JP2012251103A - Aqueous resin composition, coating agent, and thermally transferable ink ribbon - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous resin composition that can form a film having a moist-heat resistance of a level in which high-appearance coating film can be maintained without whitening the coating film or getting wrinkled in the coating film even under the circumstance of relatively high temperature and high humidity, thereby forming the coating film having superior water resistance and heat resistance.SOLUTION: The aqueous resin composition comprises: composite resin particles (A) consisting of a vinyl polymer (a1) having an amide group and an aryl group and a hydrophilic group-containing urethane resin (a2); and an aqueous vehicle (B).

Description

  The present invention relates to an aqueous resin composition that can be used for various applications such as a coating agent and an adhesive.

  The coating agent is required to be able to form a film capable of imparting design properties and the like to various substrate surfaces and imparting a protective function and the like of the substrate surface. In particular, in recent years, coating agents that can form films with performances such as moisture and water resistance, heat resistance, etc. at levels that can protect the object to be coated even under various temperature and humidity environments have come from the industry. It has been demanded.

  The moisture and heat resistance is a characteristic that can maintain a high-appearance film without causing whitening or wrinkles of the film even in a relatively high temperature and high humidity environment, such as an electronic device such as a mobile phone. This is one of the characteristics that are particularly required in recent years, as well as water resistance and heat resistance in various usage environments.

  Examples of the resin composition capable of forming a film having excellent heat resistance and water resistance include a hydrophilic copolymer (A) containing (meth) acrylamide (a1) and a carboxyl group-containing vinyl monomer (a2), for example. A heat-sensitive recording paper protective layer resin containing an aqueous resin made of a hydrophobic copolymer (C) containing polyvinyl alcohol (B) and a cyano group-containing vinyl monomer (c1) is known (see, for example, Patent Document 1). .)

  However, the resin for the heat-sensitive recording paper protective layer cannot form a film having practically sufficient moisture and heat resistance, and the heat resistance and water resistance are not at sufficient levels.

JP 2011-51338 A

  The problem to be solved by the present invention is that it has a level of moisture and heat resistance capable of maintaining a high-appearance film without causing whitening or wrinkles of the film even in a relatively high temperature and high humidity environment. An object is to provide an aqueous resin composition capable of forming a film and capable of forming a film excellent in water resistance and heat resistance.

  As a result of investigations to solve the above problems, the present inventors have selected a vinyl polymer having a specific functional group of an amide group and an aryl group, and the vinyl polymer and a hydrophilic group-containing urethane. It has been found that an aqueous resin composition containing composite resin particles combined and combined with a resin can form a film excellent in moist heat resistance, water resistance, heat resistance and the like.

  That is, the present invention provides composite resin particles (A) formed from a vinyl polymer (a1) having an amide group and an aryl group and a hydrophilic group-containing urethane resin (a2), and an aqueous medium (B). The present invention relates to an aqueous resin composition and a coating agent characterized by containing.

  Further, the present invention is a thermal transfer type ink ribbon in which an ink layer, a support layer, and a back layer are sequentially laminated, wherein the back layer is a layer formed using the coating agent. The present invention relates to a thermal transfer type ink ribbon.

  Since the aqueous resin composition of the present invention can form a film excellent in moisture and heat resistance, water resistance and heat resistance, it is possible to form a coating agent for surface coating of various substrates and an adhesive for bonding various substrates. Can be used for etc.

  More specifically, the aqueous resin composition of the present invention is a laminated film used for surface coating of parts constituting automobiles, home appliances, etc., surface coating of building materials, surface coating of plastic moldings, liquid crystal displays, etc. Further, it can be used for the surface coating of the thermal transfer type ink ribbon which is easily affected by local heat.

  The present invention relates to composite resin particles (A) formed from a vinyl polymer (a1) having an amide group and an aryl group, and a hydrophilic group-containing urethane resin (a2), an aqueous medium (B), and a necessity. Accordingly, it is an aqueous resin composition containing other additives, wherein the composite resin particles (A) are dispersed in the aqueous medium (B).

First, the composite resin particle (A) will be described.
In the composite resin particle (A) used in the present invention, the vinyl polymer (a1) having an amide group and an aryl group and the hydrophilic group-containing urethane resin (a2) each independently form a resin particle and are aqueous. They are not present in the medium (B) but are composited to form composite resin particles.

  Specifically, the composite resin particles (A) include a composite resin particle in which a part or all of the vinyl polymer (a1) is contained inside the resin particles formed by the hydrophilic group-containing urethane resin (a2). It is preferable to form. More specifically, the vinyl polymer (a1) is preferably dispersed in the hydrophilic group-containing urethane resin (a2) particles in the form of a single particle or a plurality of particles. It is preferable to form core-shell type resin particles composed of the vinyl polymer (a1) and the hydrophilic group-containing urethane resin (a2) as a shell layer. As the composite resin particle (A), it is preferable that the vinyl polymer (a1) is almost completely covered with the hydrophilic group-containing urethane resin (a2). A part of the vinyl polymer (a1) may be present on the outermost part of the composite resin particle (A) as long as the effect is not impaired.

  Further, as the composite resin particles (A), when the vinyl polymer (a1) is more hydrophilic than the hydrophilic group-containing urethane resin (a2), the vinyl polymer In the resin particles formed by (a1), part or all of the hydrophilic group-containing urethane resin (a2) may be present to form composite resin particles.

  On the other hand, the aqueous resin composition in which the vinyl polymer (a1) and the hydrophilic group urethane resin (a2) do not form the composite resin particles (A) and are separately dispersed in the aqueous medium (B). In some cases, a film excellent in moisture and heat resistance and water resistance cannot be formed.

  In addition, the composite resin particles (A) may form a covalent bond between the vinyl polymer (a1) and the hydrophilic group-containing urethane resin (a2), and may be crosslinked within the particles. Although the bond may not be formed, it is preferable that the covalent bond is formed from the viewpoint of further improving the heat resistance of the obtained film.

  On the other hand, when the film-forming property of the aqueous resin composition of the present invention is further improved, it is preferable to use composite resin particles that do not form the covalent bond.

  The composite resin particles (A) preferably have an average particle diameter in the range of 5 nm to 1000 nm from the viewpoint of achieving both excellent heat and moisture resistance, water resistance, heat resistance, water dispersion stability, and the like. The average particle diameter here refers to an average particle diameter on a volume basis measured by a dynamic light scattering method, as will be described later in Examples.

  Moreover, as said composite resin particle (A), mass ratio [(a1) / (a2)] of the said vinyl polymer (a1) and the said hydrophilic group urethane resin (a2) is 99/1-5/95. It is preferable to use an aqueous resin composition that is capable of forming a film having excellent film-forming properties and excellent heat and moisture resistance and heat resistance. It is particularly preferable for obtaining.

  The composite resin particles (A) have a hydrophilic group necessary for dispersion in the aqueous medium (B). The hydrophilic group is preferably supplied by the hydrophilic group-containing urethane resin (a2).

  As the hydrophilic group, an anionic group, a cationic group, and a nonionic group can be used. Among them, an anionic group or a cationic group is preferably used, and an anionic group is more preferably used. .

  As the anionic group, for example, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonate group, or the like in which part or all of them are neutralized with a basic compound or the like can be used. Among these, the use of a carboxyl group or a carboxylate group is preferable for producing composite resin particles (A) having good water dispersibility.

  Examples of basic compounds that can be used for neutralization of the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, Na, K, Li, and Ca. A metal base compound etc. are mentioned.

  Moreover, as said cationic group, a tertiary amino group etc. can be used, for example. The tertiary amino group may be partially or entirely neutralized with acetic acid or propionic acid.

