JP2014065827A - Topcoat agent, and display device and touch panel including topcoat layer obtained by using topcoat agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a topcoat agent from which a coating film (topcoat layer) having such fingerprint resistance can be formed that even when a fingerprint adheres to the film, the fingerprint gradually becomes less visible with time, thereby an appearance failure is hardly induced, and that a fingerprint can be easily wiped off with a cloth or the like.SOLUTION: The topcoat agent comprises a cationic urethane resin (A) having an alicyclic structure and an aqueous medium (B). The cationic urethane resin (A) includes the alicyclic structure in an amount ranging from 2,000 mmol/kg to 5,500 mmol/kg with respect to the mass of the cationic urethane resin (A).

Description

  The present invention relates to a top coat agent that can be used for forming a top coat layer of, for example, a device or a touch panel for displaying characters and images.

  Coating agents are used in various applications including home appliances, building members, and automobiles for the purpose of imparting design properties to various substrate surfaces and protecting the substrate surfaces.

  As the application field of the coating agent becomes wide as described above, the required properties also vary widely.

  For example, in coating agents used for coating the surface of optical members such as touch panels and household appliances, fingerprints that adhere when touched with a finger, etc. are not noticeable. In many cases, a removable characteristic (fingerprint resistance) is required.

  Examples of the coating agent having excellent fingerprint resistance include, for example, an unsaturated double bond-containing acrylic copolymer, a bifunctional or higher unsaturated double bond-containing monomer, a polyether skeleton-containing urethane (meth) acrylate (A), and A composition containing a (meth) acrylate having a cyclic structure and containing at least one reactive unsaturated double bond and a refractive index of 1.52 or more is known (see, for example, Patent Document 1). ).

  By using the composition, a coating film (topcoat layer) having good fingerprint resistance can be formed, but the fingerprint once attached to the coating film surface is as long as it is not wiped off using a cloth or the like. Since it remains on the surface of the coating film and stands out, it may cause poor appearance.

JP 2010-191370 A

  The problem to be solved by the present invention is that the fingerprint is not noticeable over time even when the fingerprint is attached, and it is difficult to cause a bad appearance and can be easily wiped off with a cloth or the like. It is providing the topcoat agent which can form the coating film (topcoat layer) provided with property.

  As a result of studies to solve the above problems, the present inventors have found that the above problems can be solved by introducing a predetermined structure into the urethane resin.

  That is, the present invention contains a cationic urethane resin (A) having an aliphatic cyclic structure and an aqueous medium (B), and the cationic urethane resin (A) is a mass of the cationic urethane resin (A). It has an aliphatic cyclic structure in the range of 2,000 mmol / kg to 5,500 mmol / kg.

  If it is the top coat agent of the present invention, the top coat layer of touch panels provided in smart phones, automatic cash dispensers, ticket vending machines, etc. that are often touched, enamel leather products, glasses, windows that require aesthetics It can be used for forming a top coat layer such as glass or a windshield of a vehicle.

  The topcoat agent of the present invention contains a cationic urethane resin (A) having an aliphatic cyclic structure in the range of 2,000 mmol / kg to 5,500 mmol / kg and an aqueous medium (B), The cationic urethane resin (A) is dissolved or dispersed in the aqueous medium (B).

  As the cationic urethane resin (A) used in the present invention, one having an aliphatic cyclic structure is used for forming a coating film having excellent fingerprint resistance.

  Examples of the aliphatic cyclic structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a propylcyclohexyl group, a tricyclo [5,2,1,0,2,6] decyl group, and a bicyclo [ 4,3,0] -nonyl group, tricyclo [5,3,1,1] dodecyl group, propyltricyclo [5,3,1,1] dodecyl group, norbornene group, isobornyl group, dicyclopentanyl group, And an adamantyl group. Among them, it is preferable to use a cyclohexyl group, norbornene group, isobornyl group, or adamantyl group in order to form a topcoat layer having even better fingerprint resistance, and it is more preferable to use a cyclohexyl group.

  The aliphatic cyclic structure is present in a range of 2,000 mmol / kg to 5,500 mmol / kg with respect to the mass of the cationic urethane resin (A).

  Here, in place of the cationic urethane resin (A), when a urethane resin having an aliphatic cyclic structure ratio of less than 2,000 mmol / kg or a urethane resin exceeding 5,500 mmol / kg is used, it is excellent. In some cases, a coating film having high fingerprint resistance cannot be formed.

  When the aliphatic cyclic structure is present in a range of 2,500 mmol / kg to 4,000 mmol / kg with respect to the mass of the cationic urethane resin (A), it has further excellent fingerprint resistance. It is preferable when forming a coating film.

  As the cationic urethane resin (A), an aliphatic cyclic structure derived from a polyol (a1) having an aliphatic cyclic structure, which will be described later, is 100 mmol / kg to the mass of the cationic urethane resin (A). It is preferable to use the one having 2,500 mmol / kg in order to provide a more excellent fingerprint resistance and to form a coating film having good substrate followability and adhesion. The content of the aliphatic cyclic structure represents the amount of the aliphatic cyclic structure present in the urethane resin (A), and is the amount of the raw material used for the production of the urethane resin (A). Is based.

  In addition, the cationic urethane resin (A) used in the present invention has a cationic group for imparting good water dispersion stability and the like in the aqueous medium (B).

  As the cationic group, for example, a tertiary amino group or the like can be used. The tertiary amino group is quaternized with a part or all of which is neutralized with acetic acid, propionic acid or the like, or with a quaternizing agent such as dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride or the like. It may be a thing. The cationic group may be present in the side chain of the urethane resin as a molecular chain, a main chain structure constituting the urethane resin, or the urethane resin as a main chain.

  The cationic group is present in the range of 10 mmol / kg to 1,000 mmol / kg of the entire cationic urethane resin (A), and the cationic urethane resin (A) in the aqueous medium (B) is present. It is preferable for imparting good water dispersion stability, and more preferably in the range of 30 mmol / kg to 700 mmol / kg.

  The cationic urethane resin (A) has a high affinity with a fatty acid, which is one of the components of fingerprints, and further includes the following general groups containing a cationic group for forming a coating film in which fingerprints are less noticeable. It is preferable to use one having a structure represented by the formula [I].

[Wherein R ¹ represents an alkylene group having an aliphatic or aliphatic cyclic structure, a dihydric phenol residue, or a polyoxyalkylene group, and R ² and R ³ independently represent an aliphatic or aliphatic group. R ⁴ represents a hydrogen atom or a residue of a quaternizing agent introduced by a quaternization reaction, and X ⁻ represents an anionic counter ion. ]

  Moreover, the said cationic urethane resin (A) may have 1 or more types chosen from the group which consists of a hydrolysable silyl group and a silanol group.

