JP2016017136A - Urethane resin composition and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane resin composition having excellent adhesiveness to a resin film substrate such as a polyester film and a polypropylene film and capable of forming a coating film having good soft feeling properties, and to provide a laminate using the composition.SOLUTION: A urethane resin composition comprises a urethane resin (A) obtained by reacting a urethane resin (a1) having an isocyanate group and a compound (a2) having one or more primary amino groups, silica (B) and an aqueous medium (C).SELECTED DRAWING: None

Description

  The present invention is a urethane resin composition that can be used for a coating agent such as a polyester film or a polypropylene film, has excellent adhesion to a substrate, and can form a coating film with good soft feel, and uses the same. Relates to the laminated body.

  In recent years, the main body of home appliances such as refrigerators, televisions, air conditioners and the like, as well as remote controls, mobile phones, smartphones, personal computer and other information terminal housings, automobile interior and exterior materials, wallpaper, cosmetic boxes, book covers, etc. For example, a material having a soft feel when touched with a hand, that is, having a soft feel is required.

  In order to impart the above soft feel, there is a method of applying a coating agent or the like on the surface of various articles. As a material for imparting this soft feel, an isocyanate compound obtained by reacting a polyester polyol having two or more hydroxyl groups in one molecule and hexamethylene diisocyanate is further reacted with (meth) acrylate having a hydroxyl group. An active energy curable topcoat composition containing an active energy ray curable urethane (meth) acrylate and a photopolymerization initiator has been proposed (see, for example, Patent Document 1). However, this active energy ray-curable topcoat composition has a problem that the touch (soft feeling) such as high elasticity and low grip required for soft feel is insufficient.

  Therefore, there has been a demand for a material that can form a coating film with good soft feel and that has excellent adhesion to a substrate.

JP 2007-131700 A

  The problem to be solved by the present invention is, for example, a urethane resin that has excellent adhesion to a resin film substrate such as a polyester film and a polypropylene film and that can form a coating film with good soft feel. It is to provide a composition and a laminate using the composition.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a reaction between a urethane resin (a1) having an isocyanate group and a compound (a2) having one or more primary amino groups. The urethane resin composition which can solve the said subject was discovered by combining and using the obtained urethane resin (A) and silica (B).

  That is, the present invention relates to a urethane resin (A), silica (B) and a urethane resin (A1) obtained by reacting a urethane resin (a1) having an isocyanate group with a compound (a2) having one or more primary amino groups. The present invention relates to a urethane resin composition containing an aqueous medium (C).

  The urethane resin composition of the present invention is a main body of home appliances such as a refrigerator, a TV, an air conditioner and the like, a remote controller thereof, a casing of an information terminal such as a mobile phone, a smartphone, a personal computer, an automobile interior member, wallpaper, a cosmetic box, a book cover, etc. By applying to the surface of an article that is directly touched and forming a coating film, it is possible to impart soft feel properties with excellent tactile sensation to the surface of various articles. In particular, it can form a coating film with excellent adhesion and good soft feel to resin film substrates such as polyester film and polypropylene film. It can be suitably used for a layer-forming coating agent or the like. Moreover, the laminated body of this invention can be used conveniently for a book cover, wallpaper, a cosmetic box, etc., for example.

  The urethane resin composition of the present invention comprises a urethane resin (A) obtained by reacting a urethane resin (a1) having an isocyanate group with a compound (a2) having one or more primary amino groups, silica ( B) and an aqueous medium (C) are contained.

  Furthermore, as the urethane resin (A), the equivalent ratio of the primary amino group of the compound (a2) to the isocyanate group of the urethane resin (a1) [primary amino group of the compound (a2) / the above When using what is obtained by making it react on the conditions from which the isocyanate group which a urethane resin (a1) has is 0.4-0.99, forming the coating film which has the especially outstanding base-material adhesiveness It is preferable and it is more preferable that it is 0.5-0.95. Moreover, when forming the coating film which has the outstanding adhesiveness, it is preferable to make it react on the conditions whose urea content will be 150-1000 mmol / kg.

  Examples of the urethane resin (A) include a urethane resin (a1) having an isocyanate group obtained by reacting a polyol (a1-1) and a polyisocyanate (a1-2), and the primary amino group. What was obtained by making it react with the compound (a2) which has this is mentioned.

  Examples of the polyol (a1-1) include polyester polyol, polycarbonate polyol, polyether polyol, and polyolefin polyol. Among these, polyether polyol is preferable because durability of a coating film formed using the urethane resin composition of the present invention can be further improved. Moreover, these polyols (a1-1) can be used alone or in combination of two or more.

  Examples of the polyether polyol that can be used in the polyol (a1-1) include those obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator. Can be mentioned.

  Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, bisphenol A, glycerin, Examples include trimethylolethane and trimethylolpropane.

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

  As the polyether polyol that can be used for the polyol (a1-1), specifically, polyoxytetramethylene glycol formed by ring opening of tetrahydrofuran is preferably used.

  As said polyether polyol, since a base-material adhesiveness can be improved further, it is preferable to use the thing of the number average molecular weights 500-3,000.

  The polyether polyol is preferably used in the range of 1,000 to 3,000 with respect to the entire polyol (a1-1) used when the urethane resin (A) is produced.

  Examples of the polyester polyol that can be used for the polyol (a1-1) include those obtained by esterifying low molecular weight polyols and polycarboxylic acids, and ring-opening cyclic ester compounds such as ε-caprolactone. Examples thereof include polyesters obtained by polymerization reaction, and copolymerized polyesters thereof.

  Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, and 1,3- Examples thereof include aliphatic polyols such as butanediol, aliphatic cyclic structure-containing polyols such as cyclohexanedimethanol, bisphenol compounds such as bisphenol A and bisphenol F, and aromatic structure-containing polyols such as alkylene oxide adducts thereof.

  Examples of the polycarboxylic acid that can be used in the production of the polyester polyol include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and naphthalene. Aromatic polycarboxylic acids such as dicarboxylic acids, and anhydrides or ester-forming derivatives thereof.

  As said polyester polyol, it is preferable to use what has the number average molecular weight of the range of 200-5,000.

  Moreover, as a polycarbonate polyol which can be used for the said polyol (a1-1), what is obtained by making carbonate ester and a polyol react, the thing obtained by making phosgene, bisphenol A, etc. react are mentioned, for example. .

  Examples of the carbonate ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate, and the like.

  Examples of the polyol that can react with the carbonate ester include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5. -Relatively low molecular weight diols such as pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, cyclohexanedimethanol and the like having a molecular weight of about 50 to 2,000, polyethylene glycol, polypropylene glycol, polyhexamethylene adipate, etc. And polyester polyols.

  As said polycarbonate polyol, since a base-material adhesiveness can be improved further, it is preferable to use the thing of the number average molecular weights 500-4,000.

  Examples of the polyolefin polyol that can be used for the polyol (a1-1) include polyethylene polyol, polypropylene polyol, polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, and hydrogenated (hydrogenated) polyisoprene polyol. Can be mentioned.

  Further, as the polyol (a1-1), from the viewpoint of imparting good water dispersion stability to the urethane resin (A), a polyol having a hydrophilic group can be used in combination with the above-described one. .

  As the polyol having the hydrophilic group, for example, a polyol having an anionic group other than the above-described polyol, a polyol having a cationic group, and a polyol having a nonionic group can be used. Among these, it is preferable to use a polyol having an anionic group or a polyol having a cationic group, and it is more preferable to use a polyol having an anionic group.

  Examples of the polyol having an anionic group include a polyol having a carboxyl group and a polyol having a sulfonic acid group.

  Examples of the polyol having a carboxyl group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, 2,2′-dimethylolvaleric acid, and the like. It is done. Among these, 2,2'-dimethylolpropionic acid is preferable. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol which has the said carboxyl group react with various polycarboxylic acids can also be used.

  Examples of the polyol having a sulfonic acid group include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, and 5 [4-sulfophenoxy] isophthalic acid, and salts thereof, and the aromatic structure. The polyester polyol obtained by making it react with the low molecular-weight polyol illustrated as what can be used for manufacture of the polyester polyol (a1-1) which has this is mentioned.

  The polyol having a carboxyl group or the polyol having a sulfonic acid group is preferably used in the range where the acid value of the urethane resin (A) is from 5 to 70, more preferably from 10 to 50. preferable. In addition, the acid value said by this invention is the theoretical value computed based on the usage-amount of acid group containing compounds, such as a polyol which has a carboxyl group used for manufacture of the said urethane resin (A).

  The anionic groups are preferably partially or wholly neutralized with a basic compound or the like in order to exhibit good water dispersibility.

  Examples of basic compounds that can be used when neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine, sodium hydroxide, Examples thereof include metal hydroxides containing potassium hydroxide and lithium hydroxide. From the viewpoint of improving the water dispersion stability of the urethane resin composition, the basic compound has a basic group / anionic group = 0.5 to 3.0 (molar ratio) of the basic compound. It is preferable to use, and it is more preferable to use in the range which becomes 0.8-2.0 (molar ratio).

  Examples of the polyol having a cationic group include a polyol having a tertiary amino group. Specific examples include N-methyl-diethanolamine, a polyol obtained by reacting a compound having two epoxies in one molecule and a secondary amine.

  It is preferable that a part or all of the cationic group is neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid and adipic acid.