  Examples of the nonionic group include a polyoxyethylene group, a polyoxypropylene group, and a polyoxyethylene-polyoxypropylene group.

  The composite resin particles in the aqueous medium (B) that the hydrophilic groups such as the anionic group and the cationic group are present in the range of 50 mmol / kg to 1000 mmol / kg with respect to the entire composite resin particles (A). It is preferable for imparting good water dispersion stability of (A).

Next, the vinyl polymer (a1) constituting the composite resin particle (A) will be described.
In the aqueous resin composition of the present invention, the vinyl polymer (a1) having a combination of an amide group and an aryl group is used to form a film excellent in moisture and heat resistance, water resistance and heat resistance. Is particularly important.

  Here, in the aqueous resin composition obtained by using a vinyl polymer having no amide group and not having an aryl group instead of the vinyl polymer (a1), a film excellent in moisture and heat resistance and water resistance It may be difficult to form.

  On the other hand, the aqueous resin composition obtained by using a vinyl polymer having an amide group and having an aryl group instead of the vinyl polymer (a1) has a certain degree of moisture and heat resistance. Although a film can be formed, it may not be a practically sufficient level. Moreover, the film | membrane formed using the said aqueous resin composition may cause a heat resistant and alcohol-resistant fall.

  As the vinyl polymer (a1), with respect to the total amount of the vinyl polymer (a1), from the viewpoint of forming a film having excellent heat resistance, water resistance, and alcohol resistance together with excellent moisture and heat resistance. The vinyl polymer (a1) contains 0.5 mmol / g to 15 mmol / g of amide groups and 0.5 mmol / g to 10 mmol / g of aryl groups with respect to the total amount of the composite resin particles (A). The amide group is preferably contained in an amount of 2.0 mmol / g to 11 mmol / g and the aryl group is preferably contained in an amount of 1.0 mmol / g to 7.0 mmol / g. It is preferable to contain 0.0 mmol / g-5.0 mmol / g, and to contain 1.0 mmol / g-2.0 mmol / g of aryl groups.

  As said vinyl polymer (a1), what has other functional groups other than the said amide group and aryl group as needed can be used.

  Examples of the other functional groups include nitrile groups and basic nitrogen atom-containing groups such as amino groups, and further improve the alcohol resistance without impairing the heat and moisture resistance, water resistance, and heat resistance of the film to be formed. From the viewpoint, a nitrile group or an amino group is preferable.

  The nitrile group is used in a range where the equivalent ratio with the amide group [nitrile group / amide group] is 10/90 to 90/10, and has excellent heat and water resistance, as well as excellent moisture and heat resistance, It is preferable when forming a film excellent in alcohol resistance.

  Further, as the basic nitrogen atom-containing group, those having an amino group are more preferably used, and those having a tertiary amino group are particularly preferably used.

  The basic nitrogen atom-containing group may be one having 0.03 mmol / g to 0.70 mmol / g based on the total amount of the vinyl polymer (a1). It is preferable for forming a film excellent in alcohol resistance without damaging.

  Moreover, as said vinyl polymer (a1), it is preferable to use what has the weight average molecular weight of the range of 100,000-1 million from a viewpoint of improving the water resistance, alcohol resistance, etc. of a membrane | film | coat.

  Next, the hydrophilic group-containing urethane resin (a2) constituting the composite resin particle (A) will be described.

  The hydrophilic group-containing urethane resin (a2) is important for imparting a hydrophilic group to the composite resin particles (A) and forming a film excellent in wet heat resistance, water resistance, and heat resistance.

  Here, instead of the hydrophilic group-containing urethane resin (a2), in the aqueous resin composition obtained in the same manner as the present invention except that, for example, a hydrophilic group-containing vinyl polymer is used, the heat and moisture resistance and heat resistance are In some cases, it is not possible to form a film having excellent properties.

  As the hydrophilic group-containing urethane resin (a2), those having an aromatic ring structure are preferably used. In particular, it is possible to use the hydrophilic group-containing urethane resin containing 1% to 40% by weight of the aromatic ring structure with respect to the entire hydrophilic group-containing urethane resin (a2). It is preferable for forming a film excellent in heat resistance and alcohol resistance.

  The said aromatic ring structure can be introduce | transduced in a urethane resin (a2) by using an aromatic ring structure containing polyol as a polyol used for manufacture of the said hydrophilic group containing urethane resin (a2).

  Moreover, the hydrophilic group which the said hydrophilic group containing urethane resin (a2) has can use an anionic group, a cationic group, and a nonionic group, However, It is especially using an anionic group or a cationic group. Preferably, an anionic group is used.

  As the anionic group, for example, a carboxyl group, a sulfonic acid group, a carboxylate group, a sulfonate group, or the like in which part or all of them are neutralized with a basic compound or the like can be used. Among these, the use of a carboxyl group or a carboxylate group is preferable for producing composite resin particles (A) having good water dispersibility.

  Examples of basic compounds that can be used for neutralization of the anionic group include organic amines such as ammonia, triethylamine, pyridine, morpholine, alkanolamines such as monoethanolamine, Na, K, Li, and Ca. A metal base compound etc. are mentioned.

  Moreover, as said cationic group, a tertiary amino group etc. can be used, for example. The tertiary amino group may be partially or entirely neutralized with acetic acid or propionic acid.

  Examples of the nonionic group include a polyoxyethylene group, a polyoxypropylene group, and a polyoxyethylene-polyoxypropylene group.

  In the aqueous medium (B), the hydrophilic group such as the anionic group and the cationic group is present in the range of 15 mmol / kg to 2000 mmol / kg with respect to the entire hydrophilic group-containing urethane resin (a2). It is preferable for imparting good water dispersion stability of the composite resin particles (A).

  The hydrophilic group can be introduced into the urethane resin (a2) by using a hydrophilic group-containing polyol as a part of the polyol or polyisocyanate used in the production of the urethane resin (a2).

  As said hydrophilic group containing urethane resin (a2), it is preferable to use what has a weight average molecular weight of the range of 5000-500000, It is excellent in film forming property to use the thing of 20000-100,000, and It is preferable for obtaining an aqueous resin composition capable of forming a film excellent in moisture and heat resistance, water resistance and heat resistance.

Next, a method for producing the composite resin particle (A) will be described.
The composite resin particles (A) include, for example, a hydrophilic group-containing urethane resin (a2) obtained by reacting a polyol (a2-1) containing a hydrophilic group-containing polyol and a polyisocyanate (a2-2). A step (W) of producing an aqueous dispersion of the hydrophilic group-containing urethane resin (a2) by dispersing in water, and a vinyl monomer is polymerized in the aqueous dispersion to produce a vinyl polymer (a2). It can be obtained by the step (X).

  Specifically, a polyol (a2-1) containing a hydrophilic group-containing polyol and a polyisocyanate (a2-2) in the absence of a solvent or in an organic solvent or in the presence of a reactive diluent such as a vinyl monomer To obtain a hydrophilic group-containing urethane resin (a2), and then neutralize part or all of the hydrophilic group of the urethane resin (a2) with a basic compound or the like as necessary. Then, an aqueous dispersion of the hydrophilic group-containing urethane resin (a2) is produced by dispersing the obtained neutralized product in the aqueous medium (B).

  Next, the vinyl monomer is supplied into the aqueous dispersion of the hydrophilic group-containing urethane resin (a2) obtained above, and the vinyl monomer is contained in the hydrophilic group-containing urethane resin (a2) particles. A vinyl polymer (a1) is produced by radical polymerization.

  Thus, an aqueous resin composition in which the composite resin particles (A) in which the vinyl polymer (a1) is present inside the hydrophilic group-containing urethane resin (a2) particles is dispersed in an aqueous medium (B) is produced. Can do.

