate etc. can be mentioned.
• the usage-amount of a catalyst is 0.1 mass% or less normally with respect to a polyurethane resin.
• organic solvent that is inert to the isocyanate and compatible with water examples include ester solvents (for example, ethyl acetate, butyl acetate, ethyl cellosolve acetate), ketone solvents (for example, , Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), ether solvents (eg, dioxane, tetrahydrofuran, propylene glycol monomethyl ether, etc.), amide solvents (eg, dimethylformamide, N-methylpyrrolidone, etc.), etc. it can.
• ester solvents for example, ethyl acetate, butyl acetate, ethyl cellosolve acetate
• ketone solvents for example, , Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.
• ether solvents eg, dioxane,
• the acid value or amine value of the polyurethane resin of the present invention is 12.5 to 81.0 (KOH mg / g), preferably 20 to 60 (KOH mg / g). If it is these ranges, it is preferable at the point of the adhesiveness to a film.
• the number average molecular weight of the polyurethane resin of the present invention is preferably 10,000 to 6000000, more preferably 100,000 to 4000000.
• the number average molecular weight is 10,000 or more, the drying property and blocking resistance of the coating film of the coating agent using the same are improved.
• the number average molecular weight is 6000000 or less, the adhesiveness of the polyurethane resin solution is suitable and preferable.
• the glass transition temperature of the polyurethane resin composition in the present invention is preferably 30 ° C. or higher, more preferably 40 ° C. or higher. If it is these ranges, it is preferable at the point of the heat resistance of a coating film, and blocking resistance.
• the content of the polyurethane resin in the aqueous dispersion is preferably 1 to 60% by mass, more preferably 10 to 50% by mass. Within these ranges, the stability of the aqueous dispersion is good.
• an aqueous dispersion of the polyurethane resin and an acetylene compound represented by the following general formula (1) is used.
• the compound represented by the general formula (1) in combination, a coating film having excellent adhesion to a wide variety of plastic films and free from cissing and uneven coating can be obtained.
• R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.
• Y 1 and Y 2 each independently represents an alkylene group having 2 to 6 carbon atoms.
• x and y represent an average added mole number and satisfy 1 ⁇ x + y ⁇ 30.
• Examples of the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms represented by R 2 and R 3 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl Group, 2-butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group and the like.
• R 2 and R 3 represent a cyclic alkyl group
• the alkyl group preferably has 3 to 8 carbon atoms.
• R 2 and R 3 are more preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
• Examples of the linear, branched or cyclic alkyl group having 1 to 8 carbon atoms represented by R 1 and R 4 include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group , Isobutyl group, 2-butyl group, t-butyl group, hexyl group, cyclohexyl group, octyl group and the like.
• R 1 and R 4 represent a cyclic alkyl group
• the alkyl group preferably has 3 to 8 carbon atoms.
• a linear, branched or cyclic alkyl group having 3 to 8 carbon atoms is preferable, and an isobutyl group is particularly preferable.
• X and y represent the average number of moles added.
• the sum of x and y is 1 to 30 (1 ⁇ x + y ⁇ 30), preferably 2 to 25, more preferably 3 to 24, and more preferably 3 to 20. . Within these ranges, it is preferable because the stability of the aqueous dispersion is good and the coating appearance is good.
• Y 1 and Y 2 each independently represents an alkylene group having 2 to 6 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, still more preferably an alkylene group having 2 or 3 carbon atoms, An alkylene group (ethylene group) is particularly preferred.
• Examples of the acetylene compound represented by the general formula (1) include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6. -Diol, 2,5,8,11-tetramethyl-6-dodecin-5,8-diol, 2,5-dimethyl-3-hexyne-2,5-diol, etc., and alkylene oxide adducts thereof (preferably Is an ethylene oxide adduct).
