JP5590406B2 - Aqueous urethane resin composition, coating agent, steel sheet surface treatment agent, cured product and laminate - Google Patents

Description

  The present invention relates to an aqueous urethane resin composition that can be used in various fields such as coating agents and adhesives for various substrates including plastic substrates, metal substrates, and wood substrates.

  The coating agent has the role of protecting the surface of the substrate from external factors in addition to the role of imparting design properties to the surface of various substrates. In recent years, the demand for high durability of the formed film has increased. ing.

  In recent years, an aqueous coating agent containing urethane (meth) acrylate has attracted attention as a coating agent capable of forming a film having high durability. Since the coating agent usually forms a film by causing a crosslinking reaction by light irradiation or heating, it is often possible to form a film having higher durability than other coating agents.

  Examples of the urethane (meth) acrylate-containing aqueous coating agent include at least one polyisocyanate compound (i), at least one polyol (ii), and at least one reactive group capable of reacting with an isocyanate group. Containing at least one hydrophilic compound (iii) capable of reacting with an isocyanate group, at least one capable of dispersing the polyurethane prepolymer in an aqueous medium and providing a salt, directly or after reaction with a neutralizing agent At least one (meth) acrylated compound (iv) containing two reactive groups and at least one (meth) acrylated compound containing essentially one reactive group capable of reacting with an isocyanate group ( v) a (meth) acrylated polyurethane prepolymer obtained from the reaction of the five compounds And an aqueous radiation curable composition comprising at least one ethylenically unsaturated compound (B), wherein the composition comprises a total of 3 meq (meth) acrylated groups and polymerizable ethylenically unsaturated groups. (For example, refer to Patent Document 1).

  Although the coating agent containing urethane (meth) acrylate as described above can form a film with a high crosslinking density, it may cause dissolution or deterioration of the film when various solvents such as a cleaning agent are adhered. It was. In addition, since the high crosslink density film is generally not sufficient in terms of adhesion and followability to the substrate, it may cause peeling of the film from the substrate surface immediately after curing or over time. When a force such as deformation or scratching of the film surface is applied, the film may peel off or crack.

  The aqueous radiation curable composition described in the above-mentioned document 1 is also inferior in film deterioration due to adhesion of a solvent or the like, and as described above, adhesion and followability to various substrates such as plastic substrates and metal substrates are poor. In some cases, it is sufficient to cause peeling or cracking of the film from the surface of the base material, and corrosion of the base material may not be sufficiently prevented.

Special table 2009-533504 gazette

  The problem to be solved by the present invention is to provide an aqueous urethane resin composition capable of forming a film excellent in adhesion and followability to a substrate and excellent in durability such as solvent resistance.

  As a result of investigations to solve the above-mentioned problems, the present inventors have found that the problems of the present invention can be solved with a radically polymerizable aqueous urethane resin composition having a specific amount of an aliphatic cyclic structure.

That is, the present invention relates to a polyol (A) and a polyisocyanate (B) containing an aliphatic cyclic structure-containing polyol (a1) and a hydrophilic group-containing polyol (a2) other than the aliphatic cyclic structure-containing polyol (a1 ). A urethane resin (D) having an aliphatic cyclic structure, a hydrophilic group and a polymerizable unsaturated double bond obtained by reacting a hydroxyl group-containing vinyl monomer (C) with an aqueous medium (E) And
The aliphatic cyclic structure-containing polyol (a1) contains an aliphatic cyclic structure-containing polycarbonate polyol or an aliphatic cyclic structure-containing polyester polyol,
Relative to the total weight of the urethane resin (D), the ratio of aliphatic cyclic structure contained in the urethane resin (D) is Ri range der of 2000mmol / kg~5500mmol / kg, the urethane resin (D) is, the aqueous urethane resin composition comprising der Rukoto those having a weight average molecular weight in the range of 30,000 to 200,000, relates to a coating agent, and the steel sheet surface treatment agent comprising the same.

  The aqueous urethane resin composition of the present invention can form a highly durable film excellent in adhesion and followability on various substrates including plastic substrates and metal substrates. It can be used as a coating agent for protecting the material surface or imparting design properties. In particular, it can be used as a surface protective coating agent for metal substrates such as steel plates.

  Further, the aqueous urethane resin composition of the present invention can be suitably used for surface coating of plastic substrates such as ABS resin, PC resin, ABS / PC resin, PS resin, PMMA resin, etc. It can be used for surface coating of products, OA equipment, automobile interior materials and the like.

  In addition, the aqueous urethane resin composition of the present invention can be used for, for example, galvanized steel sheets such as galvanized steel sheets and aluminum-zinc alloy steel sheets, and rust of metal substrates such as aluminum plates, aluminum alloy plates, electromagnetic steel plates, copper plates, and stainless steel plates. For example, it is possible to form a coating with excellent corrosion resistance that can prevent the occurrence of, etc., such as building materials such as outer walls, roofs, civil engineering members such as guardrails, soundproof walls, drainage grooves, home appliances, industrial machinery, automobile parts, etc. It can be used as a coating agent for painting.

  The aqueous urethane resin composition of the present invention comprises an aliphatic cyclic structure-containing polyol (a1) and a polyol (A) containing a hydrophilic group-containing polyol (a2), a polyisocyanate (B), and a hydroxyl group-containing vinyl monomer (C ), A urethane resin (D) having an aliphatic cyclic structure, a hydrophilic group and a polymerizable unsaturated double bond, an aqueous medium (E), and other additives as required The urethane resin (D) having an aliphatic cyclic structure in the range of 2000 mmol / kg to 5500 mmol / kg in the total amount of the urethane resin (D) is dissolved or dispersed in the aqueous medium (E) It is a thing.

First, the urethane resin (D) used in the present invention will be described.
The urethane resin (D) used in the present invention has an aliphatic cyclic structure of 2000 mmol / kg to 5500 mmol / kg among those having an aliphatic cyclic structure, a hydrophilic group and a polymerizable unsaturated double bond. It has in the range.

  The urethane resin (D) has an aliphatic cyclic structure in the range of 2000 mmol / kg to 5500 mmol / kg with respect to the total mass of the urethane resin (D). It is important in forming a film excellent in followability, and particularly preferably has an aliphatic cyclic structure of 3000 to 5000 mmol / kg. By using the urethane resin (D) having the specific amount of the aliphatic cyclic structure, it is possible to greatly improve the adhesion and followability of the obtained film to various substrates.

  Here, in the aqueous urethane resin composition using an urethane resin having an aliphatic cyclic structure of about 1500 mmol / kg instead of the urethane resin (D), a film excellent in adhesion to various substrates and follow-up properties May not be able to form. In addition, in the case of an aqueous urethane resin composition containing, for example, a urethane resin having an aliphatic cyclic structure of about 6000 mmol / kg instead of the urethane resin (D), a relatively flexible film excellent in followability to a substrate May not be able to form. In addition, a urethane resin having an aliphatic cyclic structure of approximately 6000 mmol / kg has a problem that gelation is likely to occur during its production. In addition, content of the said aliphatic cyclic structure shows the ratio of the aliphatic cyclic structure contained in the said urethane resin (D) with respect to the total mass of the said urethane resin (D), The said urethane resin (D) The total mass of all the raw materials such as polyol (A) and polyisocyanate (B) used in the production of the resin, and the aliphatic cyclic structure-containing polyol (a1) and aliphatic used in the production of the urethane resin (A). It is a value calculated based on the amount of an aliphatic cyclic structure contained in an aliphatic cyclic structure-containing compound such as a cyclic structure-containing polyisocyanate.

  Examples of the aliphatic cyclic structure include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a propylcyclohexyl group, a tricyclo [5,2,1,0,2,6] decyl group, and a bicyclo [4]. , 3,0] -nonyl group, tricyclo [5,3,1,1] dodecyl group, propyltricyclo [5,3,1,1] dodecyl group, norbornene group, isobornyl group, dicyclopentanyl group, adamantyl Among them, a cyclohexyl group and a norbornene group are preferable for forming a film having excellent adhesion to a substrate.

  Further, the urethane resin (D) used in the present invention is not limited to merely having an aliphatic cyclic structure in the above-mentioned range. The aliphatic cyclic structure-containing polyol (a1) and the hydrophilic group-containing polyol ( It is important to use what is obtained by reacting the polyol (A) containing a2), the polyisocyanate (B), and the hydroxyl group-containing vinyl monomer (C).