  When producing the composite resin particles (A), when the hydrophilic group-containing urethane resin (a2) has a high viscosity and is not excellent in workability, a normal organic solvent such as methyl ethyl ketone or N-methylpyrrolidone, A reactive diluent can be used. In particular, the use of a vinyl monomer that can be used for the production of the vinyl polymer (a1) as the reactive diluent reduces the viscosity of the urethane resin (a2) and the solvent resistance of the resulting coating film. It is preferable for improving the productivity and improving the production efficiency of the aqueous resin composition by omitting the solvent removal step.

  First, hydrophilicity is obtained by water-dispersing the hydrophilic group-containing urethane resin (a2) obtained by reacting the polyol (a2-1) containing the hydrophilic group-containing polyol with the polyisocyanate (a2-2). The step (W) for producing an aqueous dispersion of the group-containing urethane resin (a2) will be described.

  The reaction between the polyol (a2-1) and the polyisocyanate (a2-2) is usually preferably performed in a temperature range of 50 to 150 ° C.

  In the reaction of the polyol (a2-1) and the polyisocyanate (a2-2), for example, the equivalent ratio of the isocyanate group that the polyisocyanate has to the hydroxyl group that the polyol (a2-1) has is 1.05. It is preferable to carry out in the range of 3, more preferably in the range of 1.1 to 2.

  As a polyol that can be used for the production of the hydrophilic group-containing urethane resin (a2), a polyol (a2-1) containing a hydrophilic group-containing polyol can be used.

  As the hydrophilic group-containing polyol, for example, an anionic group-containing polyol, a cationic group-containing polyol, a nonionic group-containing polyol, or the like can be used, and among them, an anionic group-containing polyol or a cationic group-containing polyol is used. It is preferable to use an anionic group-containing polyol in order to maintain good storage stability.

  As said anionic group containing polyol, anionic group containing polyols, such as a carboxyl group containing polyol and a sulfonic acid group containing polyol, can be used, for example.

  Examples of the carboxyl group-containing polyol include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolvaleric acid, and the like. Among them, it is preferable to use 2,2′-dimethylolpropionic acid. Moreover, the carboxyl group-containing polyester polyol obtained by making the said carboxyl group-containing polyol and various polycarboxylic acids react can also be used.

  Examples of the sulfonic acid group-containing polyol include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof, and the low molecular weight polyol. Polyester polyol obtained by reacting can be used.

  Further, as the cationic group-containing polyol, for example, a tertiary amino group-containing polyol can be used. Specifically, N-methyl-diethanolamine, a compound having two epoxies in one molecule, and a secondary amine. A polyol obtained by reacting with can be used.

  Further, as the nonionic group-containing polyol, polyalkylene glycol having a structural unit derived from ethylene oxide can be used.

  The hydrophilic group-containing polyol is preferably used in a range of 1% by mass to 15% by mass with respect to the total amount of the polyol that can be used for the production of the hydrophilic group-containing urethane resin (a2).

  As a polyol that can be used for the production of the hydrophilic group-containing urethane resin (a2), in addition to the hydrophilic group-containing polyol, other polyols can be used in combination as required.

  As said other polyol, polyether polyol, polyester polyol, polyester ether polyol, polycarbonate polyol etc. can be used, for example. Among these, the use of polyester polyol is preferable when a film having further excellent heat resistance and alcohol resistance is formed.

  Examples of the polyester polyol include a ring-opening polymerization reaction of a cyclic ester compound such as an aliphatic polyester polyol, an aromatic polyester polyol, or ε-caprolactone obtained by esterifying a low molecular weight polyol and a polycarboxylic acid. Polyesters, copolymerized polyesters thereof, and the like can be used.

  Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol and the like.

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid, aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid, and the like. An anhydride or an ester-forming derivative can be used.

  Among these, it is preferable to use an aromatic polyester polyol for forming a film excellent in heat resistance and alcohol resistance. As said aromatic polyester polyol, what is obtained by making the said low molecular weight polyol and aromatic polycarboxylic acid react can be used.

  In addition, as the polyether polyol, for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, Trimethylolethane, trimethylolpropane and the like, bisphenol A, bisphenol F, bisphenol B, bisphenol AD, and the like can be used.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.

  Moreover, as said polyester ether polyol, what reacted the polyether polyol which the said alkylene oxide added to the said initiator and polycarboxylic acid can be used, for example. As the initiator and the alkylene oxide, the same ones exemplified as those usable when the polyether polyol is produced can be used. Moreover, as said polycarboxylic acid, the thing similar to what was illustrated as what can be used when manufacturing the said polyester polyol can be used.

  Moreover, as said polycarbonate polyol, what is obtained by making carbonate ester and a polyol react, for example, what is obtained by making phosgene, bisphenol A, etc. react can be used.

  As the carbonate ester, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used.

  Examples of the polyol capable of reacting with the carbonate ester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3- Butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptane Diol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 3-methyl-1,5-pentanediol, 2- Ethyl-1,3-hexanediol, 2-methyl-1,3-propa Diol, 2-methyl-1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexane Relatively low molecular weight dihydroxy compounds such as dimethanol, hydroquinone, resorcin, bisphenol-A, bisphenol-F, 4,4′-biphenol, polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, Polyester polyols such as hexamethylene adipate, polyhexamethylene succinate, and polycaprolactone can be used.

  The polyester polyol, polyether polyol, polyester ether polyol, and polycarbonate polyol are used in a total range of 50% by mass to 95% by mass with respect to the total amount of polyol used for the production of the hydrophilic group-containing urethane resin (a2). It is preferable to do. Moreover, it is preferable that the said aromatic polyester polyol is also used in 50 mass%-95 mass% with respect to the whole quantity of the polyol used for manufacture of the said hydrophilic group containing urethane resin (a2).

  Other polyols that can be used for the production of the hydrophilic group-containing urethane resin (a2) include, in addition to those described above, for example, cyclobutanediol, cyclopentanediol, cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol Hydrogenated bisphenol A, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Neopentyl glycol, 1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (molecular weight 300-6000), dipropylene glycol, tripropylene glycol -Le, bishydroxyeth Shibenzen, bisphenol - Le A, hydroquinone and relatively low molecular weight polyols such as those of alkylene oxide adducts, can also be suitably combined use.

  Examples of the polyisocyanate (a2-2) used for producing the hydrophilic group-containing urethane resin (a2) include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexa Use aliphatic or aliphatic cyclic structure-containing diisocyanates such as methylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate alone or in combination of two or more. Can be used. Among these, it is more preferable to use isophorone diisocyanate and tolylene diisocyanate for improving heat resistance and alcohol resistance.

  Examples of a method for obtaining a dispersion by dispersing the hydrophilic group-containing urethane resin (a2) obtained by the above method in an aqueous medium (B) include, for example, part or all of the hydrophilic groups possessed by the urethane resin (a2). May be neutralized with the above-described basic compound, if necessary, and the resulting neutralized product may be dispersed in the aqueous medium (B). The aqueous dispersion can be produced by mixing the hydrophilic group-containing urethane resin (a2) and the aqueous medium (B) using a machine such as a homogenizer as necessary.

  In addition, as the hydrophilic group-containing urethane resin (a2), a polymer having a high molecular weight using a chain extender such as polyamine as necessary is used for forming a film excellent in moisture and heat resistance and heat resistance. You may do it.

  Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 3,3′-. Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, Diamines containing one primary amino group and one secondary amino group such as N-methylaminopropylamine; polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; hydrazine, N Hydrazines such as N′-dimethylhydrazine and 1,6-hexamethylenebishydrazine; Dihydrazides such as succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, and isophthalic acid dihydrazide; Semicarbazides such as 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane can be used.