  Further, the tertiary amino group as the cationic group is preferably partly or entirely quaternized. Examples of the quaternizing agent include dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like. Among these, it is preferable to use dimethyl sulfate.

  Examples of the polyol having a nonionic group include a polyol having a polyoxyethylene structure.

  It is preferable to use the polyol which has the said hydrophilic group in 0.3-10 mass% in the whole quantity of the polyol (a1-1) used for manufacture of the said urethane resin (A).

  Moreover, as said polyol (a1-1), other polyol can be used as needed besides the above-mentioned polyol.

  Examples of the other polyol include ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5. -Relatively low molecular weight polyols such as pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, and cyclohexanedimethanol.

  Examples of the polyisocyanate (a1-2) that can react with the polyol (a1-1) include 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, and phenylene diisocyanate. , Aromatic polyisocyanates such as tolylene diisocyanate, naphthalene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, aliphatic such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate Polyisocyanate having a cyclic structure Sulfonate, and the like.

  The urethane resin (A) is, for example, a urethane resin having an isocyanate group by reacting the polyol (a1-1) and the polyisocyanate (a1-2) in the absence of a solvent or in the presence of an organic solvent. When (a1) is produced and then there is a hydrophilic group in the urethane resin (a1), an aqueous medium (C) is prepared by neutralizing part or all of the hydrophilic group as necessary. ) And mixing with the compound (a2) having a primary amino group and reacting with the isocyanate group of the urethane resin (a1).

  For example, the reaction of the polyol (a1-1) and the polyisocyanate (a1-2) has an equivalent ratio of the isocyanate group of the polyisocyanate (a1-2) to the hydroxyl group of the polyol (a1-1). , Preferably in the range of 1.05 to 2.50, more preferably in the range of 1.10 to 2.00.

  Examples of the organic solvent that can be used in producing the urethane resin (A) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate solvents such as ethyl acetate and butyl acetate; acetonitrile and the like. Nitrile solvents of the following: amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.

  In addition, in order to reduce the burden on safety and the environment, the organic solvent removes part or all of the organic solvent by, for example, distilling under reduced pressure during or after the production of the urethane resin (A). May be.

  When the urethane resin (A) is produced, by using the compound (a2) having a primary amino group as its raw material, the urethane resin (A) has excellent adhesion to various substrates of the coating film. Can be.

  The compound (a2) having a primary amino group preferably has at least one active hydrogen atom other than the active hydrogen atom contained in one primary amino group. Examples of the functional group having an active hydrogen atom other than the active hydrogen atom contained in one primary amino group include a primary amino group, a secondary amino group, a hydroxyl group, a mercapto group, and a carboxyl group. For example, in the case of hydrazine, one of two primary amino groups is a functional group having two active hydrogen atoms.

  Examples of the compound (a2) having a primary amino group include hydrazine, dicarboxylic acid dihydrazide, carbohydrazide, 1,3-bis (hydrazinocarbonoethyl) -5-isopropylhydantoin, ethanolamine, diethanolamine, and diamino. Ethanol or the like can be used, and it is preferable to use hydrazine, dicarboxylic acid dihydrazide, or carbohydrazide, and it is preferable to use hydrazine because the adhesion to the substrate can be further improved.

  Examples of the dicarboxylic acid dihydrazide include a combination of one or more of malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide can do. Of these, the use of hydrazine is preferable for imparting excellent adhesion.

  Moreover, the water-based conversion of the urethane resin (A) produced by the above method can be performed, for example, by the following method.

  [Method 1] After neutralizing or quaternizing some or all of the hydrophilic groups of the urethane resin (a1) obtained by reacting the polyol (a1-1) and the polyisocyanate (a1-2), A method in which water is dispersed by introducing water, and then the urethane resin (A) is dispersed in water by chain extension using the compound (a2) having the primary amino group.

  [Method 2] Urethane resin (a1) obtained by reacting polyol (a1-1) with polyisocyanate (a1-2) and compound (a2) having the primary amino group in a reaction vessel The urethane resin (A) is produced by batch or partial charge and chain extension reaction, and then part or all of the hydrophilic groups in the obtained urethane resin (A) are neutralized or quaternized. , A method of adding water to disperse water.

  In [Method 1] to [Method 2], an emulsifier may be used as necessary. In addition, when water is dissolved or dispersed, a machine such as a homogenizer may be used as necessary.

  Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Fatty acid salts such as sodium oleate, alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc. Anionic emulsifiers; Cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. It is. Among these, it is preferable to use an anionic or nonionic emulsifier because the storage stability of the urethane resin composition of the present invention can be maintained.

  The urethane resin (A) aqueous dispersion in which the urethane resin (A) obtained by the above method is dispersed in the aqueous medium (C) is 10-50 masses of the urethane resin (A) in the total amount of the aqueous dispersion. % Is preferable because the storage stability of the urethane resin composition of the present invention is further improved.