  Part or all of the aliphatic cyclic structure of the urethane resin (D) is a structure derived from the aliphatic cyclic structure-containing polyol (a1) used when producing the urethane resin (D). This is important in solving the problems of the present invention. Here, instead of the urethane resin (D), the aliphatic cyclic structure-containing polyol (a1) is not used, but a general aliphatic polyol and an aliphatic cyclic structure-containing polyisocyanate are reacted. When the obtained urethane resin having an aliphatic cyclic structure in the range of 2000 mmol / kg to 5500 mmol / kg is used, it may be impossible to achieve both excellent substrate adhesion and followability.

  On the other hand, it is not necessary for all of the aliphatic cyclic structure present in the urethane resin (D) to be a structure derived from the aliphatic cyclic structure-containing polyol (a1), and a part thereof is an aliphatic cyclic structure. It may be derived from a contained polyisocyanate, a chain extender or the like.

  The urethane resin (D) has an aliphatic cyclic structure in the range of 2000 mmol / kg to 5500 mmol / kg, and 300 mmol of the aliphatic cyclic structure derived from the aliphatic cyclic structure-containing polyol (a1). / Kg to 2000 mmol / kg is preferably used, and using 300 mmol / kg to 1500 mmol / kg imparts appropriate mechanical strength to the film to be formed. It is preferable because the property can be improved.

  In addition, the urethane resin (D) has a hydrophilic group from the viewpoint of providing an aqueous urethane resin composition excellent in storage stability and imparting good water dispersion stability in the aqueous medium (E). Is preferably used.

  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 obtaining a urethane resin (D) 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 hydrophilic group such as the anionic group and the cationic group is present in the range of 50 mmol / kg to 1000 mmol / kg with respect to the entire urethane resin (D). ) Is preferable for imparting good water dispersion stability.

  Moreover, it is important to use what has a polymerizable unsaturated double bond with the said aliphatic cyclic structure and a hydrophilic group as said urethane resin (D).

  The polymerizable unsaturated double bond is an unsaturated double bond having radical polymerizability, and examples thereof include a vinyl group such as a (meth) acryloyl group. More specifically, vinyl groups such as (meth) acryloyl groups derived from vinyl monomers such as various (meth) acrylic monomers can be mentioned.

  Here, in the aqueous urethane resin composition containing the urethane resin not having the polymerizable unsaturated double bond instead of the urethane resin (D), a film excellent in durability such as solvent resistance is formed. It can be difficult.

  Therefore, as the urethane resin (D), it is preferable to use a resin having a polymerizable unsaturated double bond in the range of 200 mmol / kg to 2000 mmol / kg with respect to the entire urethane resin (D). It is more preferable to use what is in the range of kg to 1000 mmol / kg because a film having further excellent durability can be formed while achieving both excellent substrate adhesion and followability.

  The polymerizable unsaturated double bond may be present in the molecule of the urethane resin (D), but is more preferably present at the molecular end or molecular side chain of the urethane resin (D). The presence is particularly preferable because a relatively flexible film excellent in followability to the substrate can be formed.

  The urethane resin (D) having an aliphatic cyclic structure in the range of 2000 mmol / kg to 5500 mmol / kg, a hydrophilic group, and a polymerizable unsaturated double bond as described above has excellent substrate adhesion and followability. It is preferable to use those having a weight average molecular weight of 5,000 to 500,000, more preferably 10,000 to 500,000, and those having a weight average molecular weight in the range of 30,000 to 200,000. It is more preferable to use those having a weight average molecular weight in the range of 40,000 to 100,000.

  The urethane resin (D) includes, for example, a step (I) of producing a urethane resin (D ′) having an isocyanate group at a molecular end by reacting a polyol (A) and a polyisocyanate (B), and the urethane. It can manufacture by passing through process (II) with which resin (D ') and a hydroxyl-containing vinyl monomer (C) are made to react.

First, the step (I) will be described.
The step (I) is a step of producing a urethane resin (D ′) having an isocyanate group at a molecular end by reacting the polyol (A) with the polyisocyanate (B).

  Here, as the polyol (A) and the polyisocyanate (B), those having an aliphatic cyclic structure or a hydrophilic group may be used in the urethane resin (D). It is preferable when introducing a sex group. Especially, it is preferable to use what contains an aliphatic cyclic structure containing polyol (a1) and a hydrophilic group containing polyol (a2) as said polyol (A), and also, as said polyisocyanate (B), it is aliphatic. It is more preferable to use those containing the cyclic structure-containing polyisocyanate (b1) in order to improve adhesion to various substrates and followability.

  As said polyol (A), an aliphatic cyclic structure containing polyol (a1) and a hydrophilic group containing polyol (a2) can be used as above-mentioned.

  Examples of the aliphatic cyclic structure-containing polyol (a1) include cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, cyclohexanedimethanol, hydroxypropylcyclohexanol, tricyclo [5, 2,1,0,2,6] decane-dimethanol, bicyclo [4,3,0] -nonanediol, dicyclohexanediol, tricyclo [5,3,1,1] dodecanediol, bicyclo [4,3, 0] nonanedimethanol, tricyclo [5,3,1,1] dodecane-diethanol, hydroxypropyltricyclo [5,3,1,1] dodecanol, spiro [3,4] octanediol, butylcyclohexanediol, 1, 1'-bicyclohexylidene Ol, cyclohexane triol, hydrogenated bisphenol - Le A, such as 1,3-adamantane-diol, generally can be used 100 to 500 as low molecular weight aliphatic cyclic structure-containing polyol (a1-1). The molecular weight of the aliphatic cyclic structure-containing polyol is based on the formula weight.

  The aliphatic cyclic structure-containing polyol (a1) contains an aliphatic cyclic structure obtained by reacting the low molecular weight aliphatic cyclic structure-containing polyol (a1-1) with other components. Polycarbonate polyols, aliphatic cyclic structure-containing polyester polyols, aliphatic cyclic structure-containing polyether polyols, and the like can be used.

  As the aliphatic cyclic structure-containing polycarbonate polyol, for example, a product obtained by reacting the low molecular weight aliphatic cyclic structure-containing polyol (a1-1) with dimethyl carbonate, phosgene or the like may be used. it can.

  As said aliphatic cyclic structure containing polycarbonate polyol, it is preferable to use the aliphatic cyclic structure containing polycarbonate polyol which has a number average molecular weight of 800-3000, and what has a number average molecular weight of 800-2000 is used. Is more preferable.

  Examples of the aliphatic cyclic structure-containing polyester polyol include those obtained by esterifying a polyol containing the above-described low molecular weight aliphatic cyclic structure-containing polyol (a1-1) and a polycarboxylic acid. Can be used.

  Examples of the polycarboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, Isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, and anhydrides or ester-forming derivatives thereof can be used.

  As the aliphatic cyclic structure-containing polyester polyol, in addition to the aliphatic cyclic structure-containing polyol (a1-1), other polyols such as neopentyl glycol and 2-butyl-2-ethylpropanediol are optionally used. A combination of polyols can be used. Specifically, it is preferable to use a combination of a polyol having a branched structure such as neopentyl glycol together with the aliphatic cyclic structure-containing polyol (a1-1) from the viewpoint of improving the followability to the substrate.

  The aliphatic cyclic structure-containing polyester polyol includes generally known aliphatic polyols such as neopentyl glycol, and aliphatic cyclic structures such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. What is obtained by reacting the contained polycarboxylic acid or its acid anhydride can be used.

  In addition, as the aliphatic cyclic structure-containing polyether polyol, for example, the low molecular weight aliphatic cyclic structure-containing polyol (a1-1) is used as an initiator, and an alkylene oxide such as ethylene oxide or propylene oxide is added. A polymerized product can be used.

  As the aliphatic cyclic structure-containing polyol (a1), from the viewpoint of imparting excellent substrate adhesion, the aliphatic cyclic structure-containing polyol (a1-1) such as cyclohexanedimethanol among the above-described ones, It is preferable to use an aliphatic cyclic structure-containing polycarbonate polyol or the aliphatic cyclic structure-containing polyester polyol.

  The amount of the aliphatic cyclic structure-containing polyol (a1) varies depending on the aliphatic cyclic structure amount to be introduced into the urethane resin (D), the combination of the polyol (A) and the molecular weight thereof, etc. It is preferable that it is the range of 2 mass%-20 mass% with respect to the total mass of the said polyol (A) and polyisocyanate (B).

  In addition, as the hydrophilic group-containing polyol (a2), those having an aliphatic cyclic structure and having a hydrophilic group can be used. For example, an anionic group-containing polyol, a cationic group-containing polyol, Nonionic group-containing polyols can be used, and among them, anionic group-containing polyols or cationic group-containing polyols are preferably used, and anionic group-containing polyols are more preferably used.