  The polyamine is preferably used in such a range that the equivalent ratio of the amino group of the polyamine and the isocyanate group of the urethane resin (a2) is 1.9 or less (equivalent ratio). It is more preferable to use in the range of 0 (equivalent ratio).

  The chain extension reaction is preferably carried out by preparing an aqueous dispersion of the hydrophilic group-containing urethane resin (a2) by the above method and then mixing the aqueous dispersion with a chain extender such as the polyamine.

  Moreover, when manufacturing the said hydrophilic group containing urethane resin (a2), a reactive diluent can be used as needed. As the reactive diluent, it is preferable to use a vinyl monomer that can be used in the production of the vinyl polymer (a1).

  As a method for producing a hydrophilic group-containing urethane resin (a2) using a vinyl monomer as the reactive diluent, the polyol and polyisocyanate are reacted in the presence of the vinyl monomer to form a hydrophilic group. A containing urethane resin (a2) is produced, and then a mixture of the urethane resin (a2) and the vinyl monomer is dispersed in the aqueous medium (B).

  Next, the resin formed by the hydrophilic group-containing urethane resin (a2) by polymerizing the vinyl monomer inside the hydrophilic group-containing urethane resin (a2) particles dispersed in the aqueous medium (B). An aqueous resin composition containing composite resin particles (A) in which the vinyl polymer (a1) is present inside the particles and an aqueous medium (B) can be obtained.

  Next, the step (X) for producing a vinyl polymer (a2) by polymerizing a vinyl monomer in the aqueous dispersion obtained in the step (W) will be described.

  As the vinyl polymer (a1) constituting the composite resin particles (A) used in the present invention, those obtained by polymerizing various vinyl monomers in the presence of a polymerization initiator or the like can be used. Specifically, the vinyl polymer (a1) is obtained by radical polymerization of a vinyl monomer mixture containing an amide group-containing vinyl monomer or an aryl group-containing vinyl monomer in the presence of a polymerization initiator or the like. What is obtained can be used.

  As the amide group-containing vinyl monomer, for example, (meth) acrylamide or the like is preferably used for forming a film having excellent heat resistance.

  Examples of the amide group-containing vinyl monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N. -Diethylmethacrylamide, N, N'-methylenebisacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, diacetone acrylamide and the like can be used. Among these, the use of N, N-dimethylaminopropyl (meth) acrylamide is preferable in that a tertiary amino group can be introduced together with an amide group, and a film excellent in wet heat resistance and heat resistance is formed.

  The amide group-containing vinyl monomer is preferably used in the range of 5% by mass to 90% by mass with respect to the total amount of the vinyl monomer mixture that can be used for the production of the vinyl polymer (a1). It is more preferable to use in the range of 35% by mass to 90% by mass.

  Examples of the aryl group-containing vinyl monomer that can be used include styrene, chlorostyrene, chloromethylstyrene, α-methylstyrene, and the like. Of these, styrene or α-methylstyrene is preferably used, and styrene is preferably used.

  The aryl group-containing vinyl monomer is preferably used in the range of 5% by mass to 90% by mass with respect to the total amount of the vinyl monomer mixture that can be used for the production of the vinyl polymer (a1). It is more preferable to use in the range of 5% by mass to 65% by mass.

  When the vinyl polymer (a1) having a basic nitrogen atom-containing group such as a tertiary amino group is used, the vinyl monomer having a basic nitrogen atom-containing group as the vinyl monomer. Can be used.

  Examples of the vinyl monomer having a basic nitrogen atom-containing group include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meta). ) Acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxy Ethyl] pyrrolidine, N- [2- (meth) acryloyloxyethyl] morpholine, 4- [N, N-dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2-vinylpyridine, 4-vinylpyridine N, N-dimethylaminopropylacrylamide, N, N-dimethyl Tertiary amino group-containing vinyl monomers such as aminopropylmethacrylamide; secondary amino group-containing vinyl monomers such as N-methylaminoethyl (meth) acrylate and Nt-butylaminoethyl (meth) acrylate; amino Primary amino group-containing vinyl monomers such as methyl acrylate, aminoethyl acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate, etc. can be mentioned. It is preferable to use a monomer.

  The vinyl monomer having a basic nitrogen atom-containing group is in the range of 0.1% by mass to 10% by weight with respect to the total amount of the vinyl monomer mixture that can be used for the production of the vinyl polymer (a1). It is preferable to use in the range of 0.1 mass% to 5 mass%.

When the vinyl polymer (a1) having a nitrile group is used, a nitrile group-containing compound such as acrylonitrile can be used as the vinyl monomer.
The nitrile group-containing compound is preferably used in the range of 0.1% by mass to 45% by weight with respect to the total amount of the vinyl monomer mixture that can be used for the production of the vinyl polymer (a1). It is more preferable to use in the range of mass% to 45 mass%.

  In addition to the vinyl monomer having an amide group or aryl group, the vinyl monomer having a basic nitrogen atom-containing group, or a nitrile group-containing compound, the vinyl monomer may contain other vinyl monomers as necessary. The body may be contained.

  Examples of the other vinyl monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, and hexyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) Alkyl group-containing (meth) acrylates such as acrylate, n-undecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. Can be used Le monomer, it is preferable to use inter alia n- butyl acrylate and 2-ethylhexyl acrylate.

  Examples of the other vinyl monomers include hydroxyl group-containing (meth) acrylic monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, cyclohexylmaleimide, isopropylmaleimide, N -Imido group-containing vinyl monomers such as cyclohexylmaleimide, itaconimide, styrene sulfonic acid, allyl sulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene sulfonic acid, sodium vinyl sulfonate, etc. Monomers, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, vinyl acetate, vinyl propionate, vinyl laurate, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl It may be used ether.

  Among these, the other vinyl monomers include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, diacetone acrylamide, N-methylol (meth) acrylamide, and n-butoxymethyl. Using a resin having a crosslinkable functional group such as acrylamide, N-isobutoxymethylacrylamide, and the like, a composite resin in which the vinyl polymer (a1) and the hydrophilic group-containing urethane resin (a2) form a covalent bond An aqueous resin composition containing particles can be obtained, and with such an aqueous resin composition, it is possible to further form a film excellent in moist heat resistance and heat resistance.

  The amount of the other vinyl monomer used is preferably in the range of 0% by mass to 30% by mass, and 0.05% by mass to 30% by mass with respect to the total amount of the vinyl monomer. preferable. Moreover, when using the vinyl monomer which has a crosslinkable functional group as said other vinyl monomer, with respect to the total amount of said vinyl monomer which can be used for manufacture of said vinyl polymer (a1). It is preferable that it is the range of 0.05 mass%-5 mass%.

  For the polymerization of the vinyl monomer, the vinyl monomer and the polymerization initiator are separately supplied into the aqueous dispersion of the hydrophilic group-containing urethane resin (a2), or a mixture thereof is supplied in a batch or divided. And a method of polymerizing the vinyl monomer in the hydrophilic group-containing urethane resin (a2) particles dispersed in the aqueous medium (B).

  Examples of the polymerization initiator that can be used in producing the vinyl polymer (a2) include radical polymerization initiators such as persulfates, organic peroxides, and hydrogen peroxide, and 4,4′-azobis ( An azo initiator such as 4-cyanovaleric acid) or 2,2′-azobis (2-amidinopropane) dihydrochloride can be used. The radical polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent described later.