  The hydrolyzable silyl group is a functional group in which the hydrolyzable group is directly bonded to a silicon atom, and examples thereof include a functional group represented by the following general formula. The hydrolyzable silyl group becomes a silanol group to be described later by being hydrolyzed.

(In the formula [II], R ⁵ is a monovalent organic group such as an alkyl group, aryl group or aralkyl group, and R ⁶ is a halogen atom, alkoxy group, acyloxy group, phenoxy group, aryloxy group, mercapto group, amino group. A group, an amide group, an aminooxy group, an iminooxy group or an alkenyloxy group, and x is an integer of 0 to 2.)

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, neopentyl, 1-methylbutyl, 2-methylbutyl, hexyl, and isohexyl groups. It is done.

  Examples of the aryl group include a phenyl group, a naphthyl group, and a 2-methylphenyl group. Examples of the aralkyl group include a benzyl group, a diphenylmethyl group, and a naphthylmethyl group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.

  Examples of the acyloxy group include acetoxy, propanoyloxy, butanoyloxy, phenylacetoxy, acetoacetoxy, and the like. Examples of the aryloxy group include phenyloxy, naphthyloxy, and the like. Examples of the group include an allyloxy group, a 1-propenyloxy group, and an isopropenyloxy group.

R ⁶ is preferably an alkoxy group from the viewpoint that it is easy to form a siloxane bond by hydrolysis condensation and to easily remove alcohol by-produced by condensation, and in particular, a methoxy group, an ethoxy group, a propoxy group, It is preferably an isopropoxy group or a butoxy group.

  The silanol group is a functional group in which a hydroxyl group is directly bonded to a silicon atom, and is a functional group mainly generated by hydrolysis of the hydrolyzable silyl group described above.

  The hydrolyzable silyl group or silanol group may be a functional group that is relatively easily hydrolytically condensed, such as a trimethoxysilyl group, a triethoxysilyl group, a methyldimethoxysilyl group, or a methyldiethoxysilyl group. preferable.

  In the topcoat agent containing the cationic urethane resin (A) having such a functional group, a cross-linking reaction proceeds between the functional groups of the hydrolyzable silyl group or silanol group, so that the water resistance is further improved. It is possible to form a coating film having The hydrolyzable silyl group or silanol group can improve the adhesion of the coating film to the glass substrate, and can further improve the durability of the coating film and the ease of wiping off the attached fingerprint.

  The hydrolyzable silyl group and silanol group are present in an amount of 10 mmol / kg to 400 mmol / kg with respect to the entire cationic urethane resin (A), so that the film forming property is excellent and the attached fingerprint can be easily wiped off. It is preferable when obtaining the topcoat agent which can form the outstanding coating film.

  The cationic urethane resin (A) preferably has a weight average molecular weight in the range of 5,000 to 500,000, preferably 20,000 to 100,000. It is preferable when obtaining the aqueous resin composition which is excellent in film forming property and can form the coating film excellent in water resistance.

  The cationic urethane resin (A) includes a polyol (a1) containing a polyol (a1-1) having an aliphatic cyclic structure and a polyol (a1-2) having a cationic group, and an aliphatic cyclic It can manufacture by making polyisocyanate (b1) containing polyisocyanate (b1-1) which has a structure react.

  As said polyol (a1), the polyol (a1-1) which has the said aliphatic cyclic structure, and the polyol (a1-2) which has a cationic group are used as an essential component, and another polyol is used as needed. Can be used in combination.

  Examples of the polyol (a1-1) having an aliphatic cyclic structure include cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5,2,1,0,2,6] decane-dimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4 , 3,0] nonanedimethanol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol 1,1'-bicyclohex It is possible to use a polyol (a1-1-1) having an aliphatic cyclic structure having a low molecular weight of about 100 to 500, such as redenediol, cyclohexanetriol, hydrogenated bisphenol A, 1,3-adamantanediol. preferable. Among these, it is preferable to use cyclohexanedimethanol in order to form a topcoat layer having even better fingerprint resistance. In addition, the molecular weight of the polyol having the aliphatic cyclic structure is based on the formula weight.

  The polyol (a1-1) having an aliphatic cyclic structure is obtained by reacting the polyol (a1-1-1) having a low molecular weight aliphatic cyclic structure with another component. A polycarbonate polyol having an aliphatic cyclic structure, a polyester polyol having an aliphatic cyclic structure, a polyether polyol having an aliphatic cyclic structure, and the like can be used.

  Examples of the polycarbonate polyol having an aliphatic cyclic structure include those obtained by reacting the polyol (a1-1-1) having a low molecular weight aliphatic cyclic structure with dimethyl carbonate, phosgene and the like. Can be used.

  By using the polycarbonate polyol having the aliphatic cyclic structure, it is possible to form a top coat layer having excellent slip resistance as well as fingerprint resistance. The slipperiness is a characteristic that is preferably required for a topcoat layer such as a touch panel.

  As the polycarbonate polyol having an aliphatic cyclic structure, it is preferable to use a polycarbonate polyol having an aliphatic cyclic structure having a number average molecular weight of 800 to 3,000, and a number average molecular weight of 800 to 2,500. It is more preferable to use what has.

  Examples of the polyester polyol having an aliphatic cyclic structure include those obtained by esterifying a polyol (a1-1-1) having an aliphatic cyclic structure and a polycarboxylic acid, It is possible to use those obtained by esterifying the aliphatic polyol or aromatic polyol of the above and a polycarboxylic acid having an aliphatic cyclic structure.

  Examples of the polycarboxylic acid that can be esterified with the polyol (a1-1-1) having an aliphatic cyclic structure include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, and fumaric acid. 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, and anhydrides or ester-forming derivatives thereof Can do.

  Examples of the chain aliphatic polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 3-methylpentanediol. it can. As said aromatic polyol, bisphenol compounds, such as bisphenol A and bisphenol F, those alkylene oxide adducts, etc. can be used, for example.

  Examples of the polycarboxylic acid having an aliphatic cyclic structure that can be esterified with the chain aliphatic polyol or aromatic polyol include hexahydrophthalic acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexane. Dicarboxylic acids and their anhydrides can be used.

  Moreover, as the polyether polyol having the aliphatic cyclic structure, for example, the above-described polyol (a1-1-1) having a low molecular weight aliphatic cyclic structure is used as an initiator, for example, ethylene oxide or propylene oxide. A product obtained by addition polymerization of alkylene oxide can be used.

  Moreover, as a polyol (a1-2) which has a cationic group which can be used for manufacture of the said polyol (a1), the polyol which has a tertiary amino group can be used, for example, specifically, N-methyl- Diethanolamine, polyol (a1-2-1) obtained by reacting a compound having two epoxy groups with a secondary amine, or the like can be used.

  A part or all of the cationic group of the polyol (a1-2) may be neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, and adipic acid. The cationic urethane resin (A) may be produced using the polyol (a1-2) and then neutralized.