  As the anionic group-containing polyol, for example, a carboxyl group-containing polyol or a sulfonic acid group-containing polyol can be used.

  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.

  The carboxyl group-containing polyol and sulfonic acid group-containing polyol are preferably used in the range where the acid value of the urethane resin (D) is 10 to 70, and more preferably in the range of 10 to 50. 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 carboxyl group containing polyol used for manufacture of the said urethane resin (D).

  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 for neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, and diethylethanolamine, NaOH, KOH, and LiOH. A metal hydroxide containing etc. can be used. The basic compound is preferably used in the range of basic compound / anionic group = 0.5 to 3.0 (molar ratio) from the viewpoint of improving the water dispersion stability of the resulting coating agent. It is more preferable to use in the range which becomes 0.9-2.0 (molar ratio).

  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.

  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. As the quaternizing agent, for example, dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like can be used, and dimethyl sulfate is preferably 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 (a2) is preferably used in the range of 2% by mass to 10% by mass with respect to the total mass of the polyol (A) and the polyisocyanate (B).

  As the polyol (A), in addition to the aliphatic cyclic structure-containing polyol (a1) and the hydrophilic group-containing polyol (a2), other polyol (a3) may be used in combination as necessary. it can.

  As said other polyol (a3), what does not have an aliphatic cyclic structure or a hydrophilic group among polyether polyol, polycarbonate polyol, polyester polyol, etc. can be used, for example. A relatively low molecular weight polyol having no aliphatic cyclic structure or hydrophilic group can also be used. Especially, it is preferable to use the said polycarbonate polyol or polyester polyol as said other polyol (a3), when providing the favorable softness | flexibility of a membrane | film | coat and base-material followability.

Specifically, as the other polyol (a3), polyester polyols such as general-purpose aliphatic and / or aromatic polyester polyols and polyether polyols such as polyoxytetramethylene glycol and polypropylene glycol are used. It is particularly preferred.
The number average molecular weight of the other polyol (a3) is preferably in the range of 500 to 3000, and more preferably in the range of 750 to 2000.

  The other polyol (a3) is 0% by mass with respect to the total amount of the polyol (A) from the viewpoint of imparting good flexibility and substrate followability to the film without impairing excellent substrate adhesion. It is preferable to use in the range of -90 mass%.

  Examples of the polyisocyanate (B) include norbornene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate. Aromatic polyisocyanates, hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and other polyisocyanates having an alicyclic structure It can be used over door. Among them, it is preferable to use an aliphatic polyisocyanate from the viewpoint of preventing yellow discoloration, and from the viewpoint of further improving the scratch resistance and alkali resistance in addition to the above-mentioned discoloration prevention, an aliphatic cyclic structure-containing polyisocyanate. It is preferable to use (b1).

  The reaction between the polyol (A) and the polyisocyanate (B) is carried out, for example, in the absence of a solvent or in the presence of an organic solvent, the aliphatic cyclic structure-containing polyol (a1) and the hydrophilic group-containing polyol (a2). And the polyol (A) containing other polyol (a3) as needed, and the said polyisocyanate (B) can be performed in the range of about 50 to 150 degreeC of reaction temperature.

  In the reaction of the polyol (A) and the polyisocyanate (B), for example, the equivalent ratio of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (A) is in the range of 0.8 to 2.5. Preferably, it is carried out in the range of 0.9 to 1.5.

Examples of the organic solvent that can be used in the step (I) include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; dimethylformamide An amide such as N-methylpyrrolidone can be used alone or in combination of two or more. When the organic solvent is used, from the viewpoint of reducing the environmental burden, the organic solvent may be removed by distillation or the like as necessary during or after the production of the urethane resin (D ′) or the urethane resin (D). It is preferable to remove.
As described above, the urethane resin (D ′) or an organic solvent solution thereof can be obtained through the step (I).

Next, process (II) is demonstrated.
In the step (II), the urethane resin (D) having a polymerizable unsaturated double bond is obtained by reacting the urethane resin (D ′) obtained above with the hydroxyl group-containing vinyl monomer (C). It is a process to obtain. Specifically, in the step (II), the isocyanate group of the urethane resin (D ′) obtained in the step (I) is reacted with the hydroxyl group of the hydroxyl group-containing vinyl monomer (C).

  The reaction between the isocyanate group and the hydroxyl group is performed, for example, by mixing the urethane resin (D ′) alone or an organic solvent solution thereof with the hydroxyl group-containing vinyl monomer (C), and in a range of approximately 50 ° C. to 100 ° C. It can be performed for about 1 to 5 hours.

The hydroxyl group-containing vinyl monomer (C) has an equivalent ratio [hydroxyl group / isocyanate group] of the hydroxyl group of the hydroxyl group-containing vinyl monomer (C) and the isocyanate group of the urethane resin (D ′) of 0.05 to Use in the range of 0.7 is preferable for forming a film having both excellent durability and appropriate mechanical strength and elongation. Moreover, also when using the chain extender mentioned later, it is preferable to use in the range of the said equivalent ratio, and to leave a part of isocyanate group in the urethane resin obtained.
Examples of the hydroxyl group-containing vinyl monomer (C) used in the step (II) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Hydroxyl-containing mono (meth) acrylates such as hydroxy-3-phenoxypropyl (meth) acrylate and cyclohexanedimethanol monoacrylate can be used.

Moreover, as said hydroxyl-containing vinyl monomer (C), hydroxyl-containing poly (meth) acrylates, such as a hydroxyl-containing di (meth) acrylate, can be used.
Examples of the hydroxyl group-containing poly (meth) acrylate include glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth). One or more selected from (meth) acrylates such as acrylates and (meth) acrylate esters of sugar alcohols such as sorbitol can be used. Moreover, what added further alkylene oxide, aliphatic ester, caprolactone, etc. to these (meth) acrylates can also be used. As said alkylene oxide adduct, an ethylene oxide adduct, a propylene oxide adduct, etc. can be used.

  As the hydroxyl group-containing vinyl monomer (C), the crosslinking density of the film can be increased even if the amount used is small, and as a result, a film having excellent durability can be formed. It is preferable to use (meth) acrylate, and specifically, it is more preferable to use pentaerythritol tri (meth) acrylate or the like.

  The hydroxyl group-containing vinyl monomer (C) is the polyol (A), the polyisocyanate (B), the hydroxyl group-containing vinyl monomer (C) used in the production of the urethane resin (D), and will be described later. When a chain extender is used, it is used in the range of 0.1% by mass to 20% by mass with respect to the total mass of the raw materials containing the chain extender in order to improve substrate adhesion, followability and durability. Is preferable.

  As described above, an aliphatic cyclic structure, a hydrophilic group, and a polymerizable unsaturated double bond in the range of 2000 mmol / kg to 5500 mmol / kg are obtained through the above-described steps (I) and (II). The urethane resin (D) which has can be manufactured.

Moreover, the urethane resin (D) includes, for example, an aliphatic cyclic structure-containing polyol (a1), a hydrophilic group-containing polyol (a2), and the hydrophilic group-containing polyol (a2), in addition to the manufacturing method described above. Separately, a step (III) for producing a urethane resin (D ″) having a carboxyl group by reacting a polyol containing a carboxyl group-containing polyol and the like with a polyisocyanate (B), and a urethane resin (D ″) And a step (IV) of reacting a part or all of the carboxyl groups possessed by) with a (meth) acrylic monomer having a functional group reactive with a carboxyl group such as glycidyl (meth) acrylate It can also manufacture by going through.
According to this production method, a urethane resin having a polymerizable unsaturated double bond in the molecular side chain can be produced.

  Further, the urethane resin (D) is, in addition to the production method described above, for example, a polyol containing an aliphatic cyclic structure-containing polyol (a1) and a hydrophilic group-containing polyol (a2), a polyisocyanate (B), Moreover, it can also be produced by reacting a hydroxyl group obtained by reacting an epoxy group-containing compound with (meth) acrylic acid or the like and a compound having a polymerizable unsaturated double bond.

  Specifically, a hydroxyl group is newly formed by reacting an epoxy group of the epoxy group-containing compound with a carboxyl group of (meth) acrylic acid or the like to cleave the epoxy group, A polymerizable unsaturated double bond derived from meth) acrylic acid is introduced. This hydroxyl group has a polymerizable unsaturated double bond in the molecular side chain by reacting with a part of the isocyanate group or carboxyl group in the urethane prepolymer obtained by reacting the polyol with the polyisocyanate. A urethane resin can be manufactured.

