WO2013014837A1 - Aqueous polyurethane resin composition, and highly-adhesive polyester film to which said aqueous polyurethane resin composition has been applied - Google Patents

Abstract

Provided are: an aqueous polyurethane resin composition having excellent adhesiveness to synthetic resins, and tackiness and blocking resistance after application, said composition having (A) a polyol, (B) a polyisocyanate, (C) a hydrophilic compound represented by general formula (1), (D) a monohydroxy vinyl ether compound represented by general formula (2), and water as essential components; and a highly-adhesive polyester film having a highly-adhesive layer obtained by applying the aqueous polyurethane resin composition to at least one surface of the polyester film. The aqueous polyurethane resin composition is characterized in that the amount of an alkylene oxide unit represented by (C₂H₄-O)_n in the (C) component is 3 to 20 mass% of the solid content comprising the (A) to (D) components, and the content of the (D) component is 3 to 25 mass% of the aforementioned solid content.

Description

Water-based polyurethane resin composition, easy-adhesive polyester film formed by applying this

The present invention relates to a water-based polyurethane resin composition and an easily adhesive polyester film obtained by applying this to at least one side of a polyester film substrate, and more specifically, adhesion to a synthetic resin, tackiness after application, and resistance to resistance. It is related with the water-based polyurethane resin composition excellent in blocking property, and the easily adhesive polyester film excellent in adhesiveness with a base film and energy-beam curable resin, and also excellent in transparency (haze) of a film.

Polyurethane resins can be used as coatings and molded articles having wear resistance, adhesiveness, non-tackiness, rubber elasticity, etc., and are therefore widely used in paints, adhesives, binders, coating agents, and the like.
In recent years, many water-based polyurethane resin compositions have been reported from the viewpoint of safety against environmental pollution, occupational health, etc., but water-based polyurethane resin compositions are more resistant to water than solvent-based or solvent-free ones. There is a problem that physical properties such as heat resistance and adhesiveness are inferior.

When using a water-based polyurethane resin composition as a gravure ink for laminating or a coating agent, it is necessary to have excellent physical properties such as water resistance, heat resistance, and tensile properties. It is necessary to have excellent adhesion, tack and blocking resistance, for example, an aqueous polyurethane resin reacted with a specific hydroxycarboxylic acid, a binder for printing ink using the same (Patent Document 1), and a polyol component. For example, an aqueous polyurethane resin composition using polyester glycol and a polyol having 3 or more hydroxyl groups, and a coating agent for a plastic film (Patent Document 2) using the aqueous polyurethane resin composition have been reported.
However, the performance of these urethane resins is not fully satisfactory.

In recent years, water-based polyurethane resin compositions have begun to be used as coating layers for the purpose of improving the adhesion of polyester films used as optical films.

Among the polyester films, the biaxially stretched polyester film used particularly for optics is excellent in transparency, dimensional stability, mechanical properties, heat resistance, electrical properties, gas barrier properties, chemical resistance, etc. In addition to plate making materials, display materials, transfer materials, window pasting materials, etc., they are used in membrane switches, antireflection films used for flat displays, optical films such as diffusion sheets, prism sheets, transparent touch panels and the like.
However, in these applications, when other materials are applied or laminated on the polyester film, there is a problem that the adhesiveness deteriorates depending on the materials used.

Moreover, as one method for improving the adhesiveness of a polyester film, a method is known in which various resins are applied to the surface of the polyester film and an application layer having an easy adhesion property is provided.
For example, acrylic resin using melamine as a crosslinking agent (Patent Document 3), acrylic resin using oxazoline as a crosslinking agent, urethane resin or polyester resin (Patent Document 4), copolymerized polyester resin and polyurethane resin (Patent Document 5), specific (Patent Documents 6 to 9) using a polyurethane resin as a coating agent is disclosed.

However, in such an existing easily-adhesive coating layer, when an active energy ray curable resin such as a UV curable resin is used as a top coat layer (hard coat layer), compared to the case where a solvent-based top coat is used, The active energy ray curable resin such as a curable resin has a low degree of penetration into the easy-adhesion layer, and the effect of swelling the easy-adhesion layer is small, so that there is a drawback that a sufficient adhesive force cannot be obtained.

Furthermore, a polyester film having a hard coat layer such as an easily adhesive coating layer and an active energy ray curable resin layer has a haze due to factors such as a difference in refractive index between the coating layer and the polyester film and hard coat layer. There is also a problem that the transparency is lowered and the transparency is lowered.

JP 2004-231813 A JP 2002-234931 A Japanese Patent Laid-Open No. 08-281890 Japanese Patent Laid-Open No. 11-286092 JP 2000-229395 A JP-A-61-261326 Japanese Patent Laid-Open No. 01-218832 Japanese Patent Laid-Open No. 02-158633 JP 2009-220376 A

Accordingly, a first object of the present invention is to provide a water-based polyurethane resin composition that is excellent in adhesion to a synthetic resin or ink, tackiness after application, and blocking resistance.
Moreover, the 2nd objective of this invention is providing the easily adhesive polyester film excellent in the transparency (haze) of a film while being excellent in adhesiveness with a base film and energy-beam curable resin.

As a result of intensive studies in order to achieve the above various objects, the present inventors have solved the above problems by using an aqueous polyurethane resin composition containing a hydrophilic compound having a specific structure as an essential component. It has been found that it can be solved, and the present invention has been reached.

That is, the present invention comprises (A) polyol, (B) polyisocyanate, (C) a hydrophilic compound represented by the following general formula (1), and (D) a monohydroxy vinyl ether compound represented by the following general formula (2). And an aqueous polyurethane resin composition containing water as an essential component, wherein the alkylene oxide unit represented by (C ₂ H ₄ -O) _n in the component (C) is the components (A) to (D). An aqueous polyurethane resin composition characterized in that the solid content is 3 to 20% by mass and the content of the component (D) is 3 to 25% by mass of the solids; A coating agent comprising a polyurethane resin composition; an easy adhesion comprising an easy adhesion layer formed by applying the aqueous polyurethane resin composition to at least one surface of a polyester film Polyester film; and, on the polyurethane resin layer of the easy adhesive polyester film is an optical film characterized by having a hard coat layer further composed of an active energy ray curable resin.

In the formula, R ¹ is a residue obtained by removing one hydroxyl group from a divalent to tetravalent alcohol or a group represented by RNHCO—, R ² is a methyl group or an ethyl group, and n is an integer of 5 to 35. And R is a residue obtained by removing one isocyanate group from a trimer compound of diisocyanate.

In the formula, R ³ is an alkylene group having 2 to 9 carbon atoms, and m is 1 or 2.

R ^{1 in the} general formula (1) is a residue obtained by removing one hydroxyl group from a trivalent alcohol, and n is preferably an integer of 10 to 20.
The average particle size of the dispersoid in the aqueous polyurethane resin composition is preferably 100 nm or less.

The aqueous polyurethane resin composition of the present invention is excellent in adhesion to a substrate, adhesiveness and blocking resistance, and can be suitably used as a coating agent or an adhesive. In particular, by applying the aqueous polyurethane resin composition of the present invention to the surface of a polyester film, an easily adhesive polyester film having low haze, good transparency, and good adhesion to the hard coat layer is obtained. be able to.