  Further, the tertiary amino group as the cationic group of the polyol (a1-2) may be partially or entirely quaternized, but the polyol (a1-2) may be used as a cationic urethane. You may quaternize after manufacturing resin (A).

  The polyol (a1-2-1) obtained by reacting a compound having two epoxy groups with a secondary amine can be used for introducing a cationic group into the side chain of the urethane resin. It can be used for introducing the structure represented by the general formula [I] into the cationic urethane resin (A).

  In the polyol (a1-2-1), for example, a compound having two epoxy groups and a secondary amine are blended so that the equivalent of the secondary amino group (NH group) is 1 equivalent to 1 equivalent of the epoxy group. It can be easily obtained by a ring-opening addition reaction at room temperature or under heating without a catalyst.

  Examples of the compound having two epoxy groups include ethanediol-1,2-diglycidyl ether, 1,2-propanediol-diglycidyl ether, 1,3-propanediol-diglycidyl ether, 1,4-butane. Diol-diglycidyl ether, 1,5-pentanediol-diglycidyl ether, 3-methyl-1,5-pentanediol-diglycidyl ether, neopentyl glycol-diglycidyl ether, 1,6-hexanediol-diglycidyl ether , Polybutadiene-diglycidyl ether, 1,4-cyclohexanedimethanol-diglycidyl ether, 2,2-bis (4-hydroxycyclohexyl) -propane (hydrogenated bisphenol A) diglycidyl ether, hydrogenated dihydroxydiphe Isomeric mixtures of Rumetan diglycidyl ether of (hydrogenated bisphenol F) can be used.

  Examples of the compound having two epoxy groups include resorcinol-diglycidyl ether, hydroquinone-diglycidyl ether, 2,2-bis (4-hydroxyphenyl) -propane (bisphenol A) diglycidyl ether, dihydroxydiphenylmethane. Diglycidyl ether of bisphenol F, diglycidyl ether of 4,4-dihydroxy-3-3'-dimethyldiphenylpropane, diglycidyl ether of 4,4-dihydroxydiphenylcyclohexane, 4,4-dihydroxydiphenyl Diglycidyl ether, 4,4-dihydroxydibenzophenone diglycidyl ether, bis (4-hydroxyphenyl) -1,1-ethane diglycidyl ether, bis (4-hydroxyphenyl) L) -1,1-isobutane diglycidyl ether, bis (4-hydroxy-3-tert-butylphenyl) -2,2-propane diglycidyl ether, bis (2-hydroxynaphthyl) methane diglycidyl ether, Diglycidyl ether of bis (4-hydroxyphenyl) sulfone (bisphenol S) or the like can be used.

  Examples of the compound having two epoxy groups include diethylene glycol-diglycidyl ether, dipropylene glycol-diglycidyl ether, and polyoxyalkylene glycol-diglycidyl ether having 3 to 60 repeating oxyalkylene units. Polyoxyethylene glycol-diglycidyl ether and polyoxypropylene glycol-diglycidyl ether, ethylene oxide-propylene oxide copolymer diglycidyl ether, polyoxytetraethylene glycol-diglycidyl ether, and the like can be used.

  Among these, in order to further improve the water dispersibility of the cationic urethane resin (A) and to form a coating film having further excellent fingerprint resistance, polyoxyalkylene glycol diglycidyl ether, particularly polyethylene glycol It is preferred to use diglycidyl ether and / or polypropylene glycol-diglycidyl ether and / or diglycidyl ether of ethylene oxide-propylene oxide copolymer.

  The epoxy equivalent of the diglycidyl ether of the polyoxyalkylene glycol is preferably 1000 g / equivalent or less, more preferably 500 g / equivalent or less.

  As the secondary amine, a known compound can be used, but a branched or straight chain aliphatic secondary amine is preferable from the viewpoint of easy reaction control.

  Examples of such secondary amine that can be used include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-sec-butylamine, di-n. -Pentylamine, di-n-peptylamine, di-n-octylamine, diisooctylamine, dinonylamine, diisononylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, di- Examples include n-pentadecylamine, di-n-octadecylamine, di-n-nonadecylamine, and di-n-eicosylamine.

  Among these, it is difficult to volatilize when the polyol (a1-2-1) is produced, or a part or all of the tertiary amino group contained is neutralized with an acid, or 4 with a quaternizing agent. For reasons such as the ability to reduce steric hindrance when classifying, an aliphatic secondary amine having 2 to 18 carbon atoms is preferred, and an aliphatic secondary amine having 3 to 8 carbon atoms is more preferred.

  The reaction between the compound having two epoxy groups and the secondary amine is a reaction ratio of the epoxy group possessed by the compound having two epoxy groups and the NH group possessed by the secondary amine [NH group / epoxy group. The equivalence ratio is preferably in the range of 0.5 / 1 to 1.1 / 1, more preferably in the range of 0.9 / 1 to 1/1.

  The reaction between the compound having two epoxy groups and the secondary amine can be carried out under solvent-free conditions, but for the purpose of facilitating the reaction control or reducing the stirring load by reducing the viscosity or evenly. In order to make it react, it can also carry out using an organic solvent.

  Such an organic solvent may be any organic solvent that does not inhibit the reaction, for example, a ketone such as acetone or methyl ethyl ketone, an ether such as tetrahydrofuran, an acetate such as ethyl acetate, a hydrocarbon such as n-hexane or toluene, a hydrocarbon such as dichloromethane, and the like. Chlorinated hydrocarbons and amides such as dimethylformamide can be used.

  Among the organic solvents described above, when an organic solvent having a low boiling point is used, it is preferable to perform a pressure reaction in a closed system in order to prevent scattering due to volatilization.

  The compound having two epoxy groups and the secondary amine may be fed together and reacted in a reaction vessel, or either one of the compound having two epoxy groups and the secondary amine is charged into the reaction vessel, You may make it react by dripping the other.

  The reaction between a compound having two epoxy groups and a secondary amine is usually highly reactive and does not usually require a catalyst. However, when the substituent of the secondary amine nitrogen atom is large and the reaction with the compound is slowed by steric hindrance, proton donating properties represented by phenol, acetic acid, water, alcohol, etc. The substance may be used as a catalyst.

The reaction temperature is preferably in the range of room temperature to 160 ° C, more preferably in the range of 60 to 120 ° C. The reaction time is not particularly limited, but is usually in the range of 30 minutes to 14 hours. The end point of the reaction can be confirmed by disappearance of the absorption peak near 842 cm ⁻¹ due to the epoxy group by infrared spectroscopy (IR method).

  The said polyol (a1-2) is 0.5 mass%-25 with respect to the whole quantity of the said polyol (a1) used for manufacture of the said cationic urethane resin (A) from a viewpoint which provides the outstanding storage stability. It is preferable to use in the range of mass%.