  Examples of the epoxy group-containing compound include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and bisphenol A. A compound having two or more epoxy groups such as diglycidyl ether, bisphenol F diglycidyl ether, and a diglycidyl compound obtained by adding an alkylene oxide to them can be used.

  The aqueous urethane resin composition of the present invention can be produced by mixing and stirring the urethane resin (D) produced by the above method and the aqueous medium (E). Specifically, the urethane resin (D) produced by the above method or an organic solvent solution thereof and the aqueous medium (E) can be mixed by using a homogenizer or the like as necessary.

  Examples of the aqueous medium (E) 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 (E) suppresses a rapid increase in viscosity when the aqueous urethane resin composition of the present invention is produced, and the productivity of the aqueous urethane resin composition, ease of coating, and drying properties. From the viewpoint of improving, etc., the content is preferably in the range of 30% by mass to 80% by mass and more preferably in the range of 40% by mass to 75% by mass with respect to the total amount of the aqueous urethane resin composition.

When the urethane resin (D) is mixed with the aqueous medium (E) or mixed with the aqueous medium (E), the urethane resin (D) has a hydrophilic group such as an anionic group. In order to improve the water dispersion stability of urethane resin (D), it is preferable to neutralize part or all. For the neutralization, the above-described basic compounds can be used.
Moreover, when using the organic solvent solution of the said urethane resin (D), after mixing with an aqueous medium (E), it is preferable to remove an organic solvent by methods, such as a distillation method.

  When the urethane resin (D) is produced, the polyol (A), the polyisocyanate (B), or a hydroxyl group-containing vinyl monomer (C) is used from the viewpoint of further improving the durability of the resulting film. In addition to (), a chain extender can be used if necessary.

  As the chain extender, polyamine and other active hydrogen atom-containing compounds can be used.

  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, N-methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; Razide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3-semicarbazide-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5 5-Trimethylcyclohexane can be used, and ethylenediamine is preferably used.

  Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and saccharose. Glycols such as methylene glycol, glycerin and sorbitol; phenols such as bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenylsulfone, hydrogenated bisphenol A, hydroquinone , And water can be used alone or in combination of two or more thereof within a range in which the storage stability of the coating agent of the present invention is not lowered.

  The chain extender such as polyamine reacts with an isocyanate group that can remain in the urethane resin (D) to form a high molecular weight urethane resin (D). Therefore, when a chain extender such as the polyamine is used, the equivalent ratio of the isocyanate group of the urethane resin (D ′) and the hydroxyl group of the hydroxyl group-containing vinyl monomer (C) is as described above. It is preferable to adjust so that an isocyanate group remains in the urethane resin (D) obtained.

The chain extender such as the polyamine is used in such a range that the equivalent ratio of the amino group of the polyamine and the isocyanate group that can remain in the urethane resin (D) is 1.9 or less (equivalent ratio). It is preferable to use within a range of 0.3 to 1.0 (equivalent ratio). By using the chain extender in the above-described range, the durability and mechanical strength of the film to be formed can be improved.
The reaction between the chain extender and the urethane resin (D) can be performed either before mixing the urethane resin (D) and the aqueous medium (E) or after mixing with the aqueous medium (E). Is possible.

  The aqueous urethane resin composition of the present invention obtained by the above method is excellent in durability by performing radical polymerization due to the polymerizable unsaturated double bond of the urethane resin (D), and various A cured product such as a film having excellent adhesion and followability to the substrate can be formed.

  When the water-based urethane resin composition is cured to form a cured product such as a film or a film, radicals are generated by light irradiation or heating, and radicals of polymerizable unsaturated double bonds of the urethane resin (D). It is preferable to use a polymerization initiator that advances the polymerization. As the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator can be used.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl- [4- (methylthio) phenyl] -2- Acetophenones such as morpholino-1-propanone and 2,2-dimethoxy-2-phenylacetophenone; benzoins such as benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, Benzophenones such as benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone Thioxanthones such as 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone; 4,4′-dimethylaminobenzophenone ( Alias = Miheraz ketone), 4,4′-diethylaminobenzophenone, α-acyloxime ester, benzyl, methylbenzoylformate (“Bicure 55”), 2- Anthraquinones such as ethyl anthraquinone; Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Lucirin TPO”); 3,3 ′, 4,4′-tetra (tert-butylper) Oxycarbonyl) benzophenone [“BTTB” manufactured by NOF Corporation], acrylated benzophenone, and the like can be used.

  As the photopolymerization initiator, 2-hydroxy-2 can be used to prevent discoloration of the cured product of the water-based urethane resin composition over time, and to increase the thickness of the cured product of the water-based urethane resin composition. -Methyl-1-phenylpropan-1-one, one or two of 1-hydroxycyclohexyl phenyl ketone, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) ) -Phenylphosphine oxide or the like is preferably used in combination.

  As the thermal polymerization initiator that can be used for the polymerization initiator, organic peroxides can be used. Specifically, azo compounds, diacyl peroxide compounds, peroxy ester compounds, hydro Peroxide compounds, dialkyl peroxide compounds, ketone peroxide compounds, peroxyketal compounds, alkyl perester compounds, and carbonate compounds can be used.

  The amount of the polymerization initiator used is usually preferably in the range of 0.1 to 5 parts by mass, and 0.5 to 2 parts by mass with respect to 100 parts by mass of the urethane resin (D). More preferably, it is the range.

  The polymerization initiator may be used by mixing with the aqueous urethane resin composition obtained by the above method. When the urethane resin (D) and the aqueous medium (E) are mixed, the polymerization initiator is also used. You may mix together.

  The aqueous urethane resin composition of the present invention has the above-described urethane from the viewpoint of further improving the crosslink density of the film to be formed, forming a film that is highly durable and has both substrate adhesion and followability. In addition to the resin (D) and the aqueous medium (E), a polyfunctional vinyl monomer may be included as necessary.

  Unlike the hydroxyl group-containing vinyl monomer (C), it is preferable to use a polyfunctional vinyl monomer that does not have a functional group such as a hydroxyl group that can react with the urethane resin (D ′). .

  The polyfunctional vinyl monomer is present in the aqueous particles of the urethane resin (D) or in the vicinity of the particles or in the aqueous medium (E) in the aqueous medium (E), and radical polymerization proceeds by light irradiation or heating. In this case, the polyfunctional vinyl monomer can react to form a crosslinked structure.

  Examples of the polyfunctional vinyl monomer include polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate, and bisphenol A modified with ethylene oxide or propylene oxide. Modified (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra ( A (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. can be used.

  The polyfunctional vinyl monomer is used in a range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the urethane resin (D), thereby achieving both high durability and adhesion to the substrate. It is preferable for forming a coated film.

  Moreover, the aqueous urethane resin composition of the present invention may contain other additive components in addition to those described above.

  As the additive, for example, a sensitizer, a polymerization inhibitor, a curing agent, a curing accelerator, a tackifier resin, a filler, a pigment, a dye, a stabilizer, a flame retardant, and the like can be used.

  Examples of the sensitizer include biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene, triphenylene, anthracene, 9,10-diphenylanthracene, 9,10-dimethoxyanthracene, and 9,10-diethoxy. Anthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, benzophenone, 4,4′-dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone, benzaldehyde and the like can be used.

  As the polymerization inhibitor, for example, 3,5-bismutual butyl-4-hydroxytoluene, hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether (methoquinone), para-tertiary butyl catechol and the like can be used.

  As the curing accelerator, for example, organic metal salts such as cobalt naphthenate and cobalt octenoate, amines, β-diketones and the like can be used.

  As the curing agent, polyisocyanate compounds typified by tolylene diisocyanate, adducts derived from hexamethylene diisocyanate, and nurate, polyfunctional epoxy compounds, melamine compounds, metal chelates, etc. should be used. Can do.

  In addition to those described above, the aqueous urethane resin composition of the present invention includes a curing catalyst, a filler, a photocatalytic compound, an inorganic pigment, an organic pigment, an extender pigment, a wax, a surfactant, and a stabilizer as necessary. In addition, various additives such as a flow modifier, a dye, a leveling agent, a rheology control agent, an ultraviolet absorber, an antioxidant, and a plasticizer can be used.

  Examples of the curing catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate, lead octylate, cobalt octylate, and zinc octylate. Calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilaurate, di-n-butyltin maleate, p-toluenesulfone Acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid and the like can be used.