  Examples of the persulfates that are representative of the polymerization initiator include potassium persulfate, sodium persulfate, and ammonium persulfate. Specific examples of organic peroxides include, for example, peroxidation. Diacyl peroxides such as benzoyl, lauroyl peroxide, decanoyl peroxide, dialkyl peroxides such as t-butylcumyl peroxide, dicumyl peroxide, t-butylperoxylaurate, t-butylperoxybenzoate, etc. Peroxyesters, cumene hydroperoxide, paramentane hydroperoxide, hydroperoxides such as t-butyl hydroperoxide, and the like can be used.

  Examples of the reducing agent include ascorbic acid and its salt, erythorbic acid and its salt, tartaric acid and its salt, citric acid and its salt, metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium bisulfite, chloride Ferric iron or the like can be used.

  In the polymerization, an emulsifier may be used for the purpose of stabilizing the polymerization reaction. It is not appropriate to use the emulsifier excessively from the viewpoint of stably forming the composite resin particles (A). It is preferable to use in the range of 3 mass% to 10 mass%.

  Moreover, as an aqueous medium (B) used by this invention, the organic solvent mixed with water and water, and these mixtures are mentioned. 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; lactams such as N-methyl-2-pyrrolidone, and the like. 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.

  In the present invention, when the aqueous medium (B) is used as a solvent in the process of producing the composite resin particles (A), the aqueous medium (B) can be continuously used.

  The aqueous medium (B) suppresses a sudden increase in viscosity during production, and improves the productivity of the aqueous resin composition, ease of coating, drying properties, and the like. The nonvolatile content is preferably 10 to 70% by mass with respect to the total amount of the aqueous resin composition.

  Further, the aqueous resin composition of the present invention includes, in addition to those described above, for example, a film forming aid, a filler, a thixotropy imparting agent, a tackifier imparting agent, a pigment and an antibacterial agent. Can be used as long as the purpose of the above is not impaired.

  The film-forming aid is not particularly limited. For example, an anionic surfactant (such as dioctyl sulfosuccinate soda salt), a hydrophobic nonionic surfactant (such as sorbitan monooleate), a polyether-modified siloxane, Silicone oil etc. are mentioned.

  Examples of the filler include oxides of metals such as silicon, aluminum, titanium, zirconium, zinc, tin, and iron, and their hydrolysis condensates, and carbonates (for example, calcium salts, calcium / magnesium salts, magnesium salts, etc.) ), Silicic acid, silicates (eg aluminum salts, magnesium salts, calcium salts etc.), hydroxides (eg aluminum salts, magnesium salts, calcium salts etc.), sulfates (eg barium salts, calcium salts, magnesium salts etc.), Examples thereof include borates (for example, aluminum salts, zinc salts, and calcium salts), titanates (for example, potassium salts), glass fibers, and the like.

  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.

  Although it does not specifically limit as said tackifier, For example, tackifiers, such as a rosin resin type, a terpene resin type, a phenol resin type, are mentioned.

  As the pigment, known and commonly used inorganic pigments, organic pigments, extender pigments and functional 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, anthanthrone 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.

  Functional pigments include anticorrosive pigments such as zinc powder, zinc chromate, cyanamide lead, phosphor pigments such as phosphates, silicates, aluminates, and tungstic acids, conductive pigments such as carbon black, Sb / Sn coated mica / titanate whisker, aluminum coated glass beads, gold conductive paste, silver conductive paste, copper conductive paste, electromagnetic shielding pigment, magnetic pigment iron oxide, temperature indicating pigment, photocatalyst pigment titanium oxide, etc. Furthermore, lubricating pigments such as graphite, molybdenum disulfide, and polyimide particles can be used.

  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.

  Further, other additives include, for example, a crosslinking agent composed of a zirconium compound such as zirconium oxychloride, a titanium compound, an aluminum compound, a zinc compound, a sizing agent such as paraffin wax, and a reaction accelerator (metal-based, metal salt). And amines), stabilizers (ultraviolet absorbers, antioxidants, heat stabilizers, etc.), moisture removers (4-paratoluenesulfonyl isocyanate, etc.), adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.) And various additives such as an adhesion-imparting agent and an antifoaming agent.

When the aqueous resin composition of the present invention is used, for example, for forming a back layer of a thermal transfer type ink ribbon, the film is formed at a relatively low temperature of about 60 to 100 ° C. from the viewpoint of preventing damage to the substrate due to heat. Can be formed. In the aqueous resin composition of the present invention, the crosslinking agent can be used in combination. In such a case, it is preferable to select and use one that can be crosslinked at a relatively low temperature as described above.
The aqueous resin composition of the present invention can form a practically sufficient level of wet heat resistance, water resistance, and heat resistance without using the cross-linking agent. For example, environmental loads such as glyoxal It is not essential to use a crosslinking agent or the like for which there is concern.
The crosslinking agent is preferably used in the range of 0 to 10 parts by mass, preferably 0 to 1 part by mass, and 100 parts by mass with respect to 100 parts by mass of the composite resin particles (A). It is preferable that it is a part-0.5 mass part.

  As described above, the aqueous resin composition of the present invention can form a film excellent in moisture and heat resistance, water resistance, heat resistance, etc., so that the surface protection of various base materials and the design impartment to various base materials are aimed at. It can be used for the coating agent to be used.

  Examples of the base material include various plastics and films thereof, metal, glass, paper, and wood. In particular, when the coating agent of the present invention is used for various plastic substrates, a film having excellent alcohol resistance and water resistance can be formed even in a drying process at a relatively low temperature, and the film can be peeled off from the plastic substrate. Can be prevented.

  As a plastic substrate, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin) are generally used as plastic molded products such as mobile phones, home appliances, automotive interior and exterior materials, and office automation equipment. ), ABS / PC resin, polystyrene resin (PS resin), polymethylmethacrylate resin (PMMA resin), acrylic resin, polypropylene resin, polyethylene resin, etc., and plastic film base materials include polyethylene terephthalate film, polyester film, A polyethylene film, a polypropylene film, a TAC (triacetyl cellulose) film, a polycarbonate film, a polyvinyl chloride film and the like can be used.

  Examples of the metal substrate include galvanized steel sheets used for applications such as automobiles, home appliances, and building materials, plated steel sheets such as aluminum-zinc alloy steel sheets, aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, stainless steel plates, etc. Can be used.

  The coating agent of the present invention exhibits extremely excellent solvent resistance against organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, and toluene even when the cross-linked coating film has a thickness of about 5 μm. It is possible.

  The coating agent of the present invention can form a film on the surface of the substrate by coating on the substrate, drying and curing.

  Examples of the coating method for the coating agent include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.

  The drying may be natural drying at normal temperature, but may be heat-dried. The heat drying is usually preferably performed at 40 to 250 ° C. for about 1 to 600 seconds.

  Moreover, since the film | membrane formed using the coating agent of this invention is excellent in moisture heat resistance, water resistance, heat resistance, and alcohol resistance as above-mentioned, it is preferable to form the outermost layer of a final coating thing, for example. Specifically, it is preferable to use the film as a surface layer or a back surface layer of a coated object. Specifically, the coating agent is preferably used as a surface layer forming coating agent or a back surface layer forming coating agent for various substrates.

  In addition, since the coating agent of the present invention can form a film having excellent heat resistance, it can be used for surface coating of various members such as electronic devices, automobile members, building members, optical members such as optical films, and the like. it can.

  In addition, a thermal transfer type ink layer such as a melt-type wax ink can be provided as an intermediate layer or the like on a coated article formed using the coating agent of the present invention.

  Specifically, an intermediate layer such as a conventionally known thermal transfer type ink layer or heat-sensitive color forming layer is provided on the surface of various base materials, and then the back surface of the base material or the surface of the intermediate layer is coated with the present invention. A coating agent can be applied to form a surface layer and a back layer, respectively.