The aqueous polyurethane resin composition of the present invention is represented by (A) a polyol, (B) a polyisocyanate, (C) a hydrophilic compound represented by the general formula (1), and (D) the general formula (2). A monohydroxy vinyl ether compound and water.

The (A) polyol is not particularly limited, and examples thereof include polyether polyols, polyester polyols, polyester polycarbonate polyols, and crystalline or non-crystalline polycarbonate polyols.

Examples of the polyether polyols include low molecular polyols having a number average molecular weight of less than 200, bisphenol A, or ethylene oxide and / or propylene oxide adducts such as amine compounds such as ethylenediamine; and polytetramethylene ether glycol Etc.

Examples of the low molecular polyols having a number average molecular weight of less than 200 include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, diethylene glycol, triethylene glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanedio , Aliphatic diols such as 1,9-nonanediol, cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol; trimethylolethane, trimethylolpropane, hexitols, pentitols, glycerin, polyglycerin, pentaerythritol, Examples thereof include trivalent or higher polyols such as dipentaerythritol and tetramethylolpropane.

Examples of the polyester polyols include a direct esterification reaction or ester of a polyol such as a low molecular weight polyol having a number average molecular weight of less than 200 and a polycarboxylic acid having an amount less than the stoichiometric amount, or an ester-forming derivative thereof. And polyester polyols obtained by a direct esterification reaction between the polyol and a lactone or a hydroxycarboxylic acid obtained by a hydrolytic ring-opening reaction thereof.

Examples of the polyvalent carboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 2-methylsuccinic acid, and 2-methyladipine. Fats such as acid, 3-methyladipic acid, 3-methylpentanedioic acid, 2-methyloctanedioic acid, 3,8-dimethyldecanedioic acid, 3,7-dimethyldecanedioic acid, hydrogenated dimer acid, dimer acid Aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; tricarboxylic acids such as trimellitic acid, trimesic acid and castor oil fatty acid trimer A tetravalent or higher carboxylic acid such as pyromellitic acid.

Examples of the ester-forming derivative of the polyvalent carboxylic acid include the above-mentioned polycarboxylic acid anhydrides; carboxylic acid halides such as chloride and bromide; methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, And lower aliphatic esters such as amyl ester.

Examples of the lactones include γ-caprolactone, δ-caprolactone, ε-caprolactone, dimethyl-ε-caprolactone, δ-valerolactone, γ-valerolactone, and γ-butyrolactone.

Examples of the polyester polycarbonate polyols were obtained by reacting a reaction product of polyester glycol such as polycaprolactone polyol with alkylene carbonate and a reaction product of ethylene carbonate with polyhydric alcohol with an organic dicarboxylic acid. Reaction products are mentioned.

Examples of the crystalline or non-crystalline polycarbonate polyol include 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polypropylene glycol, and / or polytetramethylene. A reaction product of a diol such as glycol and a diaryl carbonate such as phosgene or diphenyl carbonate or a cyclic carbonate such as propylene carbonate may be used.

The polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline polycarbonate polyols, and amorphous polycarbonate polyols preferably have a number average molecular weight of 300 to 5,000, more preferably 500 to 3,000. preferable.
Among these polyols, in the water-based polyurethane resin composition of the present invention, it is particularly preferable to use polycarbonate polyols because adhesion under wet heat is improved.
In the present invention, only one kind of the polyol may be used, or two or more kinds may be used in combination.
Moreover, you may use together these polyols and the low molecular polyols whose number average molecular weights are less than 200 mentioned above.

The (B) polyisocyanate is not particularly limited, and examples thereof include a diisocyanate and a polyisocyanate having three or more isocyanate groups in one molecule.
Examples of diisocyanates include tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate. , Aromatic diisocyanates such as dianisidine diisocyanate and tetramethylxylylene diisocyanate; cycloaliphatic such as isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, trans and / or cis-1,4-cyclohexane diisocyanate, norbornene diisocyanate Diisocyanates; 1,6-hexamethylene diisocyanate, 2,2,4 and / or (2,4,4) -trimethylhexamethylene diisocyanate And aliphatic diisocyanates such as lysine diisocyanate.

Examples of polyisocyanates having 3 or more isocyanate groups in one molecule include triphenylmethane triisocyanate, 1-methylbenzole-2,4,6-triisocyanate, dimethyltriphenylmethane tetraisocyanate, and mixtures thereof. Trifunctional or higher isocyanates, carbodiimide-modified, isocyanurate-modified, biuret-modified, etc. of these trifunctional or higher isocyanates, blocked isocyanates in which these are blocked with various blocking agents, isocyanurates of diisocyanates described above (trimers) ) And biuret trimer.

Among these, it is preferable to use an aliphatic diisocyanate or an alicyclic diisocyanate in the present invention because it is easily available and an aqueous polyurethane resin composition excellent in weather resistance and strength is obtained. , 6-hexamethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, isophorone diisocyanate are particularly preferred.
In the present invention, only one kind of these polyisocyanates may be used, or two or more kinds may be used in combination.

In the hydrophilic compound represented by (C) the general formula (1), R ¹ represents a residue obtained by removing one hydroxyl group from a divalent to tetravalent alcohol, or a group represented by RNHCO-.
Examples of the divalent to tetravalent alcohols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentane Diol, 2-methyl-2,4-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 3,5-heptanediol, 1,8 -Aliphatic diols such as octanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, And dihydric alcohols such as cycloaliphatic diols such as cyclohexanedimethanol and cyclohexanediol; 3-4 such as trimethylolethane, trimethylolpropane, glycerin, diglycerin, pentaerythritol, tetramethylolpropane, etc. Valent alcohols.
In the aqueous polyurethane resin composition of the present invention, since (C) the hydrophilic compound is easily incorporated into the urethane main chain, R ¹ is a residue obtained by removing one hydroxyl group from a trivalent to tetravalent alcohol. Among them, R ¹ is preferably one hydroxyl group from a trivalent alcohol, since a crosslinking reaction or a terminal termination reaction is not caused at the time of urethane formation by reaction of the hydrophilic compound (C) and (B) isocyanate. The residue is preferably a residue obtained by removing one hydroxyl group from trimethylolpropane.

Further, R in the group represented by RNHCO— is a residue obtained by removing one isocyanate group from a diisocyanate trimer compound.
Examples of the diisocyanate constituting the trimer compound include the diisocyanates mentioned in the description of the (B) isocyanate.
Of these, aliphatic diisocyanates or alicyclic diisocyanates are preferably used from the viewpoint that they can be easily obtained and an aqueous polyurethane resin composition having excellent weather resistance and strength can be obtained. It is particularly preferable to use hexamethylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, or isophorone diisocyanate.

In the general formula (1), n is an integer of 5 to 35, and more preferably an integer of 10 to 20 from the viewpoint of improving the water dispersibility of the resulting urethane prepolymer.