  As said filler, various inorganic particles, such as a clay mineral, a metal, a metal oxide, glass, can be used, for example. Examples of the metal include gold, silver, copper, platinum, titanium, zinc, nickel, aluminum, iron, silicon, germanium, antimony, and metal oxides thereof.

  Examples of the photocatalytic compound include titanium oxide, zinc oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, germanium oxide, copper oxide, vanadium oxide, manganese oxide, nickel oxide, and ruthenium oxide. can do. Specifically, for example, “ST-01” [Ishihara Sangyo Co., Ltd. titanium oxide, average particle size 7 nm], “ST-21” [Ishihara Sangyo Co., Ltd. titanium oxide, average particle size 20 nm], “ AMT-100 "[Titanium Co., Ltd., titanium oxide, average particle diameter 6 nm]," TKD-701 "[Taika Co., Ltd. titanium oxide dispersion, average particle diameter 6 nm]," TKD-702 "[Taika Corporation ) Titanium oxide dispersion, average particle size 6 nm], “STS-21” (Ishihara Sangyo Co., Ltd. titanium oxide water dispersion, average particle size 20 nm), “TKS-203” (Taika Co., Ltd.) Titanium aqueous dispersion, average particle diameter of 6 nm] and the like can be used. Among them, it is preferable to use titanium oxide or zinc oxide that is chemically stable, harmless, and has high photocatalytic activity.

  The method for curing the aqueous urethane resin composition of the present invention differs depending on the kind of the polymerization initiator described above. For example, in the aqueous urethane resin composition using the photopolymerization initiator, the aqueous urethane resin composition is applied on a substrate, and then the aqueous medium (E) is removed by evaporation, etc., and then a metal halide lamp, a mercury lamp It can be hardened by irradiating predetermined ultraviolet rays using a general ultraviolet light irradiation device such as the above.

The irradiation of the energy beam such as ultraviolet rays, preferably 50 to 5000 mJ / cm ^2, more preferably 100~3000mJ / cm ^2, particularly preferably it is in the range of 300~1500mJ / cm ^2. In addition, the ultraviolet irradiation amount was based on a value measured in a wavelength region of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Nippon Battery Co., Ltd.).

  On the other hand, in the aqueous urethane resin composition using the thermal polymerization initiator, the aqueous urethane resin composition is applied on a substrate, and then the aqueous medium (E) is removed by evaporation or the like. Can be cured by heating at a temperature of preferably 50 to 250 ° C.

  Moreover, when hardening the water-based urethane resin composition of this invention, it receives the superposition | polymerization inhibition by the oxygen in the air, hardening becomes inadequate, and the target adhesive performance may not express. In order to prevent this, the active energy is irradiated or heated in the presence of an inert gas such as nitrogen, or the base material described later is laminated, and the active energy in a state where the contact of the surface of the composition with air is cut off. It is preferable to cure by irradiation or heating.

  The aqueous urethane resin composition of the present invention as described above can be used for coating agents, adhesives, pressure-sensitive adhesives, various molding materials and the like. Especially, it is preferable to use it for the coating agent for surface protection of a metal base material, and it is more preferable to use it for a steel plate surface treating agent.

  Examples of the substrate on which the coating agent and the like can be applied include various plastics and films thereof, metal, glass, paper, and wood. In particular, even when the coating agent is used for various plastic substrates, a film having excellent solvent resistance and water resistance can be formed 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.

  Moreover, since the said coating agent can form the crosslinked film formed densely which can suppress corrosion of metal material itself, it can be used suitably for the coating agent for surface protection of a metal base material.

  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.

  A laminate in which a film formed using the coating agent on the surface of the metal substrate is excellent in solvent resistance without causing peeling of the film during processing. It can be used for applications such as chemicals, building material paints, and soft feel paints.

  In addition, the coating agent exhibits excellent solvent resistance against organic solvents such as methanol, ethanol, isopropyl alcohol, acetone, methyl ethyl ketone, and toluene even when the cross-linked film has a thickness of about 5 μm. Is possible. Moreover, even if the said coating agent is a film thickness of about 1 micrometer, it can form the film | membrane excellent in chemical resistance including acid resistance, alkali resistance, etc.

  The coating agent can be formed on a substrate by coating, 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 room temperature as long as the aqueous medium (E) contained in the coating layer can be evaporated and removed, but is preferably dried by heating. The heat drying is usually preferably performed at 40 to 250 ° C. for about 1 to 600 seconds.
In addition, the curing differs depending on the type of polymerization initiator used as described above, but a film is formed by light irradiation or heating in the same manner as the method of curing the aqueous urethane resin composition. Can do.

  As described above, since the coating agent can form a film excellent in adhesion to the substrate, for example, surface coating of various plastic members of electronic equipment, for example, surface coating of members constituting automobiles, railways, etc., sunlight Various applications including surface coatings for light-receiving surfaces of photovoltaic power generation devices such as power generation devices, surface coatings for electronic components, wall materials, flooring materials, window glass, and coating materials used for surface coatings of eyeglasses, etc. Can be used.

Moreover, the said water-based urethane resin composition can be used for the molding material which can be used for manufacture of various hardened | cured materials, such as a film.
Specifically, the aqueous urethane resin composition is applied to the surface of a release paper or release film, cured by the same method as described above, and then the release paper or the like is removed to form a transparent film. A cured product can be obtained.

Cured products such as films include optical films such as retardation films and polarizing plate protective films, mobile phones, home appliances, OA equipment, automobile parts such as automobile interior and exterior materials, parts of various household appliances, electronic It can be used for manufacturing materials, building materials, medical materials such as artificial bones and artificial teeth.
In addition, since the adhesive or pressure-sensitive adhesive containing the aqueous urethane resin composition of the present invention has excellent adhesion to various substrates, for example, fixing of components constituting automobiles, home appliances, etc. It can be used for adhesive sheets.

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

[Content of aliphatic cyclic structure]
The content of the aliphatic cyclic structure of the urethane resin (D) is the total mass of all raw materials such as the polyol (A) and polyisocyanate (B) used in the production of the urethane resin (D), and the urethane resin ( Based on the amount of the aliphatic cyclic structure contained in the aliphatic cyclic structure-containing compound such as aliphatic cyclic structure-containing polyol (a1) or aliphatic cyclic structure-containing polyisocyanate used in the production of A) Calculated.

[Measurement of weight average molecular weight]
The weight average molecular weight of the urethane resin (D) was measured by gel permeation chromatograph (GPC method).

  The aqueous urethane resin composition was coated on a glass plate with a 3 mil applicator and dried at room temperature for 1 hour to form a semi-dry film. The obtained film was peeled from the glass plate, and 0.4 g was dissolved in 100 g of tetrahydrofuran to obtain a measurement sample.

  As a measuring apparatus, Tosoh Corporation high performance liquid chromatograph HLC-8220 type was used. As a column, Tosoh Corporation column TSK-GEL (HXL-H, G5000HXL, G4000HXL, G3000HXL, G2000HXL) was used in combination.

  Standard polystyrenes (manufactured by Showa Denko KK and Toyo Soda Co., Ltd.) as standard samples (molecular weights: 44.48 million, 4250,000, 288,000, 2750,000, 1.85 million, 860,000, 450,000, 411,000, 35. Calibration curves were created using 50,000, 190,000, 160,000, 96,000, 50,000, 37,000, 198,000, 196,000, 5570, 4000, 2980, 2030, 500). .

  Tetrahydrofuran was used as the eluent and sample solution, and the weight average molecular weight was measured using a RI detector with a flow rate of 1 mL / min, a sample injection amount of 500 μL, and a sample concentration of 0.4%.

[Example 1] Preparation of aqueous urethane resin composition (X-1) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,4-cyclohexanedimethanol and neopentyl glycol Aliphatic ring structure-containing polyester diol obtained by reacting with adipic acid [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 1426 mmol / kg] 100 parts by mass, 1,4-cyclohexanedimethanol 26 parts by mass, 14 parts by mass of 2,2-dimethylolpropionic acid and 107 parts by mass of dicyclohexylmethane diisocyanate were mixed with 35 parts by mass of N-ethyl-2-pyrrolidone and 61 parts by mass of methyl ethyl ketone, and the temperature of the reaction vessel was 80 ° C. Urethane prepolymer having an isocyanate group at the molecular end by reacting under An organic solvent solution was obtained.