  As a result, it is possible to obtain a thermal transfer type ink ribbon that is unlikely to cause a print head running failure or a printing failure due to the influence of heat.

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

<Preparation Example 1> Preparation of polyester polyol While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 830 parts by mass of terephthalic acid, 830 parts by mass of isophthalic acid, 1,6-hexane 685 parts by mass of diol, 604 parts by mass of neopentyl glycol and 0.5 parts by mass of dibutyltin oxide were added, and a polycondensation reaction was performed at 230 ° C. for 15 hours until the acid value became 1 or less at 180 to 230 ° C. 9. A polyester polyol having an acid value of 0.2 was obtained.

<Preparation Example 2> Preparation of Urethane Resin Water Dispersion (PU1) 1000 parts by mass of the above polyester polyol was dehydrated at 100 ° C. under reduced pressure, cooled to 80 ° C., 883 parts by mass of methyl ethyl ketone was added, and the mixture was sufficiently stirred and dissolved. 80 parts by mass of 2,2′-dimethylolpropionic acid was added, and then 244 parts by mass of isophorone diisocyanate was added and reacted at 70 ° C. for 8 hours.

  After completion of the reaction, the mixture was cooled to 40 ° C., neutralized by adding 60 parts by mass of triethylamine, and then mixed with 4700 parts by mass of water to obtain a transparent reaction product.

  Methyl ethyl ketone was removed from the reaction product under reduced pressure of 40 to 60 ° C., and then water was mixed to obtain a urethane resin aqueous dispersion (PU1) having a nonvolatile content of 25 mass% and a weight average molecular weight of 50000. .

[Example 1] Preparation of aqueous resin composition (X-1) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst. 330 parts by weight of deionized water, 80 parts by weight of the above urethane resin aqueous dispersion (PU1), Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd .; polyoxyethylene-1- (allyloxymethyl) alkyl sulfate ammonium (Salt, solid content: 100% by mass) 1.0 part by mass was stirred and heated to 80 ° C. while blowing nitrogen. After heating up to 80 ° C. and continuing the nitrogen substitution for 60 minutes, polymerization initiator V-501 (manufactured by Wako Pure Chemical Industries, Ltd., 4,4-azobis (4-cyanopentanoic acid)) was added with 25 mass% ammonia. 5 parts by mass of the 10% by mass aqueous solution neutralized using the solution was put into a reaction vessel and stirred for 5 minutes. Thereafter, 178 parts by mass of 50% by mass acrylamide, 10 parts by mass of α-methylstyrene, and 1 part by mass of N, N-dimethylaminopropylacrylamide were added dropwise over 90 minutes, respectively, and polymerization initiator V-501 (Wako Pure Chemical Industries, Ltd.) 7 parts by mass of a 10% aqueous solution obtained by neutralizing 4,4-azobis (4-cyanopentanoic acid) produced by 25% by mass with ammonia was added dropwise over 120 minutes for polymerization. After completion of the dropwise addition of the monomer mixture and the initiator, the mixture was held at the same temperature for 90 minutes.

  Thereafter, the inside of the reaction vessel is cooled to 30 ° C., 25% by mass of ammonia water and deionized water are supplied and mixed, and then filtered using a 100 mesh wire net, so that the composite resin particles (A-1) are submerged in water. A dispersed aqueous resin composition (X-1) (nonvolatile content: 20.0 mass%, pH 8) was obtained.

  Further, 100 parts by mass of the aqueous resin composition (X-1), 0.1 part by mass of BYK348 (manufactured by Big Chemie Japan, polyether-modified siloxane, concentration 100% by mass), and EMUSTAR-6315D (Nippon Seiwa Co., Ltd.) A coating agent (Y-1) having a nonvolatile content of 15% by mass was obtained by mixing 3.5 parts by mass and appropriately ion-exchanged water.

[Example 2] Preparation of aqueous resin composition (X-2) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst. 480 parts by mass of deionized water and 600 parts by mass of the urethane resin water dispersion (PU1) were added and stirred, and the temperature was raised to 80 ° C. while blowing nitrogen. After raising the temperature to 80 ° C. and continuing nitrogen substitution for 60 minutes, 8 parts by mass of a polymerization initiator 10% by mass ammonium persulfate was put into the reaction vessel and stirred for 5 minutes. Then, 138 parts by mass of 50% by mass acrylamide, 30 parts by mass of styrene, and 1 part by mass of N, N-dimethylaminopropylacrylamide were added dropwise over 90 minutes, respectively, and 4 parts by mass of 10% by mass of polymerization initiator ammonium persulfate over 120 minutes. Dropped and polymerized. After completion of the dropwise addition of the monomer mixture and the initiator, the mixture was held at the same temperature for 90 minutes.

  Thereafter, the inside of the reaction vessel is cooled to 30 ° C., 25% by mass ammonia water and deionized water are supplied and mixed, and then filtered using a 100 mesh wire netting, so that the composite resin particles (A-2) are submerged in water. A dispersed aqueous resin composition (X-2) (non-volatile content: 20.0% by mass, pH 8) was obtained.

  Further, 100 parts by mass of the aqueous resin composition (X-2), 0.1 part by mass of BYK348 (manufactured by Big Chemie Japan, polyether-modified siloxane, concentration 100% by mass), and EMUSTAR-6315D (Nippon Seiwa Co., Ltd.) A coating agent (Y-2) having a nonvolatile content of 15% by mass was obtained by mixing 3.5 parts by mass and appropriately ion-exchanged water.

[Example 3] Preparation of aqueous resin composition (X-3) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst. 450 parts by mass of deionized water, 400 parts by mass of the above urethane resin aqueous dispersion (PU1), 1.5 mass of Neogen S-20 (Daiichi Kogyo Seiyaku Co., Ltd., sodium dodecylbenzenesulfonate, concentration 20% by mass) The mixture was stirred and heated to 80 ° C. while blowing nitrogen. After raising the temperature to 80 ° C. and continuing nitrogen substitution for 60 minutes, 8 parts by mass of a polymerization initiator 10% by mass ammonium persulfate was put into the reaction vessel and stirred for 5 minutes. Thereafter, 100 parts by mass of 50% by mass acrylamide, 29 parts by mass of styrene, 20 parts by mass of butyl acrylate, and 1 part by mass of N, N-dimethylaminoethyl acrylate were added dropwise over 90 minutes, polymerization initiator 10% by mass ammonium persulfate 4 A part by mass was dropped over 120 minutes for polymerization. After completion of the dropwise addition of the monomer mixture and the initiator, the mixture was held at the same temperature for 90 minutes.

  Thereafter, the inside of the reaction vessel is cooled to 30 ° C., 25% by mass ammonia water and deionized water are supplied and mixed, and then filtered using a 100 mesh wire netting, so that the composite resin particles (A-3) are submerged in water. A dispersed aqueous resin composition (X-3) (nonvolatile content: 20.0 mass%, pH 8) was obtained.

  Further, 100 parts by mass of the aqueous resin composition (X-3), 0.1 part by mass of BYK348 (manufactured by Big Chemie Japan, polyether-modified siloxane, concentration 100% by mass), and EMUSTAR-6315D (Nippon Seiwa Co., Ltd.) A coating agent (Y-3) having a nonvolatile content of 15% by mass was obtained by mixing 3.5 parts by mass and appropriately ion-exchanged water.