  As the polyol (a1) that can be used when the cationic urethane resin (A) is produced, other polyols can be used as necessary in addition to those described above.

  As said other polyol, what does not have an aliphatic cyclic structure or a cationic group can be used, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, diethylene glycol, Triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300 to 6,000), dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, bisphenol A, hydroquinone and the like Relatively low molecular weight polyols such as alkylene oxide adducts, polyester polyols, Ether polyols, polycarbonate polyols, polyacetal polyols, polyacrylate polyols, polyesteramide polyols, polythioether polyols, may also be used high molecular weight polyol such as polyolefin polyols such as polybutadiene.

  Examples of the polyester polyol include those obtained by an esterification reaction of a low molecular weight polyol and a polycarboxylic acid, polyesters obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone, and copolymers of these. Polymerized polyester or the like can be used.

  Examples of the polyether polyol include addition polymerization of alkylene oxides such as ethylene oxide and propylene oxide using one or more compounds having two or more active hydrogen atoms such as ethylene glycol and diethylene glycol as an initiator. Or polytetramethylene glycol can be used.

  Further, as the polycarbonate polyol, those obtained by reacting glycols such as 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol with dimethyl carbonate, phosgene and the like are used. be able to.

  Moreover, as the polyisocyanate (b1) used when the cationic urethane resin (A) is produced, a polyisocyanate (b1-1) having an aliphatic cyclic structure can be used, for example, cyclohexane diisocyanate, Dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like can be used. Among these, it is preferable to use dicyclohexylmethane diisocyanate or isophorone diisocyanate in order to form a topcoat layer that is further excellent in fingerprint resistance.

  Moreover, as said polyisocyanate (b1), polyisocyanate other than polyisocyanate (b1-1) which has an aliphatic cyclic structure can also be used, for example, 4,4'- diphenylmethane diisocyanate, 2,4'- Aromatic polyisocyanates such as diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, and aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate Isocyanates can be used.

  As said polyisocyanate (b1), when giving the outstanding fingerprint resistance, 90 mass of polyisocyanate (b1-1) which has the said aliphatic cyclic structure with respect to the whole quantity of the said polyisocyanate (b1). % Is preferably used in the range of 95% by mass or more and preferably in the range of 95% by mass to 100% by mass.

  The cationic urethane resin (A) may be used in the absence of a solvent, in the presence of an organic solvent, or in the presence of a reactive diluent, the polyol (a1), the polyisocyanate (b1), and the general formula [III The compound represented by the above is charged into a reaction vessel in a batch or divided and reacted to produce a urethane resin, and part or all of the tertiary amino groups in the resulting urethane resin are neutralized with an acid. And / or quaternization with a quaternizing agent.

  The reaction is performed such that the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol (a1) and the isocyanate group of the polyisocyanate (b1) is in the range of 0.9 / 1 to 2.0 / 1. Is preferred.

  Moreover, it is preferable to perform the said reaction in the temperature range of 20 to 120 degreeC, and it is more preferable to carry out in the temperature range of 30 to 100 degreeC.

  Examples of the organic solvent that can be used as the solvent when performing the reaction include ketones such as acetone, diethyl ketone, methyl ethyl ketone, and methyl isobutyl ketone; diethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran and dioxane; Acetic esters such as ethyl acetate, butyl acetate and propyl acetate; Nitriles such as acetonitrile; n-pentane, n-hexane, cyclohexane, n-heptane, benzene, toluene and xylene Hydrocarbons such as carbon tetrachloride, chlorinated hydrocarbons such as dichloromethane, chloroform, trichloroethane; dimethylformamide, N-methylpyrrolidone, etc. It may be used amides. If necessary, the organic solvent is preferably removed during the reaction or after the reaction, for example, by a method such as heating under reduced pressure.

  Examples of acids that can be used when neutralizing some or all of the cationic groups of the urethane resin (A) obtained by the above method include formic acid, acetic acid, propionic acid, succinic acid, and glutaric acid. , Butyric acid, lactic acid, malic acid, citric acid, tartaric acid, malonic acid, adipic acid and other organic acids, sulfonic acid, paratoluenesulfonic acid, methanesulfonic acid and other organic sulfonic acids, and hydrochloric acid, sulfuric acid, nitric acid, phosphorus Inorganic acids such as acid, boric acid, phosphorous acid, and hydrofluoric acid can be used.

  Examples of the quaternizing agent that can be used for quaternizing a part or all of the cationic group include dialkyl sulfates such as dimethyl sulfate and diethyl sulfate, methyl chloride, ethyl chloride, and benzyl. Alkyl halides such as chloride, methyl bromide, ethyl bromide, benzyl bromide, methyl iodide, ethyl iodide, benzyl iodide, etc., alkyl such as methyl methanesulfonate, methyl paratoluenesulfonate, methyl arylarylsulfonate, ethylene oxide, Epoxy such as propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, etc. It can be used.

  The amount of the acid or quaternizing agent is 0.1 to 3 equivalents with respect to 1 equivalent of the tertiary amino group in order to express the excellent storage stability of the aqueous dispersion of the cationic urethane resin (A). It is preferable that it is the range of 0.3, and it is more preferable that it is the range of 0.3-2 equivalent.

  When the cationic urethane resin (A) is produced, a chain extender can be used as necessary to improve the durability of the topcoat layer.

Examples of the polyamine that can be used as the chain extender include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, and 4,4′-dicyclohexylmethane. Diamines such as diamine, 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine Diamines containing one primary amino group and one secondary amino group such as N-ethylaminoethylamine and N-methylaminopropylamine; polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine
Examples of compounds that can be used for the chain extender include hydrazines such as hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic dihydrazide, adipic dihydrazide, glutaric dihydrazide, sebacine Dihydrazides such as acid dihydrazide and isophthalic acid dihydrazide; and semicarbazides such as β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazidemethyl-3,5,5-trimethylcyclohexane Can be used.

  When the chain extender is, for example, the polyamine or hydrazine, the urethane prepolymer isocyanate obtained by reacting the amino group of the chain extender with the polyol (a1) and the polyisocyanate (b1). It is preferably used in a range where the equivalent ratio with the group is 1.9 or less (equivalent ratio), and more preferably in the range of 0.3 to 1.0 (equivalent ratio). By using the chain extender in the above-described range, the durability of the top coat layer to be formed can be improved.

  The chain extender is preferably used in the range where the urea bond equivalent of the cationic urethane resin (A) is 500 to 50,000 in order to form a topcoat layer excellent in adhesion and durability.

  Moreover, when using what has a structure shown by the said general formula [II] as said cationic urethane resin (A), while forming the coating film excellent in the adhesiveness to a glass base material, especially In order to further improve the wiping property of fingerprints, in addition to the polyol (a1), the polyisocyanate (b1) and the chain extender, a compound having a structure represented by the following general formula [III] as necessary Can be used.