  Next, by mixing 18 parts by mass of pentaerythritol triacrylate with the organic solvent solution of the urethane prepolymer, and further reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate under the condition of 80 ° C. An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane prepolymer is neutralized by mixing an organic solvent solution of the urethane prepolymer having a polymerizable unsaturated double bond with 10 parts by mass of triethylamine. Then, 562 parts by mass of water was further added and stirred sufficiently, and 11 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain extension reaction, followed by distillation under reduced pressure, so that the non-volatile content was 35% by mass and the pH was 8. An aqueous urethane resin composition (X-1) of 0 was obtained. The aliphatic cyclic structure content of the urethane resin (D-1) contained in the aqueous urethane resin composition (X-1) is 4266 mmol / Kg (of which the aliphatic cyclic structure-containing polyol (a1) is derived. The group cyclic structure content was 1211 mmol / kg), and the weight average molecular weight was 75,000.

[Example 2] Preparation of aqueous urethane resin composition (X-2) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 1,4-cyclohexanedimethanol and neopentyl glycol Aliphatic cyclic structure-containing polycarbonate diol obtained by reacting with a carbonate ester [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 1426 mmol / kg] 100 parts by mass, 1,4-cyclohexanedimethanol 26 parts by mass, 14 parts by mass of 2,2-dimethylolpropionic acid and 107 parts by mass of dicyclohexylmethane diisocyanate were mixed with 35 parts by mass of N-ethyl-2-pyrrolidone and 61 parts by mass of methyl ethyl ketone, and the temperature of the reaction vessel was 80 ° C. The urethane prepolymer having an isocyanate group at the molecular end is allowed to react under An organic solvent solution of the polymer was obtained.

  Next, by mixing 18 parts by mass of pentaerythritol triacrylate with the organic solvent solution of the urethane prepolymer, and further reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate under the condition of 80 ° C. An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane prepolymer is neutralized by mixing an organic solvent solution of the urethane prepolymer having a polymerizable unsaturated double bond with the isocyanate group and 10 parts by mass of triethylamine. Then, 562 parts by mass of water was further added and stirred sufficiently, and 11 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain extension reaction, followed by distillation under reduced pressure, so that the non-volatile content was 35% by mass and the pH was 8. An aqueous urethane resin composition (X-2) 1 was obtained. The aliphatic cyclic structure content of the urethane resin (D-2) contained in the aqueous urethane resin composition (X-2) is 4266 mmol / Kg (of which the fat derived from the aliphatic cyclic structure-containing polyol (a1)). The group cyclic structure content was 1211 mmol / kg), and the weight average molecular weight was 72,000.

[Example 3] Preparation of aqueous urethane resin composition (X-3) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,4-cyclohexanedimethanol and neopentyl glycol Aliphatic ring structure-containing polyester diol obtained by reacting with adipic acid [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 1426 mmol / kg] 100 parts by mass, 1,4-cyclohexanedimethanol 26 parts by mass, 14 parts by mass of 2,2-dimethylolpropionic acid and 107 parts by mass of dicyclohexylmethane diisocyanate were mixed with 35 parts by mass of N-ethyl-2-pyrrolidone and 61 parts by mass of methyl ethyl ketone, and the temperature of the reaction vessel was 80 ° C. Urethane prepolymer having an isocyanate group at the molecular end by reacting under An organic solvent solution was obtained.

  Next, 7 parts by mass of 2-hydroxyethyl acrylate is mixed with the organic solvent solution of the urethane prepolymer, and a part of the isocyanate group and the hydroxyl group of the 2-hydroxyethyl acrylate are reacted under the condition of 80 ° C. Thus, an organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane prepolymer is neutralized by mixing an organic solvent solution of the urethane prepolymer having a polymerizable unsaturated double bond with the isocyanate group and 10 parts by mass of triethylamine. Then, 539 parts by mass of water was further added and sufficiently stirred, and 11 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain elongation reaction, followed by distillation under reduced pressure, so that the non-volatile content was 35% by mass and the pH was 7. An aqueous urethane resin composition (X-3) 9 was obtained. The aliphatic cyclic structure content of the urethane resin (D-3) contained in the aqueous urethane resin composition (X-3) is 4445 mmol / Kg (of which the aliphatic cyclic structure-containing polyol (a1) is derived. The group cyclic structure content was 1261 mmol / kg), and the weight average molecular weight was 55000.

[Example 4] Preparation of aqueous urethane resin composition (X-4) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 1,4-cyclohexanedimethanol and neopentyl glycol Aliphatic ring structure-containing polyester diol obtained by reacting with adipic acid [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 1426 mmol / kg] 100 parts by mass, 1,4-cyclohexanedimethanol 26 parts by mass, 14 parts by mass of 2,2-dimethylolpropionic acid and 107 parts by mass of dicyclohexylmethane diisocyanate were mixed with 35 parts by mass of N-ethyl-2-pyrrolidone and 61 parts by mass of methyl ethyl ketone, and the temperature of the reaction vessel was 80 ° C. Urethane prepolymer having an isocyanate group at the molecular end by reacting under An organic solvent solution was obtained.

  Next, by mixing 18 parts by mass of pentaerythritol triacrylate with the organic solvent solution of the urethane prepolymer, and further reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate under the condition of 80 ° C. An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Subsequently, the organic solvent solution of the urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond is mixed with 26 parts by mass of dipentaerythritol hexaacrylate, and then mixed with 10 parts by mass of triethylamine. After neutralizing some or all of the carboxyl groups of the urethane prepolymer, 638 parts by mass of water are further added, and the mixture is sufficiently stirred. As a result, an aqueous urethane resin composition (X-4) having a nonvolatile content of 35% by mass and a pH of 8.0 was obtained. The aliphatic cyclic structure content of the urethane resin (D-4) contained in the aqueous urethane resin composition (X-4) is 4266 mmol / Kg (of which the aliphatic cyclic structure-containing polyol (a1) is derived. The group cyclic structure content was 1211 mmol / kg), and the weight average molecular weight was 75,000.

[Example 5] Preparation of aqueous urethane resin composition (X-5) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,4-cyclohexanedimethanol and neopentyl glycol Aliphatic ring structure-containing polyester diol obtained by reacting with adipic acid [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 1426 mmol / kg] 100 parts by mass, 1,4-cyclohexanedimethanol 26 parts by mass, 14 parts by mass of 2,2-dimethylolpropionic acid and 107 parts by mass of dicyclohexylmethane diisocyanate were mixed with 35 parts by mass of N-ethyl-2-pyrrolidone and 61 parts by mass of methyl ethyl ketone, and the temperature of the reaction vessel was 80 ° C. Urethane prepolymer having an isocyanate group at the molecular end by reacting under An organic solvent solution was obtained.

  Next, 18 parts of pentaerythritol triacrylate is mixed with the organic solvent solution of the urethane prepolymer, and further, under a condition of 80 ° C., by reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate, An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

Next, a part or all of the carboxyl groups of the urethane prepolymer was neutralized by mixing an organic solvent solution of the urethane prepolymer having a polymerizable unsaturated double bond with 10 parts by mass of triethylamine. Thereafter, 565 parts by mass of water was further added, stirred sufficiently, and further distilled under reduced pressure to obtain an aqueous urethane resin composition (X-5) having a nonvolatile content of 35% by mass and a pH of 7.8. The aliphatic cyclic structure content of the urethane resin (D-5) contained in the aqueous urethane resin composition (X-5) is 4302 mmol / Kg (of which the aliphatic cyclic structure-containing polyol (a1) is derived. The group cyclic structure content was 1221 mmol / kg), and the weight average molecular weight was 40000.

[ Reference Example 6] Preparation of aqueous urethane resin composition (X-6) 1,6-hexanediol, neopentyl glycol and adipine in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube and a stirrer 100 parts by mass of a polyester diol obtained by reacting with an acid [hydroxyl equivalent: 1000 g / equivalent, aliphatic cyclic structure content: 0 mmol / kg], 1,4-cyclohexanedimethanol: 4 parts by mass, 2,2-dimethylolpropion By mixing 9 parts by mass of acid and 46 parts by mass of dicyclohexylmethane diisocyanate with 23 parts by mass of N-ethyl-2-pyrrolidone and 39 parts by mass of methyl ethyl ketone, and reacting them at a temperature of 80 ° C. in the reaction vessel, An organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

  Next, by mixing 8 parts by mass of pentaerythritol triacrylate with the organic solvent solution of the urethane prepolymer, and further reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate under the condition of 80 ° C. An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane prepolymer was neutralized by mixing an organic solvent solution of the urethane prepolymer having a polymerizable unsaturated double bond with 7 parts by mass of triethylamine. Thereafter, 354 parts by mass of water was further added and sufficiently stirred, and 5 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain elongation reaction. An aqueous urethane resin composition (X-6) was obtained. The content of the aliphatic cyclic structure of the urethane resin (D-6) contained in the aqueous urethane resin composition (X-6) is 2255 mmol / Kg (including 166 mmol / kg derived from (a1)), and the weight average molecular weight. Was 83,000.