Examples of the alkylene group represented by R ³ in the monohydroxy vinyl ether compound represented by the general formula (2) (D) include 2-9, for example, ethylene, propylene, isopropylene, butylene, isobutylene, Examples include dibutylene, tertiary butylene, pentylene, second pentylene, tertiary pentylene, hexylene, cyclohexylene, heptylene, octylene, isooctylene, 2-ethylhexylene, tertiary octylene, nonylene, and isononylene.
M is 1 or 2, but is preferably 1.

Specific examples of the compound represented by the general formula (2) include hydroxymethyl vinyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, Examples thereof include hydroxyvinyl ether compounds such as 6-hydroxyhexyl vinyl ether, 9-hydroxynonyl vinyl ether, and diethylene glycol monovinyl ether.

The content of the hydrophilic compound (C) in the aqueous polyurethane resin composition of the present invention is such that the alkylene oxide unit represented by (C ₂ H ₄ —O) _n in the general formula (1) is a urethane prepolymer solid content. The amount is preferably 3 to 20% by mass, and more preferably 5 to 16% by mass. However, the mass of the solid content of the urethane prepolymer is the total amount of the components (A) to (D).
When the alkylene oxide unit is less than 3% by mass, the water dispersibility of the urethane prepolymer is inferior, and when the amount exceeds 20% by mass, the tensile strength of the urethane resin coating film, and the adhesion to the substrate, etc. There exists a tendency for the physical property of a coating film to fall.

Further, the content of the (D) monohydroxy vinyl ether compound is 3 to 25% by mass, preferably 5 to 20% by mass, based on the solid content of the urethane prepolymer.
(D) When the content of the monohydroxy vinyl ether compound is less than 3% by mass, the adhesive effect of the present invention is insufficient, and when it exceeds 25% by mass, tack and haze in the highly adhesive polyester film of the present invention are achieved. Etc. tend to be inferior.

Further, the blending amount of the components (A) to (D) is such that the ratio (NCO / OH) of the total isocyanate group equivalent to the total hydroxyl group equivalent of the components (A) to (D) is 1.1 to 2.5. Such a blending amount is preferable, a blending amount of 1.2 to 2.0 is more preferable, and a blending amount of 1.3 to 1.8 is particularly preferable.
Total hydroxyl equivalent is the total amount of hydroxyl equivalents of (A) polyol, (C) hydrophilic compound and (D) monohydroxy vinyl ether compound, and total isocyanate equivalent is (B) isocyanate equivalent of isocyanate, or (C) When the hydrophilic compound contains an isocyanate group, it is the total amount of the isocyanate group equivalents of the component (B) and the component (C).

When the NCO / OH ratio is 1.0 or more and less than 1.1, since the urethane prepolymer has a relatively high molecular weight, the dispersibility of the urethane prepolymer in water tends to be poor. When the prepolymer exceeds 2.5, production problems such as rapid foaming due to the generation of carbon dioxide associated with the reaction between the isocyanate group and water, and the coating film There may be a problem in the performance of the water-based polyurethane resin that effects such as adhesion to the base resin tend to be inferior.
Further, when the NCO / OH ratio is less than 1.0, a urethane prepolymer having a terminal hydroxyl group is obtained, but the viewpoint that the terminal isocyanate prepolymer is superior in water dispersibility and easy to increase the molecular weight by chain elongation. Therefore, it is generally preferable to produce a terminal isocyanate prepolymer.

The production method of the aqueous polyurethane resin composition of the present invention is not particularly limited, and a known method can be used, for example, (A) polyol and (B) isocyanate, (C) hydrophilic compound, (D) A monohydroxy vinyl ether compound and, if necessary, an ionic group introducing agent are reacted to synthesize a urethane prepolymer. The resulting urethane prepolymer is dispersed in water to obtain a urethane resin, and then chain extended in water. There is a method of chain extension using an agent.
In the synthesis of the urethane prepolymer, a solvent which is inert to the reaction and has a high affinity with water can be used as necessary.
As a method for dispersing the urethane prepolymer in water, there are (1) a prepolymer mixing method in which the prepolymer is added and dispersed in water, and (2) a phase inversion method in which water is added and dispersed in the prepolymer.
When it is necessary to add an ionic group neutralizing agent and / or an emulsifier during water dispersion of the urethane prepolymer, it may be added to water or to the urethane prepolymer. The emulsifier is added to water.

Preferable examples of the solvent which is inert to the reaction and has a high affinity with water include acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, N-methyl-2-pyrrolidone and the like.
The amount of these solvents used is 3 to 100 parts by mass with respect to 100 parts by mass of the total amount of the raw materials (A) to (D) and the ion group introduction component used for producing the prepolymer. .
Of these solvents, when a solvent having a boiling point of 100 ° C. or lower is used, it is preferable to synthesize the aqueous polyurethane resin and then remove the solvent by distillation under reduced pressure or the like.

Examples of the ionic group introducing agent include an anionic group introducing agent and a cationic group introducing agent.
Examples of anionic group-introducing agents include polyols containing carboxyl groups such as dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolvaleric acid, and 1,4-butanediol-2-sulfonic acid These polyols containing sulfonic acid groups of
Examples of cationic group introducing agents include N, N-dialkylalkanolamines; N-alkyl-N, N— such as N-methyl-N, N-diethanolamine and N-butyl-N, N-diethanolamine. Dialkanolamines; and trialkanolamines.

The blending amount of the ionic group introducing agent is preferably 0 to 30% by mass, preferably 0 to 20% by mass, of the urethane prepolymer comprising the components (A) to (D) and the ionic group introducing agent. Is more preferable, and 0 to 10% by mass is particularly preferable. When the content of the ionic group introducing agent exceeds 30% by mass, the viscosity of the urethane prepolymer increases as the cohesive energy of the urethane bond increases, causing problems such as difficulty in water dispersion.

Examples of the ionic group neutralizer include an anionic group neutralizer and a cationic group neutralizer.
Examples of anionic group neutralizing agents include trialkylamines such as trimethylamine, triethylamine, and tributylamine; N, N-dimethylethanolamine, N, N-dimethylpropanolamine, N, N-dipropylethanolamine, 1 -N, N-dialkylalkanolamines such as dimethylamino-2-methyl-2-propanol; tertiary amines such as trialkanolamines such as N-alkyl-N, N-dialkanolamines and triethanolamine Compound: Basic compounds such as ammonia, trimethylammonium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like can be mentioned.
Examples of cationic group neutralizers include organic carboxylic acids such as formic acid, acetic acid, lactic acid, succinic acid, glutaric acid, and citric acid; organic sulfonic acids such as paratoluenesulfonic acid and alkyl sulfonate; hydrochloric acid, phosphorus Inorganic acids such as acid, nitric acid and sulfonic acid; epoxy compounds such as epihalohydrin and the like, and quaternizing agents such as dialkyl sulfuric acid and alkyl halides may be mentioned.

The amount of the ionic group neutralizing agent used is preferably 0.5 to 2.0 equivalents, more preferably 0.8 to 1.5 equivalents, relative to 1 equivalent of the ionic group.
When the amount of the neutralizing agent used is less than 0.5 equivalent or more than 2.0 equivalent, the storage stability of the water-based polyurethane resin and the physical properties such as strength and elongation of the water-based polyurethane resin film may be lowered.