[Example 4] Preparation of aqueous resin composition (X-4) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst. Put 510 parts by weight of deionized water, 600 parts by weight of the above urethane resin aqueous dispersion (PU1), 0.5 parts by weight of Nucor 271A (manufactured by Nippon Emulsifier Co., Ltd., sodium alkyldiphenyl ether disulfonate, concentration 45% by weight), The mixture was stirred and heated up to 80 ° C. while blowing nitrogen. After raising the temperature to 80 ° C. and continuing nitrogen substitution for 60 minutes, 8 parts by mass of a polymerization initiator 10% by mass ammonium persulfate was put into the reaction vessel and stirred for 5 minutes. Thereafter, 80 parts by mass of 50% by mass acrylamide and 60 parts by mass of styrene were each added dropwise over 120 minutes, and 4 parts by mass of 10% by mass of a polymerization initiator ammonium persulfate were added dropwise over 150 minutes for polymerization. After completion of the dropwise addition of the monomer mixture and the initiator, the mixture was held at the same temperature for 120 minutes.

  Thereafter, the inside of the reaction vessel is cooled to 30 ° C., 25% by mass ammonia water and deionized water are supplied and mixed, and then filtered using a 100 mesh wire netting, so that the composite resin particles (A-4) are submerged in water. A dispersed aqueous resin composition (X-4) (non-volatile content: 20.0% by mass, pH 8) was obtained.

  Further, 100 parts by mass of the aqueous resin composition (X-4), 0.1 part by mass of BYK348 (manufactured by Big Chemie Japan, polyether-modified siloxane, concentration 100% by mass), and EMUSTAR-6315D (Nippon Seiwa Co., Ltd.) A coating agent (Y-4) having a nonvolatile content of 15% by mass was obtained by mixing 3.5 parts by mass and appropriately ion-exchanged water.

[Example 5] Preparation of aqueous resin composition (X-5) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst. Put 420 parts by weight of deionized water, 200 parts by weight of the urethane resin aqueous dispersion (PU1), 0.5 parts by weight of Nucor 271A (manufactured by Nippon Emulsifier Co., Ltd., sodium alkyldiphenyl ether disulfonate, concentration 45% by weight), The mixture was stirred and heated up to 80 ° C. while blowing nitrogen. After raising the temperature to 80 ° C. and continuing nitrogen substitution for 60 minutes, 8 parts by mass of a polymerization initiator 10% by mass ammonium persulfate was put into the reaction vessel and stirred for 5 minutes. Thereafter, 60 parts by mass of 50% by mass acrylamide, 30 parts by mass of styrene, and 40 parts by mass of acrylonitrile were each added dropwise over 120 minutes, and 4 parts by mass of a polymerization initiator 10% by mass ammonium persulfate were added dropwise over 150 minutes for polymerization. After completion of the dropwise addition of the monomer mixture and the initiator, the mixture was held at the same temperature for 120 minutes.

  Thereafter, the inside of the reaction vessel is cooled to 30 ° C., 25% by mass ammonia water and deionized water are supplied and mixed, and then filtered using a 100-mesh wire mesh, so that the composite resin particles (A-5) are submerged in water. A dispersed aqueous resin composition (X-5) (non-volatile content: 20.0% by mass, pH 8) was obtained.

  Further, 100 parts by mass of the aqueous resin composition (X-5), 0.1 part by mass of BYK348 (manufactured by Big Chemie Japan, polyether-modified siloxane, concentration 100% by mass), and EMUSTAR-6315D (Nippon Seiwa Co., Ltd.) A coating agent (Y-5) having a nonvolatile content of 15% by mass was obtained by mixing 3.5 parts by mass and appropriately ion-exchanged water.

[Example 6] Preparation of aqueous resin composition (X-6) In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst. 400 parts by mass of deionized water, 160 parts by mass of the above urethane resin aqueous dispersion (PU1), Aqualon KH-10 (Daiichi Kogyo Seiyaku Co., Ltd .; polyoxyethylene-1- (allyloxymethyl) alkyl sulfate ammonium (Salt, solid content: 100% by mass) 1.0 part by mass was stirred and heated to 80 ° C. while blowing nitrogen. After heating up to 80 ° C. and continuing nitrogen substitution for 60 minutes, polymerization initiator V-501 (manufactured by Wako Pure Chemical Industries, Ltd., 4,4-azobis (4-cyanopentanoic acid)) was added at 25 mass% ammonia. 8 parts by mass of the neutralized 10% by mass aqueous solution was put into the reaction vessel and stirred for 5 minutes. Thereafter, 50 parts by mass of 20% by weight methacrylamide and 90 parts by mass of styrene were added dropwise over 90 minutes, polymerization initiator V-501 (manufactured by Wako Pure Chemical Industries, Ltd., 4,4-azobis (4-cyanopentanoic acid) 4 parts by weight of 10% by weight aqueous solution neutralized with 25% ammonia was added dropwise over 120 minutes for polymerization. After completion of the dropwise addition of the monomer mixture and the initiator, the mixture was held at the same temperature for 90 minutes.

  Thereafter, the inside of the reaction vessel is cooled to 30 ° C., 25% by mass ammonia water and deionized water are supplied and mixed, and then filtered using a 100-mesh wire mesh, so that the composite resin particles (A-6) are submerged in water. A dispersed aqueous resin composition (X-6) (non-volatile content: 20.0% by mass, pH 8) was obtained.

  Further, 100 parts by mass of the aqueous resin composition (X-6), 0.1 part by mass of BYK348 (manufactured by Big Chemie Japan, polyether-modified siloxane, concentration 100% by mass), and EMUSTAR-6315D (Nippon Seiwa Co., Ltd.) A coating agent (Y-6) having a nonvolatile content of 15% by mass was obtained by mixing 3.5 parts by mass and appropriately ion-exchanged water.

[Comparative Example 1] Preparation of aqueous resin composition (X'-1) The urethane resin aqueous dispersion (PU1) obtained in Preparation Example 2 was adjusted to a non-volatile content of 20.0% with ion-exchanged water. 1 aqueous resin composition (X′-1).
Further, 100 parts by mass of the aqueous resin composition (X′-1), 0.1 part by mass of BYK348 (manufactured by Big Chemie Japan, polyether-modified siloxane, concentration 100% by mass), and EMUSTAR-6315D (Nippon Seiwa) Co., Ltd., paraffin wax, concentration 40% by mass) 3.5 parts by mass and 10.8 parts by mass of Zircosol AC-7 (Daiichi Rare Element Chemical Industries, Ltd., ammonium zirconium carbonate, concentration 13% by mass) And a suitable amount of ion-exchanged water were mixed to obtain a coating agent (Y′-1) having a nonvolatile content of 15% by mass.

[Comparative Example 2] Preparation of aqueous resin composition (X'-2) Reaction vessel equipped with stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping monomer mixture, dropping funnel for dropping polymerization catalyst Into this, 330 parts by weight of deionized water and 1.5 parts by weight of Neogen S-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., sodium dodecylbenzenesulfonate, concentration 20% by weight) are stirred and stirred at 80 ° C. while blowing nitrogen. The temperature was raised to. After raising the temperature to 80 ° C. and continuing nitrogen substitution for 60 minutes, 8 parts by mass of a polymerization initiator 10% by mass ammonium persulfate was put into the reaction vessel and stirred for 5 minutes. Thereafter, 140 parts by mass of 50% by mass acrylamide, 28 parts by mass of styrene, and 2 parts by mass of methacrylic acid were added dropwise over 90 minutes, and 4 parts by mass of 10% ammonium persulfate polymerization initiator was added dropwise over 120 minutes for polymerization. After completion of the dropwise addition of the monomer mixture and the initiator, the mixture was held at the same temperature for 90 minutes.