[Example 7] Preparation of aqueous urethane resin composition (X-7) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,4-cyclohexanedimethanol and neopentyl glycol Aliphatic ring structure-containing polyester diol obtained by reacting with adipic acid [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 1426 mmol / kg] 100 parts by mass, 1,4-cyclohexanedimethanol 26 parts by mass, 14 parts by mass of 2,2-dimethylolpropionic acid and 107 parts by mass of dicyclohexylmethane diisocyanate were mixed with 35 parts by mass of N-ethyl-2-pyrrolidone and 61 parts by mass of methyl ethyl ketone, and the temperature of the reaction vessel was 80 ° C. Urethane prepolymer having an isocyanate group at the molecular end by reacting under An organic solvent solution was obtained.

  Next, 12 parts by mass of cyclohexanedimethanol monoacrylate is mixed with the organic solvent solution of the urethane prepolymer, and further, a part of the isocyanate group and the hydroxyl group of the cyclohexanedimethanol monoacrylate are reacted under the condition of 80 ° C. Thus, an organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane resin was neutralized by mixing 10 parts by mass of triethylamine with an organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond. Thereafter, 550 parts by mass of water was further added and stirred sufficiently, and 11 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain elongation reaction, followed by distillation under reduced pressure to obtain a non-volatile content of 35% by mass and a pH of 7.9 An aqueous urethane resin composition (X-7) was obtained. The aliphatic cyclic structure content of the urethane resin (D-7) contained in the aqueous urethane resin composition (X-7) is 4588 mmol / Kg (of which the fat derived from the aliphatic cyclic structure-containing polyol (a1)). The group cyclic structure content was 1238 mmol / kg), and the weight average molecular weight was 61,000.

[Example 8] Preparation of aqueous urethane resin composition (X-8) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 1,4-cyclohexanedimethanol and neopentyl glycol Aliphatic cyclic structure-containing polyester diol obtained by reacting with adipic acid [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 1426 mmol / kg] 100 parts by mass, 1,4-cyclohexanedimethanol 15 parts by mass, By mixing 12 parts by mass of 2,2-dimethylolpropionic acid and 88 parts by mass of dicyclohexylmethane diisocyanate with 84 parts by mass of methyl ethyl ketone and reacting them at a temperature of 80 ° C. in the reaction vessel, an isocyanate is added to the molecular terminal. An organic solvent solution of a urethane prepolymer having a group was obtained.

  Next, by mixing 20 parts by mass of pentaerythritol triacrylate with the organic solvent solution of the urethane prepolymer, and further reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate under the condition of 80 ° C. An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, by mixing the organic solvent solution of urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond and 9 parts by mass of triethylamine, part or all of the carboxyl groups of the urethane prepolymer is neutralized. Then, 502 parts by mass of water was further added and stirred sufficiently, and 13 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain elongation reaction, followed by distillation under reduced pressure, so that the non-volatile content was 35% by mass and the pH was 8. An aqueous urethane resin composition (X-8) 1 was obtained. The aliphatic cyclic structure content of the urethane resin (D-8) contained in the aqueous urethane resin composition (X-8) is 3856 mmol / Kg (of which the aliphatic cyclic structure-containing polyol (a1) is derived. The group cyclic structure content was 1048 mmol / kg), and the weight average molecular weight was 69000.

[Example 9] Preparation of aqueous urethane resin composition (X-9) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,4-cyclohexanedimethanol and neopentyl glycol Aliphatic cyclic structure-containing polyester diol obtained by reacting with adipic acid [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 1426 mmol / kg] 100 parts by mass, 1,4-cyclohexanedimethanol 9 parts by mass, By melting 12 parts by mass of 2,2-dimethylolpropionic acid and 79 parts by mass of dicyclohexylmethane diisocyanate at a temperature of 80 ° C. in the reaction vessel, melting of the urethane prepolymer having an isocyanate group at the molecular end I got a thing.

  Next, 24 parts by mass of pentaerythritol triacrylate is mixed with the melt of the urethane prepolymer, and further, under a condition of 80 ° C., by reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate, A melt of urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane prepolymer was neutralized by mixing the urethane prepolymer melt having the isocyanate group and the polymerizable unsaturated double bond with 9 parts by mass of triethylamine. Thereafter, 400 parts by mass of water was further added and stirred sufficiently, and 15 parts by mass of a 20% by mass aqueous ethylenediamine solution was added to cause chain elongation reaction, whereby an aqueous urethane resin having a nonvolatile content of 35% by mass and a pH of 8.5. A composition (X-9) was obtained. The aliphatic cyclic structure content of the urethane resin (D-9) contained in the aqueous urethane resin composition (X-9) is 3557 mmol / Kg (of which the aliphatic cyclic structure-containing polyol (a1) is derived. The group cyclic structure content was 906 mmol / kg), and the weight average molecular weight was 65,000.

[Comparative Example 1] Preparation of aqueous urethane resin composition (X'-1) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,6-hexanediol and neopentyl glycol Polyester diol obtained by reacting with adipic acid [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 0 mmol / kg] 100 parts by mass, 1,4-butanediol 18 parts by mass, 2,2-dimethylolpropion By mixing 11 parts by weight of acid and 68 parts by weight of hexamethylene diisocyanate with 28 parts by weight of N-ethyl-2-pyrrolidone and 49 parts by weight of methyl ethyl ketone, the mixture is reacted under the conditions of a temperature of 80 ° C. in the reaction vessel. An organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

  Next, by mixing 18 parts by mass of pentaerythritol triacrylate with the organic solvent solution of the urethane prepolymer, and further reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate under the condition of 80 ° C. An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane prepolymer was neutralized by mixing an organic solvent solution of the urethane prepolymer having a polymerizable unsaturated double bond with 9 parts by mass of triethylamine. Thereafter, 458 parts by mass of water was further added and stirred sufficiently, and 11 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain extension reaction, followed by distillation under reduced pressure, whereby the non-volatile content was 35% by mass and the pH was 8.2. An aqueous urethane resin composition (X′-1) was obtained. The urethane resin (D′-1) contained in the water-based urethane resin composition (X′-1) had an aliphatic cyclic structure content of 0 mmol / Kg and a weight average molecular weight of 66,000.

[Comparative Example 2] Preparation of aqueous urethane resin composition (X'-2) 1,4-cyclohexanedimethanol and neopentyl glycol in a nitrogen-substituted container equipped with a thermometer, nitrogen gas inlet tube and stirrer Aliphatic cyclic structure-containing polyester diol [hydroxyl group equivalent 1000 g / equivalent, aliphatic cyclic structure content 250 mmol / kg] 150 parts by mass, 1,4-cyclohexanedimethanol 1 part by mass , 2,2-dimethylolpropionic acid 8 parts by mass and dicyclohexylmethane diisocyanate 44 parts by mass are mixed with 29 parts by mass N-ethyl-2-pyrrolidone and 50 parts by mass methyl ethyl ketone, and the temperature in the reaction vessel is 80 ° C. Reaction of the urethane prepolymer having an isocyanate group at the molecular end. To obtain a solvent solution.

  Next, by mixing 7 parts by mass of pentaerythritol triacrylate with the organic solvent solution of the urethane prepolymer, and further reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate under the condition of 80 ° C. An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane prepolymer was neutralized by mixing an organic solvent solution of the urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond and 6 parts by mass of triethylamine. Thereafter, 452 parts by mass of water was further added and sufficiently stirred, 5 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain extension reaction, and further distilled under reduced pressure, whereby the non-volatile content was 35% by mass and the pH was 8.2. An aqueous urethane resin composition (X′-2) was obtained. The content of the aliphatic cyclic structure of the urethane resin (D′-2) contained in the aqueous urethane resin composition (X′-2) is 1814 mmol / Kg (including the aliphatic cyclic structure-containing polyol (a1)). Of the aliphatic cyclic structure was 210 mmol / kg), and the weight average molecular weight was 88,000.