(In the formula [III], R ⁵ is a monovalent organic group such as an alkyl group, aryl group or aralkyl group, and R ⁶ is a halogen atom, alkoxy group, acyloxy group, phenoxy group, aryloxy group, mercapto group, amino group. A group, an amide group, an aminooxy group, an iminooxy group, or an alkenyloxy group, and x is an integer of 0 to 2. Y represents an organic residue containing at least one amino group.)

  Examples of the compound represented by the general formula [III] include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-hydroxylethyl) aminopropyltrimethoxysilane, and γ- (2-aminoethyl). ) Aminopropyltriethoxysilane, γ- (2-hydroxylethyl) aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-hydroxylethyl) aminopropylmethyldimethoxysilane, γ- (2-hydroxylethyl) aminopropylmethyldiethoxysilane or γ- (N, N-di-2-hydroxylethyl) aminopropyltriethoxysilane, γ -Aminopropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane or γ- (N-phenyl) aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptophenyltri Methoxysilane or the like can be used.

  Moreover, it is preferable that the compound shown by the said general formula [III] is the range of 0.1 mass%-10 mass% with respect to the total amount of the said polyol (a1) and polyisocyanate (b1).

  As a method for dissolving or dispersing the cationic urethane resin (A) obtained by the above method in the aqueous medium (B), for example, the cationic urethane resin (A) and the aqueous medium (B) are mixed and stirred. Can be manufactured. You may mix the said cationic urethane resin (A) and an aqueous medium (B) using machines, such as a homogenizer, as needed.

  Examples of the aqueous medium (B) include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycol; And lactams such as N-methyl-2-pyrrolidone. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.

  The topcoat agent obtained by the above method preferably contains 10% by mass to 65% by mass of the cationic urethane resin (A), and more preferably contains 15% by mass to 40% by mass.

  The top coat agent of the present invention obtained by the above method may include, for example, a film forming aid, a filler, a thixotropic agent, a tackifier, a pigment, an antibacterial agent, etc. It can be used as long as the object of the invention is not impaired.

  The film forming aid is not particularly limited, and examples thereof include anionic surfactants (such as dioctyl sulfosuccinate soda salt), hydrophobic nonionic surfactants (such as sorbitan monooleate), and silicone oil. It is done.

  Examples of the thixotropy-imparting agent include fatty acid, fatty acid metal salt, fatty acid ester, paraffin, resin acid, surfactant, polyacrylic acid and the like surface-treated filler, polyvinyl chloride powder, hydrogenated castor oil, Fine powder silica, organic bentonite, sepiolite and the like can be mentioned.

As the pigment, known and commonly used inorganic pigments and organic pigments can be used.
As the inorganic pigment, for example, titanium oxide, antimony red, bengara, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine, carbon black, graphite and the like can be used.

  Examples of the organic pigment include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, ansanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, Organic pigments such as diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments can be used. Two or more kinds of these pigments can be used in combination. These pigments may be surface-treated and have a self-dispersing ability with respect to an aqueous medium.

  As the antibacterial agent, for example, silver chloride, trifuranide, dichlorofluanide, fluorophorpet, zinc pyrithione, methyl 2-benzimidazole carbanate, 2- (4-thiazolyl) benzimidazole and the like can be used.

  Furthermore, other additives include, for example, reaction accelerators (metal-based, metal salt-based, amine-based, etc.), stabilizers (ultraviolet absorbers, antioxidants, heat-resistant stabilizers, etc.), moisture removal agents (4- And various additives such as adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.), adhesion-imparting agents, antifoaming agents, and leveling agents.

  The topcoat agent of the present invention can be suitably used, for example, as a coating agent for forming a topcoat layer used for functional protection such as surface protection, designability, and visibility improvement of various substrates.

  As a base material which can apply | coat the said topcoat agent and can form a topcoat layer, a glass base material, a metal base material, a plastic base material, paper, a wood base material, a fiber base material etc. are mentioned, for example. Moreover, it can also be used for the base material of porous body structures, such as a urethane foam.

  Examples of plastic base materials include polycarbonate base materials, polyester base materials, acrylonitrile-butadiene-styrene base materials, polyacryl base materials, polystyrene base materials, polyurethane base materials, epoxy resin base materials, polyvinyl chloride base materials, and polyamide base materials. Can be used.

  As said metal base material, galvanized steel plates, such as a galvanized steel plate and an aluminum zinc alloy steel plate, an iron plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate etc. can be used, for example.

  The base material may be a planar material made of the above material or may have a curved portion, or may be a base material made of fibers such as a nonwoven fabric.

  The top coat agent of the present invention is applied to the surface of the base material directly or on the surface of the base material on which a primer layer or the like has been previously provided, and then dried and cured, for example. A coat layer can be formed.

  Examples of a method for applying the top coat agent or the like on the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.

  In addition, a top coat layer is formed on the surface of the release paper by applying the top coat agent etc. on the release paper, then drying and curing, and further applying an adhesive or an adhesive on the top coat layer A top coat layer can be formed on the surface of the substrate by bonding to a substrate made of fibers such as nonwoven fabric and peeling the release paper.

  The method for drying and proceeding with curing may be a method of curing for about 1 to 10 days at room temperature, but from the viewpoint of rapidly proceeding curing, at a temperature of 50 to 250 ° C., 1 to A method of heating for about 600 seconds is preferable. Moreover, when using the plastic base material which is easy to deform | transform and discolor at comparatively high temperature, it is preferable to cure at comparatively low temperature of about 30 degreeC-100 degreeC.

  Although the film thickness of the topcoat layer formed using the topcoat agent of this invention can be suitably adjusted according to the use etc. which a base material is used for, it is preferable that it is normally about 0.1 micrometer-20 micrometers.

  As described above, the laminate in which the topcoat layer is provided on the base material has a fingerprint that is not noticeable even when touched by a finger, and can be easily wiped off by using a cloth or the like. For example, displays such as anti-reflection films, optical filters, optical lenses, spectacle lenses, mirrors, etc., touch panels provided in smartphones, automatic cash dispensers, ticket vending machines, etc. It can be used for top coat layers such as devices, home appliances and displays, enamel leather products that require aesthetics, glasses, window glass, and vehicle windshields.

  Hereinafter, the present invention will be specifically described by way of examples and comparative examples.

Synthesis Example 1 Synthesis of Polyol (Z) Having Tertiary Amino Group Polyethylene glycol-diglycidyl ether (epoxy equivalent 185 g / equivalent) in a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device ) After charging 543 parts by mass, the flask was purged with nitrogen. Next, after heating using an oil bath until the temperature in the flask reaches 70 ° C., 380 parts by mass of di-n-butylamine is added dropwise over 30 minutes using a dropping device. The reaction was allowed for 10 hours. After completion of the reaction, using an infrared spectrophotometer (FT / IR-460Plus, manufactured by JASCO Corporation), it is confirmed that the absorption peak near 842 cm ⁻¹ due to the epoxy group of the reaction product has disappeared. A polyol (Z) having a tertiary amino group (amine equivalent 315 g / equivalent, hydroxyl equivalent 315 g / equivalent) was prepared.