• 2,4,7,9-tetramethyl-5-decyne-4,7-diol and an ethylene oxide adduct (1 ⁇ x + y ⁇ 30, more preferably 2 ⁇ x + y ⁇ 25) are preferable.
• the acetylene compound represented by the general formula (1) can be used alone or in combination with various additives.
• acetylene compound represented by the general formula (1) a commercially available product may be used.
• Surfynol series for example, manufactured by Air Products or Nissin Chemical Industry Co., Ltd.
• Surfynol series for example, manufactured by Air Products or Nissin Chemical Industry Co., Ltd.
• Surfynol 420, Surfynol 440, Surfynol 465 Olphine series (for example, Orphine E1010, Orphine E1020), Dynal series (for example, Dynal 604)
• Dow Chemical Company General Aniline Company, etc.
• the content of the acetylene compound represented by the general formula (1) in the aqueous dispersion in the present invention is preferably 0.01 to 2% by mass, more preferably 0.1 to 1.5% by mass. Within these ranges, coating unevenness can be suppressed and coating properties are favorable. In addition, when 2 or more types of acetylene compounds are included, it is preferable to satisfy
• the polyurethane resin aqueous dispersion of the present invention is used as it is as a coating agent for plastic films, but if necessary, pigments and dyes, water for adjusting solid content and viscosity, anti-blocking agent, dispersion stabilizer, Add thixotropic agents, antioxidants, UV absorbers, antifoaming agents, thickeners, dispersants, surfactants, catalysts, fillers, lubricants, antistatic agents, etc., and add these to ball mills, sand grind mills, etc. You may use the composition obtained by mixing as a coating agent for plastic films.
• a crosslinking agent such as an aminoplast compound, an epoxy compound, or a carbodiimide compound.
• the coating agent for plastic film to which these cross-linking agents are added exhibits very excellent adhesion and improves water resistance and solvent resistance.
• the target film to which the coating agent for plastic film of the present invention is applied is not particularly limited.
• polyester film unstretched polyethylene terephthalate film (hereinafter referred to as PET film)
• nylon film stretched nylon film, unstretched nylon) Film
• stretched polypropylene film hereinafter referred to as OPP film
• acrylic film hereinafter referred to as AC film
• PC film polycarbonate film
• a film can also be preferably used.
• stretched polypropylene films, PET films, and AC films that have been subjected to surface treatment such as corona discharge treatment can be more preferably used. Adhesion can be improved by surface treatment such as corona discharge treatment.
• Table 1 shows the composition of polyester glycol used in Examples and Comparative Examples.
• Example 1 440 parts of polyester glycol A, 20 parts of trimethylolpropane and 800 parts of methyl ethyl ketone were added and dissolved with sufficient stirring, and then 450 parts of isophorone diisocyanate was added and reacted at 75 ° C. for 1 hour. Thereafter, 130 parts of dimethylolpropionic acid and 44 parts of triethylamine were added and reacted at 75 ° C. to obtain a prepolymer solution having a terminal isocyanate group having an NCO content of 1.8%. Next, this prepolymer was cooled to 40 ° C., 2700 parts of water was added, and the mixture was stirred at high speed with a homomixer and emulsified.
• Methyl ethyl ketone was distilled off from the resin solution under reduced pressure. Furthermore, 0.2% by mass of Surfinol 440 in the aqueous dispersion was added to obtain an aqueous dispersion 1 having a polyurethane resin content of 30%. The physical properties of the obtained polyurethane resin 1, adhesion to various films, repelling and coating unevenness were measured. The results are shown in Table 2.
• Surfynol 104E acetylene glycol surfactant (2,4,7,9-tetramethyl-5-decyne-4,7-diol: R 2 in the general formula (1) described above, manufactured by Air Products And R 3 is a methyl group, R 1 and R 4 are isobutyl groups, Y 1 and Y 2 are ethylene groups, and x + y is 0)