Examples of the emulsifier include ordinary anionic surfactants and nonionic surfactants, and primary amine salts, secondary amine salts, tertiary amine salts, quaternary amine salts, pyridinium salts, and the like. Known emulsifiers such as cationic surfactants and amphoteric surfactants such as betaine type, sulfate type and sulfonic acid type can be exemplified.

Examples of the anionic surfactant include alkyl sulfates such as sodium dodecyl sulfate, potassium dodecyl sulfate and ammonium dodecyl sulfate; polyoxyethylene ether sulfates such as sodium dodecyl polyglycol ether sulfate and ammonium polyoxyethylene alkyl ether sulfate; sodium Sulfolicinolate; Alkyl sulfonates such as alkali metal salts of sulfonated paraffins and ammonium salts of sulfonated paraffins; Fatty acid salts such as sodium laurate, triethanolamine oleate and tolethanolamine abiates; Sodium benzene sulfonate, Alkaline phenol hydroxyethylene Alkyl aryl sulfones such as alkali metal sulfate High alkyl naphthalene sulfonate; naphthalene sulfonic acid formalin condensate; dialkyl sulfosuccinate; polyoxyethylene alkyl sulfate salt; polyoxyethylene alkyl aryl sulfate salt; polyoxyethylene ether phosphate; polyoxyethylene alkyl ether acetic acid Salt; N-acyl amino acid salt; N-acylmethyl taurine salt and the like.

Examples of the nonionic surfactant include fatty acid partial esters of polyhydric alcohols such as sorbitan monolaurate and sorbitan monooleate; polyoxyethylene glycol fatty acid esters; polyglycerin fatty acid esters; and alcohols having 1 to 18 carbon atoms. Examples include ethylene oxide and / or propylene oxide adduct; ethylene oxide and / or propylene oxide adduct of alkylphenol; ethylene glycol and / or propylene oxide adduct of alkylene glycol and / or alkylene diamine.
Examples of the alcohol having 1 to 18 carbon atoms constituting these nonionic surfactants include methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, tertiary butanol, amyl alcohol, isoamyl alcohol, and tertiary amyl alcohol. Hexanol, octanol, decane alcohol, lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like.

Examples of the alkylphenol include phenol, methylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 3,5-di-tert-butylphenol, 4- (1,3-tetramethylbutyl) phenol, 4-isooctylphenol, 4-nonylphenol, 4-tert-octylphenol, 4-dodecylphenol, 2- (3,5-dimethylheptyl) phenol, 4- (3,5-dimethylheptyl) phenol, naphthol, bisphenol A, bisphenol F etc. are mentioned.

Examples of the alkylene glycol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1 , 4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 1,6-hexanediol, etc. It is done.
Moreover, as alkylenediamine, what substituted the alcoholic hydroxyl group of these alkylene glycol by the amino group etc. are mentioned.
The ethylene oxide and propylene oxide adducts of these compounds may be random adducts or block adducts.

Examples of the cationic surfactant include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, didecyldimethylammonium chloride, laurylbenzyldimethylammonium chloride, didecyldimethylammonium chloride, alkylpyridinium bromide and imidazolinium. Examples thereof include laurate.

Examples of the amphoteric surfactant include coconut oil fatty acid amidopropyldimethylacetate betaine, lauryldimethylamino acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxymethylimidazolinium betaine, laurylhydroxysulfobetaine, lauroylamidoethylhydroxyethyl Examples include betaine types such as metal salts of carboxymethyl betaine and hydroxypropyl phosphate; amino acid types such as metal salts of β-laurylaminopropionic acid, sulfate ester types, and sulfonic acid types.

The amount of the emulsifier component used is not particularly limited, but from the viewpoint of physical properties such as the strength and elongation of the coating film obtained by applying the aqueous polyurethane resin composition, the total amount of polyurethane resin solids is 100 parts by mass. The amount is preferably 0 to 30 parts by mass, and more preferably 0 to 20 parts by mass. When it exceeds 30 mass parts, there exists a possibility that the physical property of an above-described urethane resin film may fall.

As the chain extender, it can be used by appropriately selecting from the conventionally used chain extenders such as the low molecular weight polyol compound having a number average molecular weight of less than 200 and the low molecular polyamine compound.
Such chain extender components include, for example, low molecular diols such as ethylene diamine, propylene diamine, hexamethylene diamine, tolylene diamine, piperazine, 2-methylpiperazine and the like; Polyether diamines such as diamine and polyoxyethylene diamine; mensen diamine, isophorone diamine, norbornene diamine, aminoethyleminoethanol, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, bis (aminomethyl) Cycloaliphatic diamines such as cyclohexane, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane; m-xylenediamine, α- (m / p Aminophenyl) Ruamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldimethyldiphenylmethane, diaminodiethyldiphenylmethane, dimethylthiotoluenediamine, diethyltoluenediamine, α, α'-bis (4-aminophenyl) -p-diisopropylbenzene, etc. Polysamines such as aromatic diamines; succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, phthalic acid dihydrazide, hydrazine hydrate, 1,6-hexamethylenebis (N, N-dimethylsemicarbazide), 1,1, Examples include hydrazines such as 1 ′, 1′-tetramethyl-4,4 ′-(methylene-di-para-phenylene) disemicarbazide, and water.

The amount of the chain extender component used is such that the ratio of the isocyanate reactive group equivalent of the chain extender to the isocyanate group equivalent of the urethane prepolymer before the chain extension reaction is 0.1 to 1.0 from the viewpoint of physical properties of the urethane resin. It is preferable that the amount is as follows.

You may mix | blend the compound which has an unsaturated bond with the water-based polyurethane resin composition which concerns on this invention.
Examples of the compound having an unsaturated bond include ethylene, propylene, butylene, isobutylene, pentene, vinyl acetate, vinyl alcohol, styrene, acrylonitrile, (meth) acrylic acid, maleic acid, itaconic acid, crotonic acid, and (meth) acrylic. Examples include acid esters, urethane acrylates, and epoxy acrylates.
Examples of the (meth) acrylic acid ester include (meth) acrylic acid and alkyl alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, and octyl alcohol; ethylene Glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, neo Pentyl glycol, 3-methyl-2,4-pentanediol, 2,4-pentanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, etc. Low molecular weight diols; 2-methoxyethanol, 4-methoxybut Nord, ether alcohols polyoxyethylene glycol monomethyl ether; ester compounds of polyether diols such as polyoxyethylene glycol.

Moreover, a reaction terminator can be used for the water-based polyurethane composition according to the present invention, if necessary.
Examples of the reaction terminator include alcohol compounds and monoamine compounds. These may be used alone or in combination of two or more. Examples of the alcohol compound include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, hexanol, octanol and the like. Examples of the monoamine compound include ethylamine, propylamine, 2-propylamine, butylamine, 2- Alkylamines such as butylamine, tert-butylamine and isobutylamine; aromatic amines such as aniline, methylaniline, phenylnaphthylamine and naphthylamine; cycloaliphatic amines such as cyclohexaneamine and methylcyclohexaneamine; 2-methoxyethylamine and 3-methoxypropyl Amines, ether amines such as 2- (2-methoxyethoxy) ethylamine; ethanolamine, propanolamine, butylethanolamine, 1-amine Alkanolamines such as no-2-methyl-2-propanol, 2-amino-2-methylpropanol, diethanolamine, diisopropanolamine, dimethylaminopropylethanolamine, dipropanolamine, N-methylethanolamine, N-ethylethanolamine Etc.