[Example 1]
A polyester polyol (hydroxyl value 59) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid and adipic acid in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device. 0.054 mg KOH / g) 554 parts by mass and polycarbonate polyol (hydroxyl value 111.4 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol, and 120 ° C. to 130 ° C. at a reduced pressure of 0.095 MPa. Dehydrated at ℃.

  After dehydration, the mixture was cooled to 70 ° C., 79 parts by mass of cyclohexanedimethanol, 509 parts by mass of ethyl acetate, and 329 parts by mass of N-methyl-2-pyrrolidone were added and sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 577 parts by weight of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.2 parts by weight of stannous octylate were added and reacted at 70 ° C for 2 hours.

  After completion of the reaction, 87 parts by mass of the polyol (Z) having a tertiary amino group obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55 ° C., and “aminosilane A1100” [Nihon Unicar Co., Ltd. Manufactured, γ-aminopropyltriethoxysilane] 55 parts by mass and reacted for 1 hour, 1560 parts by mass of ethyl acetate was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Subsequently, 40 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Subsequently, 30 mass parts of 89 mass% phosphoric acid aqueous solution was added, and it hold | maintained at 45 degreeC for 1 hour, Then, it cooled to 40 degreeC and the water dispersion was prepared by adding 3850 mass parts of ion-exchange water. The aqueous dispersion was distilled under reduced pressure to prepare a topcoat agent (I) comprising a cationic urethane resin composition having a nonvolatile content of 30% by mass.

[Example 2]
Polyester polyol having an aliphatic cyclic structure obtained by reacting cyclohexanedimethanol, neopentyl glycol and adipic acid in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device (number average) 1070 parts by mass) (molecular weight 2000, aliphatic cyclic structure amount 1425 mmol / kg) were charged, and dehydrated at 120 ° C. to 130 ° C. at a reduced pressure of 0.095 MPa.

  After dehydration, the mixture was cooled to 70 ° C., 502 parts by mass of ethyl acetate and 322 parts by mass of N-methyl-2-pyrrolidone were added, and the mixture was sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 316 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.2 part by mass of stannous octylate were added and reacted at 70 ° C for 2 hours.

  After completion of the reaction, 84 parts by mass of the polyol (Z) having a tertiary amino group obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55 ° C., and “aminosilane A1100” [Nihon Unicar Co., Ltd. Manufactured, γ-aminopropyltriethoxysilane] 59 parts by mass was added and reacted for 1 hour, and then 1543 parts by mass of ethyl acetate was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Subsequently, 23 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Subsequently, 29 mass parts of 89 mass% phosphoric acid aqueous solution was added, and it hold | maintained at 45 degreeC for 1 hour, Then, it cooled to 40 degreeC and the water dispersion was prepared by adding 3850 mass parts of ion-exchange water. The aqueous dispersion was distilled under reduced pressure to prepare a topcoat agent (II) comprising a cationic urethane resin composition having a nonvolatile content of 30% by mass.

[Example 3]
A polyester polyol (hydroxyl value 59) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid and adipic acid in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device. 0.054 mg KOH / g) 554 parts by mass and polycarbonate polyol (hydroxyl value 111.4 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol, and 120 ° C. to 130 ° C. at a reduced pressure of 0.095 MPa. Dehydrated at ℃.

  After dehydration, the mixture was cooled to 70 ° C., 422 parts by mass of ethyl acetate and 277 parts by mass of N-methyl-2-pyrrolidone were added, and the mixture was sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 406 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.2 part by mass of stannous octylate were added and reacted at 70 ° C for 2 hours.

  After completion of the reaction, 78 parts by mass of the tertiary amino group-containing polyol (Z) obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55 ° C., and “aminosilane A1100” [Nippon Unicar Co., Ltd. Manufactured, γ-aminopropyltriethoxysilane] 59 parts by mass and reacted for 1 hour, 1320 parts by mass of ethyl acetate were added to prepare a urethane prepolymer solution having a terminal isocyanate group. Subsequently, 34 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Subsequently, 27 mass parts of 89 mass% phosphoric acid aqueous solution was added, and it hold | maintained at 45 degreeC for 1 hour, Then, it cooled to 40 degreeC and the water dispersion was prepared by adding 3850 mass parts of ion-exchange water. The aqueous dispersion was distilled under reduced pressure to prepare a topcoat agent (III) comprising a cationic urethane resin composition having a nonvolatile content of 30% by mass.

[Example 4]
A polyester polyol (hydroxyl value 59) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid and adipic acid in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device. 0.054 mg KOH / g) 554 parts by mass and polycarbonate polyol (hydroxyl value 111.4 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol, and 120 ° C. to 130 ° C. at a reduced pressure of 0.095 MPa. Dehydrated at ℃.

  After dehydration, the mixture was cooled to 70 ° C., 79 parts by mass of cyclohexanedimethanol, 563 parts by mass of ethyl acetate, and 356 parts by mass of N-methyl-2-pyrrolidone were added, and sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 577 parts by weight of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.2 parts by weight of stannous octylate were added and reacted at 70 ° C for 2 hours.

  After completion of the reaction, 78 parts by mass of the tertiary amino group-containing polyol (Z) obtained in Synthesis Example 1 and 46 parts by mass of polyethylene glycol monomethyl ether (hydroxyl value 27.0 mgKOH / g) were added and reacted for 4 hours. Then, after cooling to 55 ° C., 73 parts by mass of “aminosilane A1100” (manufactured by Nihon Unicar Co., Ltd., γ-aminopropyltriethoxysilane) was added and reacted for 1 hour, and then 1709 parts by mass of ethyl acetate was added. -A urethane prepolymer solution having a thio group was prepared. Subsequently, 37 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Next, 15 parts by mass of acetic acid was added and held at 45 ° C. for 1 hour, then cooled to 40 ° C., and 3850 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. The aqueous dispersion was distilled under reduced pressure to prepare a topcoat agent (IV) comprising a cationic urethane resin composition having a nonvolatile content of 30% by mass.

[Example 5]
A polyester polyol (hydroxyl value 59) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid and adipic acid in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device. 0.054 mg KOH / g) 554 parts by mass and polycarbonate polyol (hydroxyl value 111.4 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol, and 120 ° C. to 130 ° C. at a reduced pressure of 0.095 MPa. Dehydrated at ℃.