• Surfynol 420 an acetylene glycol surfactant manufactured by Air Products (in the general formula (1) described above, R 2 and R 3 are methyl groups, and R 1 and R 4 are isobutyl groups) Y 1 and Y 2 are ethylene groups, and x + y is 1)
• Surfynol 440 an acetylene glycol surfactant manufactured by Air Products (in the general formula (1), R 2 and R 3 are methyl groups, and R 1 and R 4 are isobutyl groups Y 1 and Y
• Surfynol 485 an acetylene glycol surfactant manufactured by Air Products (in the general formula (1), R 2 and R 3 are methyl groups, and R 1 and R 4 are isobutyl groups Y 1 and Y 2 are ethylene groups, and x + y is 24) ⁇ BYK-347: Polyether-modified polydimethylsiloxane surfactant (by Big Chemie Japan) ⁇ Furgent 100: Fluorosurfactant (manufactured by Neos)
• OPP film 100 ⁇ m thick, corona discharge-treated stretched polypropylene film 2.
• AC film 100 ⁇ m thick, corona discharge-treated stretched acrylic film PET film: 100 ⁇ m thick, stretched polyethylene terephthalate film treated with corona discharge
• the aqueous dispersion of the polyurethane resin was evaluated by the method shown below.
• (1) Glass transition temperature The temperature at which the loss elastic modulus (E ′′) in dynamic viscoelasticity is maximized is the glass transition temperature, and the measurement conditions are a frequency: 10 Hz and a heating rate: 2 ° C. per minute. .
• (2) Adhesiveness The aqueous dispersions obtained in Examples and Comparative Examples were applied to the above various films to a dry film thickness of 10 ⁇ m, dried at room temperature (25 ° C.), and then heat treated at 80 ° C. for 5 minutes. It was. The adhesion of the coating film was evaluated based on the cross-cut tape method of JIS K5400.
• Adhesiveness was evaluated based on the degree to which the film peeled off from the film when a 2 mm square was formed in a grid pattern on the coated surface and a cellophane adhesive tape was applied and this was rapidly peeled off.
• the evaluation results were displayed as follows. ⁇ : Not peeled off at all ⁇ : 80% or more of film remaining ⁇ : 20% or less (4) Repelling and uneven coating
• the aqueous dispersions obtained in Examples and Comparative Examples were applied to an A4 size (18 cm ⁇ 25 cm) OPP film so as to have a dry film thickness of 10 ⁇ m, and the repellency and uneven coating on the coating surface were evaluated according to the following criteria. ⁇ : No repellency was observed. ⁇ : One to four cisterns were observed. ⁇ : Five or more cisterns were observed.
• the aqueous dispersions belonging to the technical scope of the present invention are excellent in adhesion to a wide variety of films and can provide a coating film free from cissing and uneven coating.
• Comparative Examples 1 to 3 which do not contain an acetylene compound, have poor repelling / coating unevenness, and the structures of Polyester Glycol (A) do not satisfy the requirements.
• Comparative Examples 4, 5 and the amount of Polyester Glycol (A) do not satisfy the requirements.
• Comparative Examples 6 and 7 have poor adhesion. It can be seen that none of the comparative examples can achieve both adhesion and repelling / coating unevenness.
• the primer obtained from the aqueous dispersion of the polyurethane resin of the present invention is excellent in adhesion to a wide variety of films, it can be suitably used as a film primer. Moreover, since it is highly transparent and highly uniform, it is particularly suitably used as a primer for optical films such as polarizing plates, diffusion sheets, prism sheets and ITO films.

Landscapes

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

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=53887552

Family Applications (1)

Country Status (5)

Cited By (1)

Families Citing this family (1)

Citations (10)

Family Cites Families (5)

• 2014
  • 2014-10-27 JP JP2014218109A patent/JP5758040B1/ja active Active
• 2015
  • 2015-10-01 WO PCT/JP2015/077895 patent/WO2016067824A1/ja active Application Filing
  • 2015-10-01 CN CN201580046826.4A patent/CN106795263A/zh active Pending
  • 2015-10-01 KR KR1020177004724A patent/KR102405157B1/ko active IP Right Grant
  • 2015-10-20 TW TW104134276A patent/TWI564343B/zh active

Patent Citations (10)

Also Published As

Similar Documents

Legal Events