  Thereafter, the inside of the reaction vessel is cooled to 30 ° C., 25% by mass of ammonia water and deionized water are supplied and mixed, and then filtered using a 100 mesh wire net, so that the composite resin particles (A-1) are submerged in water. A dispersed aqueous resin composition (X′-2) (nonvolatile content: 20.0 mass%, pH 8) was obtained.

  Moreover, except using the said aqueous resin composition (X'-2) instead of the said aqueous resin composition (X'-1), it is the same method as the said Comparative Example 1, and non-volatile matter 15 mass% A coating agent (Y′-2) was obtained.

[Comparative Example 3] Preparation of aqueous resin composition (X'-3) Reaction vessel equipped with stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping monomer mixture, dropping funnel for dropping polymerization catalyst 550 parts by weight of deionized water, 600 parts by weight of the above urethane resin aqueous dispersion (PU1), Neogen S-20 (Daiichi Kogyo Seiyaku Co., Ltd., sodium dodecylbenzenesulfonate, concentration 20% by weight) 1.5 A mass part was added, stirred, and heated to 80 ° C. while blowing nitrogen. After raising the temperature to 80 ° C. and continuing nitrogen substitution for 60 minutes, 8 parts by mass of a polymerization initiator 10% by mass ammonium persulfate was put into the reaction vessel and stirred for 5 minutes. Thereafter, 60 parts by mass of styrene and 40 parts by mass of butyl acrylate were added dropwise over 90 minutes, and 4 parts by mass of 10% ammonium persulfate polymerization initiator was added dropwise over 120 minutes for polymerization. After completion of the dropwise addition of the monomer mixture and the initiator, the mixture was held at the same temperature for 90 minutes.

  Thereafter, the inside of the reaction vessel is cooled to 30 ° C., 25% by mass ammonia water and deionized water are supplied and mixed, and then filtered using a 100-mesh wire mesh, so that the composite resin particles (A′-3) are submerged in water. An aqueous resin composition (X′-3) (non-volatile content: 20.0 mass%, pH 8) dispersed in was obtained.

Moreover, except using the said aqueous resin composition (X'-3) instead of the said aqueous resin composition (X'-1), it is the same method as the said Comparative Example 1, and non-volatile content of 15 mass% A coating agent (Y′-3) was obtained.
[Comparative Example 4] Preparation of aqueous resin composition (X'-4) 100 parts by weight of Gohsenol Z-200 (Nippon Gosei Co., Ltd., modified polyvinyl alcohol) adjusted to 15% by mass with ion-exchanged water, BYK348 ( Big Chemie Japan Co., Ltd., polyether-modified siloxane, concentration 100% by mass) 0.075 parts by mass, EMUSTAR-6315D (Nippon Seiwa Co., Ltd., paraffin wax, concentration 40% by mass) 2.6 parts by mass, 10 A coating agent (Y′-4) having a nonvolatile content of 15% by mass was obtained by mixing 0.2 parts by mass of mass% glyoxal and appropriately mixing ion-exchanged water.

[Method for preparing specimen]
The coating agent is applied on a film made of polyethylene terephthalate having a thickness of 12 μm so that the film thickness when dried is about 5 μm, heat-treated at 80 ° C. for 15 minutes, and then at room temperature of 25 ° C. for 1 day. By curing, a test piece having a film formed on the substrate was obtained.

[Method for evaluating wet heat resistance]
The test piece obtained above was placed in a constant temperature and humidity machine with a temperature of 60 ° C. and a humidity of 90% for 24 hours, and the state of the film was observed. The state of the film surface after the test was visually observed, and the moisture and heat resistance of the film was evaluated according to the following criteria.
[Evaluation criteria]
1: Wrinkles were generated on the surface of the film.
2: The coating surface was whitened, and an adhesion phenomenon was observed when touched with a finger immediately after evaluation.
3: Whitening was observed on a very small part of the film surface, but even if it was touched with a finger immediately after evaluation, no adhesive phenomenon was observed, and there was no practical problem.
4; There was no change on the film surface.

[Water resistance evaluation method]
Two test pieces obtained as described above were prepared, and one drop of tap water was dropped on one test piece film surface with a dropper, and another film surface was bonded thereto, and a load of 1500 g was applied. The surface state was confirmed by peeling after 10 minutes.
[Evaluation criteria]
○: No blocking was observed on the surface of the film, and no peeling of the resin constituting the film was observed.
Δ: Slight blocking occurred on a very small part of the film surface, but peeling of the resin constituting the film was not observed.
X: Remarkable blocking occurred in the range of about half of the entire coating surface, and peeling of the coating from the polyethylene terephthalate substrate was observed.

[Method for evaluating heat resistance]
A 140 ° C. heat block was brought into contact with the coating surface of the test piece obtained above for 1 second. The state of the surface of the film before and after contact with the heat block was visually observed, and the heat resistance of the film was evaluated according to the following criteria.

[Evaluation criteria]
○: No blocking was observed on the surface of the film, and no fusion of the resin constituting the film to the heat block was observed.
Δ: Slight blocking occurred on a small part of the film surface, but it did not cause the resin to be fused to the heat block, and the film was not peeled off from the polyethylene terephthalate substrate. .
X: Remarkable blocking occurred in the range of about half of the entire surface of the film, and the fusion of the resin to the heat block and the peeling of the film from the polyethylene terephthalate substrate were observed.

[Alcohol resistance evaluation method]
A cotton swab soaked with ethanol was brought into contact with the film surface of the test piece obtained above, and the film surface was rubbed with a load of 500 g.

  The state of the film surface after rubbing was visually observed, and the alcohol resistance of the film was evaluated according to the following criteria.

[Evaluation criteria]
1: Peeling of the film from the substrate was observed with a rubbing frequency of less than 10 times.
2: The peeling | exfoliation from the base material of the said film | membrane was seen by the rubbing frequency of 10 times or more and less than 20 times.
3: Peeling of the film from the substrate was observed at the number of rubbing times of 20 times or more and less than 30 times.
4: Peeling of the film from the substrate was observed at a rubbing frequency of 30 times or more and less than 40 times.
5: Peeling of the film from the substrate was observed at the number of times of rubbing of 50 times or more.

Claims (9)

A composite resin particle (A) formed from a vinyl polymer (a1) having an amide group and an aryl group, a hydrophilic group-containing urethane resin (a2), and an aqueous medium (B) An aqueous resin composition. The vinyl polymer (a1) contains 0.5 mmol / g to 15 mmol / g of amide groups and 0.5 mmol / g to 10 mmol / g of aryl groups with respect to the total amount of the composite resin particles (A). The aqueous resin composition according to claim 1, wherein The aqueous resin composition according to claim 1, wherein the vinyl polymer (a1) further has an amino group. The said vinyl polymer (a1) has the said amino group in the range of 0.03 mmol / g-0.70 mmol / g with respect to the whole quantity of the said vinyl polymer (a1). An aqueous resin composition. The aqueous resin composition according to claim 1, wherein the hydrophilic group of the hydrophilic group-containing urethane resin (a2) is an anionic group or a cationic group. The hydrophilic group-containing urethane resin (a2) is obtained by reacting a polyol (a2-1) containing an aromatic polyester polyol and a hydrophilic group-containing polyol and a polyisocyanate (a2-2). Item 4. The aqueous resin composition according to Item 1. The aqueous resin composition of Claim 1 whose mass ratio [(a1) / (a2)] of the said vinyl polymer (a1) and the said urethane resin (a2) is 99/1-5/95. A coating agent comprising the aqueous resin composition according to claim 1. A thermal transfer type ink ribbon in which an ink layer, a support layer, and a back layer are laminated in order, wherein the back layer is a layer formed using the coating agent according to claim 8. ink ribbon.