  After dehydration, the mixture was cooled to 70 ° C., 79 parts by mass of cyclohexanedimethanol, 467 parts by mass of ethyl acetate, and 301 parts by mass of N-methyl-2-pyrrolidone were added and sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 577 parts by weight of 4,4'-dicyclohexylmethane diisocyanate (4,4'-H-MDI) and 0.2 parts by weight of stannous octylate were added and reacted at 70 ° C for 2 hours.

  After completion of the reaction, 43 parts by mass of N-methyldiethanolamine was added and reacted for 4 hours, followed by cooling to 55 ° C. and 53 parts by mass of “aminosilane A1100” (manufactured by Nihon Unicar Co., Ltd., γ-aminopropyltriethoxysilane). Then, 1497 parts by mass of ethyl acetate was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Subsequently, 27 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Subsequently, 40 mass parts of 89 mass% phosphoric acid aqueous solution was added, and after hold | maintaining at 45 degreeC for 1 hour, it cooled to 40 degreeC and the water dispersion was prepared by adding 3850 mass parts of ion-exchange water. The aqueous dispersion was distilled under reduced pressure to prepare a topcoat agent (V) comprising a cationic urethane resin composition having a nonvolatile content of 30% by mass.

[Example 6]
Polycarbonate polyol (hydroxyl value 120.0 mgKOH / g, aliphatic ring) obtained by using 1,6-hexanediol and cyclohexanedimethanol in a four-necked flask equipped with a thermometer, stirring device, reflux condenser and dropping device 474 parts by mass of formula structure amount 3272 mmol / kg), and dehydration was performed at 120 to 130 ° C. at a reduced pressure of 0.095 MPa.

  After dehydration, the mixture was cooled to 70 ° C., 38 parts by mass of cyclohexanedimethanol, 279 parts by mass of ethyl acetate, and 174 parts by mass of N-methyl-2-pyrrolidone were added and sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 266 parts by mass of 4,4′-dicyclohexylmethane diisocyanate (4,4′-H-MDI), 29 parts by mass of isophorone diisocyanate, and 0.2 parts by mass of stannous octylate were added, Reacted for hours.

  After completion of the reaction, 54 parts by mass of the tertiary amino group-containing polyol (Z) obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55 ° C., added with 878 parts by mass of ethyl acetate, A urethane prepolymer solution having an isocyanate group was prepared. Subsequently, 16 mass parts of 80 mass% hydrazine hydrate was added to the said urethane prepolymer solution, and chain extension reaction was performed for 1 hour.

  Next, 22 parts by mass of dimethyl sulfate was added and held at 55 ° C. for 1 hour, then cooled to 40 ° C., and 2350 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. The aqueous dispersion was distilled under reduced pressure to prepare a topcoat agent (VI) comprising a cationic urethane resin composition having a nonvolatile content of 30% by mass.

[Comparative Example 1]
A polyester polyol (hydroxyl value 59) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid and adipic acid in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device. 0.054 mg KOH / g) 554 parts by mass and polycarbonate polyol (hydroxyl value 111.4 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol, and 120 ° C. to 130 ° C. at a reduced pressure of 0.095 MPa. Dehydrated at ℃.

  After dehydration, the mixture was cooled to 70 ° C., 376 parts by mass of ethyl acetate and 242 parts by mass of N-methyl-2-pyrrolidone were added, and the mixture was sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 231 parts by mass of hexamethylene diisocyanate and 0.2 parts by mass of stannous octylate were added and reacted at 70 ° C. for 2 hours.

  After completion of the reaction, 69 parts by mass of the tertiary amino group-containing polyol (Z) obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55 ° C., and “aminosilane A1100” [Nihon Unicar Co., Ltd. Manufactured, γ-aminopropyltriethoxysilane] 38 parts by mass was reacted for 1 hour, and 1147 parts by mass of ethyl acetate was added to prepare a urethane prepolymer solution having a terminal isocyanate group. Next, 28 parts by mass of 80% hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was performed for 1 hour.

  Subsequently, 24 mass parts of 89 mass% phosphoric acid aqueous solution was added, and it hold | maintained at 45 degreeC for 1 hour, Then, it cooled to 40 degreeC and the water dispersion was prepared by adding 3850 mass parts of ion-exchange water. The aqueous dispersion was distilled under reduced pressure to prepare a topcoat agent (I ′) composed of a cationic urethane resin composition having a nonvolatile content of 30% by mass.

[Comparative Example 2]
A polyester polyol (hydroxyl value 59) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid and adipic acid in a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser and a dropping device. 0.054 mg KOH / g) 554 parts by mass and polycarbonate polyol (hydroxyl value 111.4 mg KOH / g) 262 parts by mass obtained using 1,6-hexanediol, and 120 ° C. to 130 ° C. at a reduced pressure of 0.095 MPa. Dehydrated at ℃.

  After dehydration, the mixture was cooled to 70 ° C., 40 parts by mass of cyclohexanedimethanol, 438 parts by mass of ethyl acetate, and 261 parts by mass of N-methyl-2-pyrrolidone were added and sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 306 parts by mass of isophorone diisocyanate and 0.2 parts by mass of stannous octylate were added and reacted at 70 ° C. for 2 hours.

  After completion of the reaction, 69 parts by mass of the tertiary amino group-containing polyol (Z) obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55 ° C., and “aminosilane A1100” [Nihon Unicar Co., Ltd. Manufactured, γ-aminopropyltriethoxysilane] 40 parts by mass and reacted for 1 hour, 1297 parts by mass of ethyl acetate were added to prepare a urethane prepolymer solution having a terminal isocyanate group. Next, 12 parts by mass of 80% hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was performed for 1 hour.

  Subsequently, 24 mass parts of 89 mass% phosphoric acid aqueous solution was added, and it hold | maintained at 45 degreeC for 1 hour, Then, it cooled to 40 degreeC and the water dispersion was prepared by adding 3850 mass parts of ion-exchange water. The aqueous dispersion was distilled under reduced pressure to prepare a topcoat agent (II ′) composed of a cationic urethane resin composition having a nonvolatile content of 30% by mass.

[Comparative Example 3]
Polycarbonate polyol obtained by using cyclohexanedimethanol in a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser and a dropping device (hydroxyl value 112.1 mg KOH / g, aliphatic cyclic structure amount 6028 mmol / kg) 536 parts by mass and dehydrated at 120 ° C. to 130 ° C. at a reduced pressure of 0.095 MPa.

  After dehydration, the mixture was cooled to 70 ° C., 299 parts by mass of ethyl acetate and 189 parts by mass of N-methyl-2-pyrrolidone were added, and the mixture was sufficiently stirred and mixed while cooling to 50 ° C. After stirring and mixing, 281 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.2 part by mass of stannous octylate were added and reacted at 70 ° C for 2 hours.