  The urethane resin (A) aqueous dispersion may be a mixture of two or more urethane resins having different compositions. Specifically, two or more urethane resins having different compositions of the polyol (a1) used for the production of the urethane resin can be used in combination.

  The silica (B) used in the present invention is preferably wet silica from the viewpoint of imparting excellent tactile sensation to the formed coating film. The average particle diameter of the silica (B) is preferably in the range of 1 to 30 μm and more preferably in the range of 2 to 20 μm because it can impart excellent touch feeling to the coating film. Furthermore, the range of 3-15 micrometers is further more preferable. In addition, an average particle diameter is calculated | required from the result measured by the dynamic light scattering method.

  Since the said silica (B) content maintains high base-material adhesiveness and can provide the tactile feeling excellent in the coating film, the range of 1-30 mass parts with respect to 100 mass parts of said urethane resins (A). Preferably, the range of 3-20 mass parts is more preferable.

  Examples of the aqueous medium (C) used in the present invention 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; 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.

  The aqueous medium (C) is preferably contained in the total amount of the urethane resin composition of the present invention in the range of 30 to 90% by mass because of excellent storage stability.

  The urethane resin composition of the present invention is produced, for example, by supplying and mixing the aqueous dispersion of the urethane resin (A) obtained by the above method and silica (B) in a lump or divided. Can do.

  The urethane resin composition of the present invention obtained by the above method may contain other additives as necessary in addition to the above-described components.

  In addition, the urethane resin composition of the present invention includes, as necessary, a film-forming aid, a crosslinking agent, a curing accelerator, a plasticizer, an antistatic agent, a wax, a surfactant, a light stabilizer, a flow regulator, Various additives such as dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments and extender pigments can be used.

  By using the said crosslinking agent, the heat-and-moisture resistance and abrasion resistance of the coating film of the urethane resin composition of this invention can be improved more. As said crosslinking agent, the 1 or more types chosen from the group which consists of an amino resin, an aziridine compound, a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, and an isocyanate compound can be used, for example.

  The cross-linking agent can be used to improve the scratch resistance of the primer layer. For example, the cross-linking agent is selected from the group consisting of amino resins, aziridine compounds, melamine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, and isocyanate compounds. More than species can be used.

  Moreover, the dispersion stability of the urethane resin composition of this invention can be improved further by using the said surfactant. When using a surfactant, it is preferable to use it in a range of 20 parts by mass or less with respect to 100 parts by mass of the urethane resin (A) because the substrate adhesion and water resistance of the resulting coating film can be maintained. It is preferable not to use as much as possible.

  The laminate of the present invention uses the urethane resin composition of the present invention described above, and is obtained by forming a coating film of the urethane resin composition on the surface of a substrate and drying it. .

  Examples of the substrate include a metal substrate, a plastic substrate, a glass substrate, a paper substrate, a wood substrate, and a fibrous substrate. Among these substrates, a plastic substrate is preferable in order to improve the adhesion between the urethane resin composition and the substrate.

  Materials for the plastic substrate include polyester, acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, epoxy resin , Polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC), and the like.

  Articles that can be used by the urethane resin composition of the present invention include main bodies of home appliances such as refrigerators, televisions and air conditioners and remote controllers thereof, mobile phones, smartphones, information terminal cases such as personal computers, automobile interior and exterior members, Articles that can be touched directly, such as wallpaper, makeup boxes, and book covers.

  The laminate of the present invention is a substrate in which a resin film such as a polypropylene film is bonded to a paper substrate via an adhesive layer, and the urethane resin composition of the present invention is applied to the surface and dried. It is formed by. Examples of uses of the laminate of the present invention include book covers, wallpaper, and cosmetic boxes.

  Examples of the method of applying the urethane resin composition of the present invention to the surface of the substrate include, for example, a gravure coater, a roll coater, a comma coater, a knife coater, an air knife coater, a curtain coater, a kiss coater, a shower coater, a flow coater, and a spin coater. Application methods using a coater, dipping, screen printing, spraying, brushing, applicator, bar coater and the like can be mentioned.

  Although the film thickness of the coating film formed using the urethane resin composition of this invention can be suitably adjusted according to the use used, it is preferable that it is normally the range of 0.1-50 micrometers.

  In particular, when the urethane resin composition is applied to the surface of a film such as a polypropylene film, the urethane resin composition is applied to the film surface in the course of biaxial stretching of the plastic substrate at about 200 ° C. An in-line coating method can be employed in which a coating film is formed by applying and drying the product, causing a crosslinking reaction, and then stretching the film in the transverse direction.