Further, the aqueous polyurethane resin composition of the present invention can be used by blending a crosslinking agent as required. As the crosslinking agent, there are an internal crosslinking agent and an external crosslinking agent. The internal crosslinking agent is blended during the synthesis of the urethane prepolymer, and the external crosslinking agent is blended in the water-based polyurethane resin.

Examples of the internal crosslinking agent include melamine compounds such as melamine, monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, methylated methylol melamine, butylated methylol melamine, And low molecular polyol compounds having three hydroxyl groups such as trimethylolpropane.
Among these, it is preferable to use melamine which is excellent in dispersibility of the aqueous polyurethane resin composition.

Examples of the external crosslinking agent include adducts of urea, melamine, benzoguanamine, and the like with formaldehyde; amino resins such as alkyl ether compounds composed of these adducts and alcohols having 1 to 6 carbon atoms; multifunctional epoxy compounds; Polyfunctional isocyanate compound; Block isocyanate compound; Polyfunctional aziridine compound, etc. are mentioned.

Further, when the water-based polyurethane resin is anionic, a compound capable of reacting with an anionic group such as a carboxyl group or a sulfonic acid group can be used as a crosslinking agent. Examples of such compounds include epoxy compounds such as oxazoline compounds and water-soluble epoxy resins, water-dispersed isocyanates, carbodiimide compounds, aziridine compounds, melamine compounds, and zinc complexes. Among these, it is preferable to use an oxazoline compound, an epoxy compound, or a carbodiimide compound that easily reacts with an anionic group.

Further, the water-based polyurethane resin composition of the present invention can be appropriately diluted and used, and the solid content concentration is not particularly limited. From the viewpoint of dispersibility, coating film, operability for obtaining a molded article, and the like, the solid content concentration is preferably 1 to 65% by mass, and more preferably 5 to 50% by mass.

The average particle size of the dispersoid in the aqueous polyurethane resin composition of the present invention is preferably 100 nm or less, more preferably 50 nm or less, and particularly preferably 35 nm or less, as measured by a dynamic light scattering method. .
In particular, when using an easy-adhesive polyester film coated with the aqueous polyurethane resin composition of the present invention as an easy-adhesive layer for an optical film, if the average particle size of the dispersoid exceeds 100 nm, the haze value of the film is It becomes high and transparency tends to deteriorate. On the other hand, the smaller the average particle size, the lower the haze value and the better the transparency.

The aqueous polyurethane resin composition of the present invention is suitable for coating and adhesion of synthetic resins. In this case, the synthetic resin as the adherend or the coating object is not particularly limited. Examples of such a synthetic resin include α-olefin polymers such as polypropylene, high density polyethylene, low density polyethylene, linear low density polyethylene, polybutene-1, poly-3-methylpentene, or ethylene-vinyl acetate. Copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl alcohol copolymer, ethylene-propylene copolymer Polyolefins and copolymers thereof, such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer , Vinyl chloride-vinylidene chloride copolymer Halogen-containing resins such as vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-cyclohexyl maleimide copolymer; Petroleum resin; Coumarone resin; Polystyrene; Polyvinyl acetate; Acrylic resin; Styrene and / or α-methylstyrene and other monomers (eg, maleic anhydride, phenylmaleimide, methyl methacrylate, butadiene, acrylonitrile, etc.) Copolymer (for example, AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.); linear polyester such as polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate and polybutylene terephthalate; poly Thermoplastic resins and blends thereof, such as polyamides such as enylene oxide, polycaprolactam and polyhexamethylene adipamide, polycarbonate, polycarbonate / ABS resin, branched polycarbonate, polyacetal, polyphenylene sulfide, polyurethane, and fibrous resin And phenolic resins; and thermosetting resins such as urea resins, melamine resins, epoxy resins, and unsaturated polyester resins.
Furthermore, the water-based polyurethane resin composition of the present invention can also be used for coating and adhesion of elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber and styrene-butadiene copolymer rubber.

Moreover, various commonly used additives can be added to the aqueous polyurethane resin composition of the present invention as necessary. Examples of these additives include various weathering agents such as hindered amine light stabilizers, ultraviolet absorbers and antioxidants; silane coupling agents that give particularly strong adhesion to the substrate; colloidal silica, tetraalkoxy Silane and its condensation polymer; chelating agent; and epoxy compound, pigment, dye, film-forming aid, curing agent, external cross-linking agent, viscosity modifier, leveling agent, antifoaming agent, anti-gelling agent, radical scavenger, Examples include heat resistance imparting agents, inorganic and organic fillers, plasticizers, lubricants, antistatic agents, reinforcing agents, catalysts, thixotropic agents, antibacterial agents, antifungal agents, antiseptic agents, and rust inhibitors.

Examples of the hindered amine light stabilizer include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidylmethyl methacrylate, 2,2,6,6- Tetramethyl-4-piperidylmethyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetraca Boxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) ) · Bis (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) · bis (tridecyl) -1,2,3 4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4- Piperi Ruamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8 , 12-Tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8 , 12-tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s -Triazin-6-yl] -1,5,8, 12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6 -Ylamino] undecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6 -Ylamino] undecane, 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4 , 8,10-Tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy] ) Carbonyloxy] ethyl] -2,4,8,10-spiro [5.5] undecane.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). 2-hydroxybenzophenones; 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-third octylphenyl) benzotriazole, 2- (2-hydroxy-3) , 5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-th Octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole polyethylene glycol ester, 2- [2-hydroxy-3- (2-acryloyloxy) Ethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy-3- (2- Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzotriazole, 2- [2 -Hydroxy-5- (2-methacryloyloxyethyl) phenyl] ben Zotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-amyl-5- (2-methacryloyloxy) Ethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2- Methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxypropyl) 2- (2-hydroxyphene) such as phenyl] benzotriazole B) Benzotriazoles; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6 -Diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [ 2-hydroxy-4- (3-C12 to C13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2- Hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxy-3-allylphenol ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1, 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as 3,5-triazine; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3 , 5-ditertiarybutyl-4-hydroxybenzoate, octyl (3,5-ditertiarybutyl-4-hydroxy) benzoate, dodecyl (3,5-ditertiarybutyl-4-hydroxy) benzoate, tetradecyl (3 , 5-Ditertiarybutyl-4-hydroxy) benzoate, hexadecyl (3,5-ditertiarybutyl-4-hydroxy) benzoate, octadecyl (3,5- Benzoates such as di-tert-butyl-4-hydroxy) benzoate, behenyl (3,5-di-tert-butyl-4-hydroxy) benzoate; 2-ethyl-2′-ethoxyoxanilide, 2-ethoxy-4 Substituted oxanilides such as' -dodecyl oxanilide; cyanoacrylates such as ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate Various metal salts or metal chelates.
Examples of the metal salt or metal chelate include nickel or chromium salts or chelates.