  After completion of the reaction, 50 parts by mass of the tertiary amino group-containing polyol (Z) obtained in Synthesis Example 1 was added, reacted for 4 hours, cooled to 55 ° C., 946 parts by mass of ethyl acetate was added, A urethane prepolymer solution having an isocyanate group was prepared. Next, 26 parts by mass of 80% hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was performed for 1 hour.

  Next, 20 parts by mass of dimethyl sulfate was added and held at 55 ° C. for 1 hour, then cooled to 40 ° C., and 2350 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. The aqueous dispersion was distilled under reduced pressure to prepare a topcoat agent (III ') comprising a cationic urethane resin composition having a nonvolatile content of 30% by mass.

[Fingerprint resistance evaluation method]
Using the bar coater or applicator, the top coat agent is applied to the surfaces of two types of substrates shown in the following [1] to [2] so that the film thickness of the coating film (top coat layer) is 1 μm. Each of the test plates 1 was coated and dried at 150 ° C. for 10 minutes using a hot air dryer, and then allowed to cool at 23 ° C., whereby a test plate 1 in which a coating film composed of a top coat layer was laminated on the surface of each substrate. Obtained.

〔Base material〕
[1] PET substrate: biaxially stretched PET film (Lumirror: manufactured by Toray Industries, Inc.)
[2] Glass substrate: JIS R3202 (manufactured by Engineering Test Service Co., Ltd.)

<Evaluation by appearance>
The test plate 1 was placed on a black paper so that the top coat layer was on the top surface, and a fingerprint was attached to the top coat layer.

  The appearance of the test plate 1 immediately after the fingerprint was attached was visually confirmed, and the appearance of the test plate 1 one minute after the fingerprint was attached was visually confirmed.

A: Although the fingerprint could be visually confirmed immediately after the fingerprint was attached, the fingerprint could not be visually confirmed one minute after the fingerprint was attached.
B: Immediately after the fingerprint was attached, the fingerprint could be confirmed visually. One minute after the fingerprint was attached, the fingerprint could not be clearly confirmed by visual observation, but a part of the fingerprint remained on the surface of the topcoat layer, and it was recognized that the fingerprint would have been attached. I was able to.
C: Even after 1 minute after the fingerprint was attached, the same appearance as that immediately after the fingerprint was attached could be visually confirmed.

<Evaluation by lipophilicity>
1 μL of oleic acid was adhered to the surface of the top coat layer constituting the test plate 1. After 60 seconds from the adhesion, the contact angle of the oleic acid was measured using a fully automatic contact angle meter (manufactured by Kyowa Marine Science Co., Ltd.). If the contact angle is less than 10 degrees, because it is excellent in lipophilicity, even if a fingerprint is attached, it will not stand out over time, and it will be evaluated as having excellent fingerprint resistance, and if it is less than 5 degrees In particular, it was evaluated as having excellent fingerprint resistance.

A: The contact angle was less than 5 degrees.
B: The contact angle was 5 degrees or more and less than 10 degrees.
C: The contact angle was 10 degrees or more.

<Evaluation based on fingerprint wiping ease>
The test plate 1 was placed on a black paper so that the top coat layer was on the top surface, and a fingerprint was attached to the top coat layer.

  Next, using a Kimwipe, an attempt was made to wipe the fingerprint by reciprocating 10 times with a force of 200 g in a direction perpendicular to the surface to which the fingerprint was attached.

  Thereafter, the appearance of the test plate 1 after wiping was evaluated with a haze value calculated using a haze meter (NDH5000: manufactured by Nippon Denshoku Industries Co., Ltd.).

A: Fingerprints and oil components resulting from fingerprints did not remain in the topcoat layer, and the haze value was less than 2.0%.
B: Although the fingerprint could not be confirmed on the topcoat layer, some oil content due to the fingerprint remained in the wiping trace, and the haze value was 2.0% or more and less than 5.0%. .
C: Although the fingerprint could not be confirmed on the topcoat layer, the oil component due to the fingerprint was clearly left on the wiping trace, and the haze value was 5.0% or more.

[Evaluation method of slipperiness]
A metal ball made of stainless steel (diameter 10 mm) was placed on the surface of the top coat layer constituting the test plate 1, and the dynamic friction coefficient was measured under the conditions of a load of 200 g, a moving speed of 4 mm / second, and a moving distance of 40 mm. Those having a dynamic friction coefficient of less than 0.4 were evaluated as being excellent in slipperiness, and those having a dynamic friction coefficient of less than 0.2 were particularly evaluated as being excellent in slipperiness.

A: Dynamic friction coefficient is less than 0.2 B: Dynamic friction coefficient is 0.2 or more and less than 0.4 C: Dynamic friction coefficient is 0.4 or more

  The description of “aliphatic cyclic structure ratio” in Tables 1 and 2 indicates the mass ratio of the aliphatic cyclic structure included in the total amount of the urethane resin.

Claims (7)

A cationic urethane resin (A) having an aliphatic cyclic structure and an aqueous medium (B) are contained, and the cationic urethane resin (A) is 2,000 mmol with respect to the mass of the cationic urethane resin (A). A topcoat agent having an aliphatic cyclic structure in the range of / kg to 5,500 mmol / kg. The cationic urethane resin (A) is a polyol (a1) containing a polyol (a1-1) having an aliphatic cyclic structure and a polyol (a1-2) having a cationic group, and an aliphatic cyclic The topcoat agent according to claim 1, which is obtained by reacting a polyisocyanate (b1) containing a polyisocyanate (b1-1) having a structure. The topcoat agent according to claim 1, wherein the cationic urethane resin (A) has a structure represented by the following general formula [I].

[In the formula [I], R ¹ represents an alkylene group having an aliphatic or aliphatic cyclic structure, a dihydric phenol residue, or a polyoxyalkylene group, and R ² and R ³ are each independently an aliphatic group. An alkyl group having an aliphatic or aliphatic cyclic structure, R ⁴ represents a hydrogen atom or a residue of a quaternizing agent introduced by a quaternization reaction, and X ⁻ represents an anionic counter ion. ] The cationic urethane resin (A) has an aliphatic cyclic structure derived from the polyol (a1-1) from 100 mmol / kg to 2,500 mmol / kg based on the mass of the cationic urethane resin (A). The topcoat agent according to claim 2. The topcoat agent according to claim 1, wherein the cationic urethane resin (A) has a structural unit represented by the following general formula [II].

(In the formula [II], R ⁵ is a monovalent organic group such as an alkyl group, aryl group or aralkyl group, and R ⁶ is a halogen atom, alkoxy group, acyloxy group, phenoxy group, aryloxy group, mercapto group, amino group. A group, an amide group, an aminooxy group, an iminooxy group or an alkenyloxy group, and x is an integer of 0 to 2.) The display apparatus provided with the topcoat layer formed using the topcoat agent of any one of Claims 1-5. A touch panel comprising a top coat layer formed using the top coat agent according to claim 1.