  In addition, when the heat sealant or the like is applied to the surface of a plastic film such as a polyethylene terephthalate film, the plastic film obtained by the biaxial stretching is once wound around a roll or the like, and then from the roll. An off-line coating method in which a plastic film is drawn and the urethane resin composition or the like is applied to the surface of the plastic film can be employed.

  When the heat sealant or the like is applied to the surface of the plastic film by the off-line coating method, it is preferable to perform drying at a temperature of approximately 150 ° C. or less so as not to impair the dimensional stability of the plastic film.

  By the above method, a laminate formed by crosslinking and curing the urethane resin composition or the like on the substrate surface can be formed.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.

(Preparation Example 1: Preparation of urethane resin aqueous dispersion (I))
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, under a nitrogen stream, 1000 parts by mass of polyoxytetramethylene glycol (weight average molecular weight: 2,000), 2.2′-di After adding 79.4 parts by mass of methylolpropionic acid and 668.2 parts by mass of ethyl acetate and mixing uniformly, 247.2 parts by mass of tolylene diisocyanate was added, then 0.1 part by mass of dibutyltin dilaurate was added, and For 4 hours to obtain an ethyl acetate solution of a urethane prepolymer having an isocyanate group at the molecular end (mass ratio of isocyanate group to the urethane prepolymer (isocyanate group content); 1.38% by mass). .
Next, the ethyl acetate solution of the urethane prepolymer obtained by the above method was cooled to 40 ° C., 65.9 parts by mass of triethylamine was added to neutralize the carboxyl group in the urethane prepolymer, and then ion-exchanged water 2849. 1 part by mass was added, and then 19.5 parts by mass of 80% by mass of hydrazine hydrated (hydrazine monohydrate, 80% by mass of hydrazine based on the whole) was added and reacted.
After completion of the reaction, ethyl acetate was distilled off under reduced pressure, and ion-exchanged water was added so that the nonvolatile content was 35% by mass, thereby obtaining a urethane resin aqueous dispersion (I). The equivalent ratio of the raw material of the urethane resin in the urethane resin aqueous dispersion (I) [primary amino group of hydrazine / isocyanate group of the urethane prepolymer] is 0.95, and the urea content of the urethane resin Was 490 mmol / kg.

(Preparation Example 2: Preparation of urethane resin aqueous dispersion (II))
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, under a nitrogen stream, 1000 parts by mass of polyoxytetramethylene glycol (weight average molecular weight: 2,000), 2.2′-di After adding 79.4 parts by mass of methylolpropionic acid and 668.2 parts by mass of ethyl acetate and mixing uniformly, 247.2 parts by mass of tolylene diisocyanate was added, then 0.1 part by mass of dibutyltin dilaurate was added, and Was allowed to react for about 4 hours to obtain an ethyl acetate solution of a urethane prepolymer having an isocyanate group at the molecular end (isocyanate group content: 1.38% by mass).
Then, the ethyl acetate solution of the urethane prepolymer obtained by the above method was cooled to 40 ° C., 65.4 parts by mass of triethylamine was added to neutralize the carboxyl group in the urethane prepolymer, and then ion-exchanged water 3174. 1 part by mass was added, and then 54.2 parts by mass of adipic acid dihydrazide was added and reacted.
After completion of the reaction, ethyl acetate was distilled off under reduced pressure, and ion-exchanged water was added so that the non-volatile content was 35% by mass to obtain an aqueous urethane resin dispersion (II). The equivalent ratio of the raw materials of the urethane resin in the urethane resin aqueous dispersion (II) [primary amino group of hydrazine / isocyanate group of the urethane prepolymer] is 0.95, and the urea content of the urethane resin Was 242 mmol / kg.

(Preparation Example 3: Preparation of urethane resin aqueous dispersion (III))
In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen blowing tube, under a nitrogen stream, 1000 parts by mass of polyoxytetramethylene glycol (weight average molecular weight: 2,000), 2.2′-di After adding 79.4 parts by mass of methylolpropionic acid and 884.3 parts by mass of ethyl acetate and mixing uniformly, add 247.2 parts by mass of tolylene diisocyanate, then add 0.1 parts by mass of dibutyltin dilaurate, and add 80 ° C. For 4 hours to obtain an ethyl acetate solution of a urethane prepolymer having an isocyanate group at the molecular end (mass ratio of isocyanate group to the urethane prepolymer (isocyanate group content); 1.38% by mass). .
Next, the ethyl acetate solution of the urethane prepolymer obtained by the above method was cooled to 40 ° C., 65.9 parts by mass of triethylamine was added to neutralize the carboxyl group in the urethane prepolymer, and then ion-exchanged water 2849. 1 part by mass was added, and then 28.0 parts by mass of carbohydrazide was added and reacted.
After completion of the reaction, ethyl acetate was distilled off under reduced pressure, and ion-exchanged water was added so that the nonvolatile content was 35% by mass to obtain an aqueous urethane resin dispersion (III). The equivalent ratio of the raw material of the urethane resin in the urethane resin aqueous dispersion (III) [primary amino group of hydrazine / isocyanate group of the urethane prepolymer] is 0.95, and the urea content of the urethane resin Was 244 mmol / kg.