Examples of the antioxidant include phosphorus-based, phenol-based, and sulfur-based antioxidants.
Examples of phosphorus antioxidants include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,5-di-tert-butylphenyl) phosphite, tris (nonylphenyl) Phosphite, tris (dinonylphenyl) phosphite, tris (mono, dimixed nonylphenyl) phosphite, diphenyl acid phosphite, 2,2′-methylenebis (4,6-ditertiarybutylphenyl) octyl phosphite, Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilauryl phosphite, di Butyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentyl glycol) 1,4-cyclohexanedimethyl diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphos Phyto, bis (2,5-ditertiarybutylphenyl) pentaerythritol diphosphite, bis (2,6-ditertiarybutyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-dicumyl) Phenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidenediphenyl phosphite, bis [2,2'-methylenebis (4,6-dia) Milphenyl)], isop Pyridene diphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1,3-tris (2-methyl-5-tert 3-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, tris (2-[(2,4,7,9-tetrakis-tert-butyldibenzo [ d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy Ethyl) amine, 2- (1,1-dimethylethyl) -6-methyl-4- [3-[[2,4,8,10-trakis (1,1-dimethylethyl) dibenzo [d, f] [ 1,3,2] dioxaphosphepin-6-yl] oxy] propyl] phenol 2-butyl-2-ethylpropanediol, 2,4,6-tritert-butylphenol monophosphite, and the like.

Examples of the phenolic antioxidant include 2,6-ditertiarybutyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditertiarybutyl-4- Hydroxyphenyl) propionate, distearyl (3,5-ditertiarybutyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditertiarybutyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl) -4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3 Bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (2,6-ditert-butylphenol), 4,4′-butylidenebis (6-tert-butyl- 3-methylphenol), 2,2′-ethylidenebis (4,6-ditert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris (2,6-dimethyl-3-hydroxy -4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-to (3,5-ditertiarybutyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,3,5-tris [(3,5-ditertiarybutyl-4-hydroxyphenyl) propionyl Oxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5′-ditert-butyl-4′-hydroxyphenyl) propionate] methane, 2-tert-butyl-4-methyl-6- (2-acrophenyl) Yloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl ] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propyl Pioneto], tocopherol and the like.

Examples of the sulfur-based antioxidant include dialkylthiodipropionates such as dilauryl, dimyristyl, myristyl stearyl, and distearyl esters of thiodipropionic acid, and pentaerythritol tetra (β-dodecyl mercaptopropionate). And β-alkyl mercaptopropionic esters of polyols.

The amount of each of the hindered amine light stabilizer, ultraviolet absorber, and antioxidant used is 0.001 to 10 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (D). Particularly preferred is 0.01 to 5 parts by mass. When the amount is less than 0.001 part by mass, a sufficient addition effect may not be obtained. When the amount is more than 10 parts by mass, the dispersibility and the physical properties of the coating may be adversely affected.

As a method of adding these hindered amine light stabilizers, ultraviolet absorbers or antioxidants, a method of adding to a polyol, a method of adding to a urethane prepolymer, a method of adding to a water phase at the time of water dispersion, and adding after water dispersion However, from the viewpoint of easy operation, a method of adding to a polyol and a method of adding to a urethane prepolymer are preferable.

Applications of the water-based polyurethane resin composition of the present invention include coating agents, adhesives, paints, surface modifiers, organic powder and / or inorganic powder binders, moldings, building materials, sealing agents, casting materials, and elastomers. , Foams, plastic raw materials, fiber treatment agents and the like.
More specifically, easy-adhesive polyester film coating agents, polyethylene, polypropylene, polyester, polycarbonate and other plastic coating agents, laminating adhesives, agricultural film coating agents, thermal paper coating agents, inkjet paper coating agents, Fiber coating agent, electronic material component coating agent, glass fiber sizing agent, gravure printing ink binder agent, steel plate paint, glass, slate, concrete and other inorganic structural materials, wood paint, fiber treatment agent, Examples include sponges, puffs, gloves, and condoms.

The film formed by applying the aqueous polyurethane resin of the present invention is a packaging material, window pasting material, ink jet recording material, substitute paper, polarizer protective film, photographic sensitive film, liquid crystal display / plasma display / organic EL / electronic. Examples thereof include a base film such as a display member such as paper. Among these uses, it is suitable for a plastic coating agent or adhesive, a binder for gravure printing ink, and an optically easily adhesive polyester film.

The type of polyester used in the easy-adhesive polyester film of the present invention is not particularly limited as long as it can be processed into a film, but it is a polyester using aromatic dicarboxylic acid as a dicarboxylic acid as a raw material. Preferably, for example, polyethylene terephthalate, polyethylene 2,6-naphthalate, polybutylene terephthalate, polyethylene α, β-bis (2-chlorophenoxy) ethane 4,4, -dicarboxylate, etc. Is mentioned. In particular, it is most preferable to use polyethylene terephthalate (PET) from the viewpoint of quality, economy and the like.

The polyester film may be an unstretched film, a uniaxially stretched film, or a biaxially stretched film, but when used as an easily adhesive polyester film for optics, a uniaxially or biaxially stretched film is exclusively used. It is used.

The water-based polyurethane resin composition of the present invention is used as the easy-adhesion layer of the easy-adhesive polyester film of the present invention. In this case, it is preferable to contain inorganic particles or organic particles in the composition in order to further improve the slipping property, the fixing property and the like.
The blending amount of the inorganic particles and organic particles is usually 0.5 to 10 parts by mass and preferably 1 to 5% by mass with respect to 100 parts by mass of the solid content of the aqueous polyurethane resin.
When the blending amount is less than 0.5% by mass, the blocking resistance of the film may be insufficient. When it exceeds 10% by mass, the transparency of the film is hindered and the sharpness of the image tends to decrease. .

Examples of inorganic particles include silicon dioxide, alumina, zirconium oxide, kaolin, talc, calcium carbonate, titanium oxide, barium oxide, carbon black, molybdenum sulfide, and antimony oxide, but they are inexpensive and have various particle sizes. It is preferred to use silicon dioxide.
As organic particles, for example, organic particles made of polystyrene or polyacrylate polymethacrylate resin having a crosslinked structure synthesized using a compound containing two or more carbon-carbon double bonds in one molecule such as divinylbenzene. Etc.

The optically easy-adhesive polyester film of the present invention can be appropriately produced by a known method, for example, as described below.
After sufficiently drying the polyethylene terephthalate resin in a vacuum, it is fed to an extruder, and melted and extruded from a T-die into a sheet of molten polyethylene terephthalate resin at about 280 ° C. on a rotating cooling roll, and cooled and solidified by an electrostatic application method. An unstretched polyethylene terephthalate sheet is obtained. The unstretched polyethylene terephthalate sheet may have a single layer configuration or a multilayer configuration by a coextrusion method.
Further, it is preferable that the polyethylene terephthalate resin does not substantially contain inert particles such as aluminum oxide and calcium carbonate which cause a decrease in transparency.

The obtained unstretched polyethylene terephthalate sheet is stretched 2.5 to 5.0 times in the longitudinal direction with a roll heated to 80 to 120 ° C. to obtain a uniaxially stretched polyethylene terephthalate film.
Further, the end of the film is gripped with a clip, led to a hot air zone heated to 70 to 140 ° C., and stretched 2.5 to 5.0 times in the width direction. Subsequently, it is guided to a heat treatment zone of 160 to 240 ° C., and heat treatment is performed for 1 to 60 seconds to complete crystal orientation.

In an arbitrary stage of the film production process, a coating liquid containing the aqueous polyurethane resin composition of the present invention is applied to at least one surface of the polyethylene terephthalate film to form an easy adhesion layer. The easy adhesion layer may be formed on both sides of the polyethylene terephthalate film.
The solid content concentration of the resin composition in the coating solution is preferably 2 to 35% by mass, and particularly preferably 4 to 15% by mass.

As a coating method of the coating solution, for example, brush coating, roller coating, spray coating, gravure coating, reverse roll coating, air knife coating, bar coating, curtain roll coating, dip coating, rod coating, doctor blade coating, etc. You can choose.

The easy-adhesion layer has a final dry thickness of 0.005 to 5 μm, preferably 0.05 to 2 μm, more preferably 0.05 to 0.5 μm.
When the thickness of the easy-adhesion layer is less than 0.005 μm, sufficient adhesion with the energy ray curable resin cannot be obtained. In addition, when the thickness of the coating layer exceeds 5 μm, when the films are stacked, the films are likely to be blocked by each other, or when the coated film is re-stretched to increase the strength of the film Furthermore, it tends to stick to the roll. The blocking problem is particularly prominent when an easy-adhesion layer is formed on both sides of the film.

In the easy-adhesion layer, other resins may be used in combination with the aqueous polyurethane resin composition of the present invention as long as the effect is not affected. Examples of the other resins include vinyl resins such as acrylic resins, polyester resins, alkyd resins, and polyvinyl alcohol. In the present invention, it is particularly preferable to use water-soluble polyester or polyvinyl alcohol in combination.
The blending ratio of the other resins used in combination with the solid content of the aqueous polyurethane resin composition of the present invention is preferably 0/100 to 50/50, more preferably 20/80 to 40/60 in terms of mass ratio. Is more preferable.

As a solvent other than water used for the coating solution, alcohols such as ethanol, isopropyl alcohol, and benzyl alcohol may be mixed so as to be in a range of less than 50% by mass. Furthermore, as long as it is less than 10% by mass of the coating solution, an organic solvent other than alcohols may be mixed within a range in which it can be dissolved.
However, the total amount of alcohols and other organic solvents is preferably less than 50% by mass of the coating solution.

The coating amount of the coating solution is preferably 0.05 g / m ² to 0.8 g / m ² , and more preferably 0.1 g / m ² to 0.5 g / m ² .
Moreover, it is preferable that the application quantity of the easily bonding layer after drying in the easily bonding polyester film of this invention is 0.01 g / m < ² > or more and less than 1 g / m < ² >.
If the coating amount after drying is less than 0.01 g / m ² , the adhesiveness may be reduced. If the coating amount after drying is 1 g / m ² or more, the coating will be affected by the drying air in the drying furnace. Is likely to occur.

From the viewpoint of realizing high transparency, the easily adhesive polyester film of the present invention preferably has a haze of less than 3.0%, more preferably less than 2.0%, and less than 1.0%. It is particularly preferred.

The optical film of the present invention can be obtained by further providing a hard coat layer made of an active energy ray curable resin on the easy adhesion layer of the easy adhesion polyester film of the present invention.
The active energy ray curable resin has a double bond such as an acryl group, and can be appropriately selected from known UV curable resins or electron beam curable resins. In the present invention, in particular, It is preferable to use a urethane acrylate resin, an epoxy acrylate resin, an unsaturated polyester resin, or the like.
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these.

<Manufacture of urethane prepolymer>
[Production Examples 1 to 6]
(A) polyol, (B) polyisocyanate, (C) hydrophilic compound, and (D) monohydroxy vinyl ether compound in the blending amounts shown in Table 1 below are blended and reacted at 80 to 100 ° C. for 2 to 3 hours. I let you.
After confirming that the isocyanate content reached a predetermined amount, the obtained urethane prepolymers were designated as PP-1 to PP-6.
[Comparative Production Examples 1 to 5]
Urethane prepolymers PP-7 to PP-11 were produced in the same manner as in Production Examples using the components (A) to (D) in the blending amounts shown in Table 2 below.

<Manufacture of water-based polyurethane resin>
The urethane prepolymers PP-1 to PP-6 obtained in the above production examples were poured into water so as to have a solid content of 20% by mass and dispersed at 30 to 40 ° C. for 30 minutes.
Next, ethylenediamine (hereinafter referred to as EDA) was added in such an amount that the ratio of the amino group equivalent to the isocyanate group equivalent of the urethane prepolymer (-NH / -NCO) (hereinafter referred to as EDA) was added to cause a chain extension reaction. The mixture was stirred for 1 to 2 hours until it was confirmed by an infrared spectrophotometer that the isocyanate group had disappeared, and aqueous polyurethane resin compositions PUD-1 to PUD-6 were obtained.

[Comparative Example 1]
Using the urethane prepolymers PP-7 to PP-11 obtained in the comparative production examples, aqueous polyurethane resin compositions PUD-7 to PUD-11 were obtained in the same manner as in Example 1.

The average particle size of the water-based polyurethane resin dispersed in the compositions obtained in Example 1 and Comparative Example 1 was measured by a dynamic light scattering method using LB-550 manufactured by Horiba Ltd.
The results are shown in Tables 1 and 2.

The aqueous polyurethane resin composition obtained in Example 1 and Comparative Example 1 was applied onto a stretched polypropylene film whose surface was corona discharge treated using a bar coater.
About the obtained coating film, adhesiveness, adhesiveness, and blocking resistance were evaluated on condition of the following. The results are shown in Tables 3 and 4.

<Adhesion evaluation method>
After the coated film was dried at 25 ° C. for 24 hours, the dried state of the coated surface was evaluated by finger touch according to the following criteria.
(Double-circle): Resin did not adhere to a finger and the fingerprint was not seen on the application surface at all.
○: The resin did not adhere to the finger, but a very small amount of fingerprint was seen on the coated surface.
Δ: Resin slightly adhered to fingers.
X: Resin adhered to the finger.

<Method for evaluating blocking resistance>
The coated film was dried by heating at 50 ° C. for 30 minutes, and then a load of 0.5 kg / cm ² was applied while the coated surfaces were in close contact with each other, and the coated film was left at a temperature of 40 ° C. After 24 hours from the start of standing, the site where the coated surfaces were bonded was observed for blocking and evaluated according to the following criteria. A: No blocking at all.
○: There was very little blocking.
Δ: Slightly blocking.
X: There was blocking.