(Preparation Example 4: Preparation of urethane resin aqueous dispersion (IV))
While introducing nitrogen gas in a reactor equipped with a thermometer, nitrogen gas inlet tube, and stirrer, 42.1 parts by mass of isophthalic acid, 21.4 parts by mass of sebacic acid, 9.3 parts by mass of adipic acid, ethylene glycol 7 7 parts by mass, 25.8 parts by mass of neopentyl glycol, 11.2 parts by mass of butanediol, and 0.05 parts by mass of dibutyltin oxide were esterified at 180 to 230 ° C. for 24 hours, and the acid value was reduced to 1 or less. A polycondensation reaction was performed at 230 ° C. for 24 hours until an aromatic polyester polyol (acid value 0.3, hydroxyl value 56.1, aromatic cyclic concentration 2.53 mol / kg) was obtained. The acid value is a value produced by titration according to the potassium hydroxide method, and the hydroxyl value is a value measured by a method based on a JIS test method (JIS K1557-1: 2007).

  Next, a urethane resin aqueous dispersion (IV) was obtained in the same manner as in Preparation Example 1 except that the obtained aromatic polyester polyol was used in place of the polyoxytetramethylene glycol of Preparation Example 1. The equivalent ratio of the raw material of the urethane resin in the urethane resin aqueous dispersion (IV) [primary amino group of hydrazine / isocyanate group of the urethane prepolymer] is 0.95, and the urea content of the urethane resin Was 490 mmol / kg.

(Comparative Preparation Example 1: Preparation of urethane resin aqueous dispersion (V))
While introducing nitrogen gas in a reactor equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 69.7 parts by mass of adipic acid, 49.8 parts by mass of butanediol and 0.05 part by mass of dibutyltin oxide were charged 180. After esterification at ˜230 ° C. for 24 hours, a polycondensation reaction is performed at 230 ° C. for 24 hours until the acid value becomes 1 or less, and an aliphatic polyester polyol [acid value 0.3, hydroxyl value 56.1, aromatic cyclic Concentration 0 mol / kg) was obtained.

Next, 100 parts by mass of the obtained aliphatic polyester polyol was dehydrated at 100 ° C. under reduced pressure in the reaction vessel, and after cooling to 80 ° C., 94.1 parts by mass of methyl ethyl ketone was added, and the mixture was stirred and mixed uniformly. . Next, 8.8 parts by mass of 2,2-dimethylolpropionic acid and 4.2 parts by mass of 1,4-butanediol were added, and then 28.1 parts by mass of tolylene diisocyanate and 0.08 parts by mass of dibutyltin dilaurate were added. In addition, the reaction was carried out at 80 ° C. for 12 hours to carry out the urethanization step. It was confirmed that the isocyanate value was 0.1% or less, 0.4 parts by weight of normal butanol was added, and the mixture was further reacted for 2 hours, then cooled to 50 ° C., and the nonvolatile content of the urethane resin having a hydrophilic group A 60% by weight solution was obtained.
Then, it is cooled to 50 ° C., 6.7 parts by mass of triethylamine and 710 parts by mass of water are added, methyl ethyl ketone is removed under reduced pressure at a temperature of 40 ° C. to 60 ° C., and water is added to adjust the concentration. A urethane resin aqueous dispersion (V) having a nonvolatile content of 35% by mass in which the urethane resin was dispersed in an aqueous medium was obtained. The equivalent ratio of the raw material of the urethane resin in the urethane resin aqueous dispersion (V) [primary amino group of hydrazine / isocyanate group of the urethane prepolymer] is 0, and the urea content of the urethane resin is 0 mmol. / Kg.

(Example 1: Preparation of urethane resin composition (1))
285.7 parts by mass of a nonvolatile resin 35 mass% urethane resin aqueous dispersion (I) obtained in Preparation Example 1 (100 parts by mass as urethane resin (I)) and silica (“OK-412” manufactured by Evonik Japan Co., Ltd.) Average particle diameter 6.0 μm; hereinafter abbreviated as silica (1).) The urethane resin composition (1) was obtained by mixing 11 parts by mass.

(Example 2: Preparation of urethane resin composition (2))
Urethane by mixing 285.7 parts by mass of the nonvolatile resin 35 mass% urethane resin aqueous dispersion (I) obtained in Preparation Example 1 (100 parts by mass as urethane resin (I)) and 3 parts by mass of silica (1). A resin composition (2) was obtained.

(Example 3: Preparation of urethane resin composition (3))
Urethane by mixing 285.7 parts by mass of the non-volatile component 35 mass% urethane resin aqueous dispersion (I) obtained in Preparation Example 1 (100 parts by mass as urethane resin (I)) and 20 parts by mass of silica (1). A resin composition (3) was obtained.

(Example 4: Preparation of urethane resin composition (4))
285.7 parts by mass of a non-volatile matter 35 mass% urethane resin aqueous dispersion (I) obtained in Preparation Example 1 (100 parts by mass as urethane resin (I)) and silica (“P-78F” manufactured by Mizusawa Chemical Co., Ltd.) Average particle diameter: 18 μm; hereinafter abbreviated as silica (2).) A urethane resin composition (4) was obtained by mixing 11 parts by mass.

(Example 5: Preparation of urethane resin composition (5))
285.7 parts by mass of a non-volatile matter 35 mass% urethane resin aqueous dispersion (I) obtained in Preparation Example 1 (100 parts by mass as urethane resin (I)) and silica (“3300” manufactured by Evonik Japan Co., Ltd.), average particle Diameter: 10 μm; hereinafter abbreviated as silica (3).) A urethane resin composition (5) was obtained by mixing 11 parts by mass.

(Example 6: Preparation of urethane resin composition (6))
Non-volatile content 35 mass% urethane resin aqueous dispersion (I) obtained in Preparation Example 1 285.7 parts by mass (100 parts by mass as urethane resin (I)) and silica (“OK-520, average by Evonik Japan Co., Ltd.) Particle diameter 6.4 μm; hereinafter abbreviated as silica (4).) A urethane resin composition (6) was obtained by mixing 11 parts by mass.

(Example 7: Preparation of urethane resin composition (7))
Urethane by mixing 285.7 parts by mass of the nonvolatile resin 35 mass% urethane resin aqueous dispersion (II) obtained in Preparation Example 2 (100 parts by mass as urethane resin (II)) and 11 parts by mass of silica (1). A resin composition (7) was obtained.

(Example 8: Preparation of urethane resin composition (8))
Urethane by mixing 285.7 parts by mass of the non-volatile content 35 mass% urethane resin aqueous dispersion (III) obtained in Preparation Example 3 (100 parts by mass as urethane resin (III)) and 11 parts by mass of silica (1). A resin composition (8) was obtained.

(Example 9: Preparation of urethane resin composition (9))
Urethane by mixing 285.7 parts by mass of the nonvolatile resin 35 mass% urethane resin aqueous dispersion (IV) obtained in Preparation Example 3 (100 parts by mass as urethane resin (IV)) and 11 parts by mass of silica (1). A resin composition (9) was obtained.

(Example 10: Production of laminate (1))
The urethane resin composition obtained in Example 1 so that the film thickness after drying is about 3 μm on the surface of a film base (thickness: 12 μm) made of a polypropylene sheet (hereinafter abbreviated as “PP”). By applying (1) and heating at 80 ° C. for 5 minutes, a coating film was formed on the surface of the substrate to obtain a laminate (1).

(Examples 11 to 18: Production of laminates (2) to (9))
It replaced with the urethane resin composition (1) used in Example 10, and performed similarly to Example 10 except having used the urethane resin composition (2)-(9) obtained in Examples 2-9. The laminates (2) to (9) were obtained.

(Comparative Example 1: Preparation of urethane resin composition (C1))
By mixing 285.7 parts by mass of the nonvolatile resin 35 mass% urethane resin aqueous dispersion (V) obtained in Comparative Preparation Example 1 (100 parts by mass as the urethane resin (V)) and 11 parts by mass of silica (1). A urethane resin composition (C1) was obtained.

(Comparative Example 2: Production of laminate (R1))
The urethane resin aqueous dispersion (I) obtained in Preparation Example 1 was applied to the surface of a PP film substrate (thickness 12 μm) so that the film thickness after drying was about 3 μm. By heating for a minute, the coating film was formed on the surface of the base material, and the layered product (R1) was obtained.

(Comparative Example 2: Production of laminate (R2))
The urethane resin composition (C1) obtained in Comparative Example 1 was applied to the surface of a PP film substrate (thickness: 12 μm) so that the film thickness after drying was about 3 μm, and the coating was made at 80 ° C. for 5 minutes. By heating, a coating film was formed on the surface of the substrate to obtain a laminate (R2).

  Table 1 shows the compositions of the urethane resin compositions (1) to (9) obtained in Examples 1 to 9 and the urethane resin composition (C1) obtained in Comparative Example 1. In addition, the composition (blending amount) in Table 1 is expressed as a nonvolatile content.

  The following evaluation was performed using the urethane resin compositions and laminates obtained in the above Examples and Comparative Examples.