<Ink adhesion evaluation method>
The coated film was heated at 50 ° C. for 30 minutes, and then ink was coated on the coated surface to obtain a test piece. The test piece was bent at a temperature of 180 ° C. with the ink surface facing outward. An 18 mm wide cellophane tape was pressure-bonded to the ink surface of the bent portion of the test piece, forcibly peeled, and observed for the presence or absence of ink peeling, and evaluated according to the following criteria.
A: There was no abnormality on the ink surface.
○: The ink surface peeled off very slightly.
Δ: The ink surface was slightly peeled off.
X: The ink surface was completely peeled off.

 

<Manufacture of easy-adhesive polyester film>
Polyethylene terephthalate having an intrinsic viscosity of 0.65 is dried by a conventional method and supplied to an extruder, melted at 290 ° C., extruded into a sheet, rapidly cooled on a cooling rotating roll using an electrostatic application casting method, and unstretched A PET film was prepared.
The obtained unstretched PET film was stretched 2.5 times at 85 ° C. in the longitudinal direction by a roll stretching method, and further stretched 1.3 times at 95 ° C. Next, water-based polyurethane resin compositions PUD-1 to PUD-6 were applied, respectively, stretched 3.2 times in the transverse direction at 120 ° C., and heat-treated at 225 ° C. to obtain each easily adhesive polyester film.

[Comparative Example 2]
Using the water-based polyurethane resin compositions PUD-7 to PUD-11, each easily adhesive polyester film was produced in the same manner as in Example 2.

<Haze evaluation>
Each easy-adhesive polyester film produced in Example 2 and Comparative Example 2 was cut into a size of 50 mm square, and a JIS was used using a haze measuring device (HM-150: manufactured by Murakami Color Research Laboratory Co., Ltd.). It measured by the method based on K7361 (ISO 13468), and evaluated with the following reference | standard. The results are shown in Tables 5 and 6.
A: Less than 1.0% (very good)
○: 1.0% or more and less than 3% (good)
Δ: 3.0% or more and less than 5% (somewhat poor)
×: 5.0% or more (defect)

<Manufacture of laminated polyester film>
Furthermore, 30 parts of dipentaerythritol hexaacrylate, 40 parts of tetrafunctional urethane acrylate, 27 parts of bisphenol A type epoxy acrylate, and 3 parts of 1-hydroxycyclohexyl phenyl ketone are formed on the easy adhesion layer of each of the easily adhesive polyester films obtained. The active energy ray curable resin is applied so that the thickness after curing is 3 μm, and a high pressure mercury lamp having an irradiation energy of 120 W / cm is used, and irradiation is performed for about 15 seconds from an irradiation distance of 150 mm, thereby applying a hard coat. A laminated polyester film (optical film) having a layer was obtained.

<Adhesion evaluation>
After the obtained laminated polyester film was subjected to the following conditions (1) to (3), 100 grid-like cuts reaching the base film through the coating layer in accordance with JIS-K5400, Attaching using a cutter guide with a gap of 1 mm, then sticking the cellophane adhesive tape on the cut-shaped cut surface, rubbing it completely with an eraser, and then peeling it off at a 90 ° peeling angle. Was observed and the adhesion was evaluated according to the following criteria.
The results are shown in Tables 5 and 6.
<Adhesion test conditions>
(1) Regular adhesion: 24 hours at 23 ° C./65% RH (2) Wet adhesion: 100 hours at 60 ° C./90% RH (3) Moist heat resistance: 300 hours at 60 ° C./90% RH Tested after standing for 24 hours at 23 ° C x 65% RH after standing for a specified time under each condition.
<Adhesion evaluation criteria>
A: Peeling area is less than 5% (very good)
○: peeling area is 5% or more and less than 15% (good)
Δ: peeling area 15% or more and less than 20% (slightly good)
X: Peeling area is 20% or more (defect)

The easily-adhesive polyester film of the present invention has excellent adhesion to a hard coat layer such as an energy beam-curable acrylic resin such as an electron beam or ultraviolet rays or a siloxane-based thermosetting resin, and is excellent in transparency. It was confirmed that
Moreover, it was confirmed that the transparency of the easily adhesive polyester film of the present invention is further improved by adjusting the average particle size of the urethane resin dispersed in the composition of the present invention to 35 nm or less.
As a result, the easily adhesive polyester film of the present invention is provided with a hard coat layer made of an energy ray curable resin on the easily adhesive layer, thereby reflecting as a member such as a liquid crystal display, plasma display, organic EL, and electronic paper. It can be suitably used for optical applications such as a protective film, a light diffusion sheet, a near-infrared shielding film, a transparent conductive film, an antiglare film, and a polarizer protective film, and further, a magnetic recording medium, a photographic material, and an inkjet recording material. It was confirmed that it can be suitably used as a substrate film such as dry laminate or adhesive tape.

Since the water-based polyurethane resin composition of the present invention is excellent in adhesiveness to synthetic resin, and adhesiveness and blocking resistance when applied to a synthetic resin film, it can be used in gravure ink binders for laminating, coating agents, paints, etc. The synthetic resin film to which the aqueous polyurethane resin composition of the present invention is applied is useful as a packaging material, a window pasting material, an ink jet recording material, a substitute paper, and the like.
In addition, the easily adhesive polyester film using the water-based polyurethane resin composition of the present invention has low haze and good transparency, and the optical film using the easily adhesive polyester film is resistant to moisture and heat. Therefore, it is particularly useful as a polarizer protective film, a photographic sensitive film, a display member such as a liquid crystal display, plasma display, organic EL, and electronic paper.

Claims (6)

1. Essentially, (A) polyol, (B) polyisocyanate, (C) hydrophilic compound represented by the following general formula (1), (D) monohydroxy vinyl ether compound represented by the following general formula (2), and water A water-based polyurethane resin composition as a component, wherein an alkylene oxide unit represented by (C ₂ H ₄ -O) _n in the component (C) is a solid content comprising the components (A) to (D). An aqueous polyurethane resin composition characterized in that the amount is 3 to 20% by mass, and the content of the component (D) is 3 to 25% by mass of the solid content;
   

   

   In the formula, R ¹ is a residue obtained by removing one hydroxyl group from a divalent to tetravalent alcohol or a group represented by RNHCO—, R ² is a methyl group or an ethyl group, and n is an integer of 5 to 35. And R is a residue obtained by removing one isocyanate group from a trimer compound of diisocyanate;
   

   

   In the formula, R ³ is an alkylene group having 2 to 9 carbon atoms, and m is 1 or 2.
2. The water-based polyurethane resin composition according to claim 1, wherein R ^{1 in the} general formula (1) is a residue obtained by removing one hydroxyl group from a trivalent alcohol, and n is an integer of 10 to 20. .
3. The water-based polyurethane resin composition according to claim 1 or 2, wherein the average particle size of the dispersoid is 100 nm or less.
4. A coating agent or an adhesive comprising the aqueous polyurethane resin composition according to claim 1.
5. An easy-adhesive polyester film having an easy-adhesion layer on at least one side of the polyester film, wherein the easy-adhesion layer is a layer formed by applying the aqueous polyurethane resin composition described in claim 1. Easy-adhesive polyester film.
6. 6. An optical film comprising a hard coat layer made of an active energy ray-curable resin on the easy-adhesion layer of the easy-adhesion polyester film according to claim 5.