[Method for evaluating storage stability]
The urethane resin compositions immediately after production and the comparative urethane resin compositions obtained in Examples and Comparative Examples were stored for 7 days in a normal temperature environment. The appearance of the urethane resin composition was visually observed and evaluated based on the following criteria.
(Double-circle): The aggregate was not seen at all and there was no change compared with the thing immediately after manufacture.
○: Some precipitates were confirmed, but at a practically usable level, and the precipitates could be redispersed by stirring again.
(Triangle | delta): The deposit was a little, and even if it stirred again, a part of deposit remained, and it could not fully re-disperse.
X: About 50% by mass or more of the total amount of the resin was precipitated, and could not be redispersed even by stirring again.

[Preparation of test plate]
A coating material is applied to the surface of a base material made of polypipropylene having a thickness of 12 μm so that the film thickness when dried is about 3 μm, and heated at 80 ° C. for 5 minutes. A test plate made of laminated members was prepared.

[Adhesion between substrate and paint layer (adhesion of substrate)]
A 24 mm wide adhesive tape made by Nichiban Co., Ltd. was applied to the surface of the coating layer constituting the test plate prepared by the above method.
Next, the surface of the coating layer was visually evaluated according to the following evaluation criteria when the pressure-sensitive adhesive tape was pulled in a direction perpendicular to the coating layer, and the pressure-sensitive adhesive tape was peeled off from the surface of the coating layer.
A: The paint layer did not peel at all from the substrate surface constituting the test plate.
○: A very small part of the coating layer was peeled off from the surface of the base material constituting the test plate, but the peeled range was less than 10% with respect to the total area of the film constituting the test plate.
(Triangle | delta): The coating layer of the range of 10% or more and less than 50% with respect to the area of the coating layer which comprises a test board peeled from the base-material surface which comprises a test board.
X: The coating layer of 50% or more of range with respect to the total area of the coating layer which comprises a test board peeled from the base-material surface which comprises a test board.

[Measurement of haze value (film appearance)]
The haze value of the test plate prepared by the above method was measured using a haze meter (manufactured by Suga Test Instruments Co., Ltd.). Measured by a method based on JIS test method (JIS K7136: 2000). The haze value (H) was calculated from the following formula.
H (%) = Td / Tt × 100
H: Haze (cloudiness value) (%)
Td: diffuse transmissivity (%)
Tt: Total light transmittance (%)
The haze of the paint layer was evaluated according to the following evaluation criteria.
A: Haze value is 80 to 100
○: Haze value is 60 to 79
Δ: Haze value of 40 to 59
X: Haze value is 0-39

[Soft feeling (tactile sensation)] The test plate prepared by the above-described method was evaluated in three stages based on the feeling of touching it with the hand.
○ (Good): Good soft feeling
Δ (possible): relatively good soft feeling
X (impossible): There is no soft feeling.

  The evaluation results are shown in Table 2.

  From the evaluation results of Examples 10 to 18 shown in Table 2, it was confirmed that the coating film formed was excellent in adhesion to the substrate and had transparency and good tactile sensation (soft feeling). .

  On the other hand, the comparative example 2 is an example which formed the coating film using the urethane resin composition which does not contain a silica. It was confirmed that the adhesion with the substrate was sufficient, but the transparency of the obtained coating film was remarkably poor, and the touch feeling of the coating film was not soft.

  Comparative Example 3 is an example in which a compound having a primary amino group is not used when producing a urethane resin. It was confirmed that the adhesion to the substrate was insufficient, and the touch of the formed coating film was not soft.

Claims (6)

  Urethane resin (A), silica (B) and aqueous medium (C) obtained by reacting urethane resin (a1) having an isocyanate group with compound (a2) having one or more primary amino groups A urethane resin composition characterized by containing.   The urethane resin (A) has an equivalent ratio of the primary amino group of the compound (a2) to the isocyanate group of the urethane resin (a1) [the primary amino group of the compound (a2) / the urethane resin ( The urethane resin composition according to claim 1, wherein the urethane resin composition is obtained by reacting under a condition that the isocyanate group of a1) is 0.4 to 0.99.   The urethane resin composition according to claim 1, wherein the compound (a2) having the primary amino group is a compound having at least one active hydrogen atom other than the active hydrogen atom contained in one primary amino group.   The urethane resin composition according to claim 1, wherein a content of the silica (B) is in a range of 1 to 30 parts by mass with respect to 100 parts by mass of the urethane resin (A).   The laminated body characterized by having the coating film formed by apply | coating the urethane resin composition of any one of Claims 1-4 to the surface of a base material, and drying.   The laminate according to claim 5, wherein the base material is obtained by bonding a resin film to a paper base material via an adhesive layer.