[Comparative Example 3] Preparation of aqueous urethane resin composition (X'-3) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,4-cyclohexanedimethanol and carbonate ester Aliphatic structure-containing polycarbonate diol [hydroxyl equivalent 1000 g / equivalent, aliphatic cyclic structure content 5882 mmol / kg] 100 parts by mass, 1,4-cyclohexanedimethanol 31 parts by mass, 2, 2 -13 parts by mass of dimethylolpropionic acid and 114 parts by mass of dicyclohexylmethane diisocyanate were mixed with 37 parts by mass of N-ethyl-2-pyrrolidone and 63 parts by mass of methyl ethyl ketone, and the reaction was carried out at a temperature of 80 ° C in the reaction vessel. An organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end Obtained.

  Next, by mixing 19 parts by mass of pentaerythritol triacrylate with the organic solvent solution of the urethane prepolymer, and further reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate under the condition of 80 ° C. An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane prepolymer was neutralized by mixing an organic solvent solution of the urethane prepolymer having a polymerizable unsaturated double bond with 10 parts by mass of triethylamine. Thereafter, 590 parts by mass of water was further added and sufficiently stirred, and 12 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain elongation reaction, followed by distillation under reduced pressure, whereby the non-volatile content was 35% by mass and the pH was 8.0. An aqueous urethane resin composition (X′-3) was obtained. The content of the aliphatic cyclic structure of the urethane resin (D′-3) contained in the aqueous urethane resin composition (X′-3) is 6000 mmol / Kg (including the aliphatic cyclic structure-containing polyol (a1)). Of the aliphatic cyclic structure was 2874 mmol / kg), and the weight average molecular weight was 48,000.

[Comparative Example 4] Preparation of aqueous urethane resin composition (X'-3) In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 1,6-hexanediol and neopentyl glycol 100 parts by mass of a polyester diol obtained by reacting with adipic acid [hydroxyl equivalent: 1000 g / equivalent, aliphatic cyclic structure content: 0 mmol / kg], 1,4-butanediol: 16 parts by mass, 2,2-dimethylolpropion 14 parts by mass of acid and 107 parts by mass of dicyclohexylmethane diisocyanate were mixed with 34 parts by mass of N-ethyl-2-pyrrolidone and 58 parts by mass of methyl ethyl ketone, and reacted at a temperature of 80 ° C. in the reaction vessel. An organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.

  Next, by mixing 18 parts by mass of pentaerythritol triacrylate with the organic solvent solution of the urethane prepolymer, and further reacting a part of the isocyanate group and the hydroxyl group of the pentaerythritol triacrylate under the condition of 80 ° C. An organic solvent solution of a urethane prepolymer having an isocyanate group and a polymerizable unsaturated double bond was obtained.

  Next, a part or all of the carboxyl groups of the urethane prepolymer was neutralized by mixing an organic solvent solution of the urethane prepolymer having a polymerizable unsaturated double bond with 10 parts by mass of triethylamine. Thereafter, 541 parts by mass of water was further added and stirred sufficiently, and 11 parts by mass of a 20% by mass ethylenediamine aqueous solution was added to cause chain elongation reaction, followed by distillation under reduced pressure, whereby the non-volatile content was 35% by mass and the pH was 7.9 An aqueous urethane resin composition (X′-4) was obtained. The content of the aliphatic cyclic structure of the urethane resin (D′-4) contained in the aqueous urethane resin composition (X′-4) is 3171 mmol / Kg (including the aliphatic cyclic structure-containing polyol (a1)). Of the aliphatic cyclic structure was 0 mmol / kg), and the weight average molecular weight was 80,000.

[Adhesion evaluation method]
(Evaluation method for adhesion between substrate and film)
Formulation obtained by blending 0.5 parts by mass of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) with respect to 100 parts by mass of the aqueous urethane resin composition obtained above. The liquid was applied to the surface of 8 types of base materials shown in the following [1] to [8] using a bar coater so that the film thickness of the dry film was 2 μm, and a hot air dryer was used. After drying at 80 ° C. for 180 seconds, a test plate 1 having a film laminated on the surface of each substrate was obtained by irradiating with 400 mJ / cm ² using a high-pressure mercury lamp.

〔Base material〕
All substrates were purchased from Engineering Test Service.

[1] PET: Polyethylene terephthalate, 1.0 mm x 70 mm x 150 mm
[2] PC: Polycarbonate, 1.0 mm x 70 mm x 150 mm
[3] PVC: Vinyl chloride, 2.0 mm x 70 mm x 150 mm
[4] SUS: JIS G4305 SUS304, 0.5 mm x 70 mm x 150 mm
[5] SPC: JIS G3141 SPCC-SB, 0.8 mm x 70 mm x 150 mm
[6] AL: Aluminum, JIS H4000 A1050P, 0.8 mm x 70 mm x 150 mm
[7] Glass: JIS R3202, 2.0 mm x 70 mm x 150 mm
[8] GL: Hot-dip galvanized steel sheet (45% by mass of zinc, 55% by mass of aluminum), 0.8 mm × 70 mm × 150 mm
The adhesion between the film constituting the test plate obtained above and the substrate was measured based on the JIS K5600 cross cut test method and evaluated according to the following evaluation criteria.

A: No peeling of the film was observed.
○: The area where the film was peeled off was less than 3% of the total grid area.
Δ: The area where the film was peeled was 3% or more and less than 50% of the total grid area.
X: The area where the film was peeled off was 50% or more of the total grid area.

[Evaluation method of water resistance]
(Evaluation method for water-resistant adhesion)
Formulation obtained by blending 0.5 parts by mass of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) with respect to 100 parts by mass of the aqueous urethane resin composition obtained above. A bar coater was applied to the surface of the above [8] GL: hot-dip galvanized steel sheet (45% by mass of zinc, 55% by mass of aluminum, 0.8 mm × 70 mm × 150 mm) so that the film thickness of the dried film was 2 μm After coating with a hot air dryer and drying at 80 ° C. for 180 seconds using a high-pressure mercury lamp, the coating is formed on the surface of the substrate made of a hot-dip galvanized steel sheet by irradiating 400 mJ / cm ^2. A laminated test plate 2 was obtained.
On the other hand, 100 parts by mass of the aqueous urethane resin composition obtained above is obtained by blending 0.5 parts by mass of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one). Using a bar coater on the surface of the transparent film substrate made of [1] PET (polyethylene terephthalate, 1.0 mm × 70 mm × 150 mm), so that the film thickness of the dried film becomes 2 μm. After coating and drying for 180 seconds at 80 ° C. using a hot air dryer, the test plate 3 having a film laminated on the surface of the transparent film substrate is irradiated by 400 mJ / cm ² using a high-pressure mercury lamp. Obtained.

  After immersing the test plates 2 and 3 in warm water at 40 ° C. for 24 hours and wiping off the water on the surface, the adhesion between the film and the substrate constituting the test plates 2 and 3 after immersion, respectively, It measured based on the JIS K5600 cross cut test method, and evaluated according to the following evaluation criteria.

A: No peeling of the film was observed.
○: The area where the film was peeled off was less than 3% of the total grid area.
Δ: The area where the film was peeled was 3% or more and less than 50% of the total grid area.
X: The area where the film was peeled off was 50% or more of the total grid area.

(Evaluation method for water whitening resistance)
The test plate 3 is immersed in warm water at 40 ° C. for 24 hours, and the surface water is wiped off. Then, the coating film constituting the test plate 3 is visually observed for the presence of turbidity and evaluated according to the following evaluation criteria. did.

(Double-circle): There was no change with the external appearance of the test board 3 before immersion, and whitening was not recognized.
○: Slight whitening was confirmed in a very small part, but it was at a level where there was no practical problem.
Δ: Slight whitening was observed throughout the test plate 3.
X: Remarkable whitening was recognized over the whole test plate 3.

[Evaluation method of solvent resistance]
Formulation obtained by blending 0.5 parts by mass of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) with respect to 100 parts by mass of the aqueous urethane resin composition obtained above. The surface of the above [8] GL: hot dip galvanized steel sheet (45% by mass of zinc, 55% by mass of aluminum, 0.8 mm × 70 mm × 150 mm) so that the film thickness of the dried film becomes 2 μm. The surface of the hot-dip galvanized steel sheet substrate was coated with a bar coater, dried at 80 ° C. for 180 seconds using a hot air dryer, and then irradiated with 400 mJ / cm ² using a high-pressure mercury lamp. A test plate 4 having a film laminated thereon was obtained.

The surface of the film after rubbing was visually observed and evaluated based on the following criteria.
A: There is no change on the surface of the film.
○: Although some dissolution of the film was observed, it was at a level where there was no practical problem.
Δ: Dissolution or desorption from the substrate was observed in the range of 10% or more and less than 30% with respect to the entire coating surface.
X: Dissolution or desorption from the substrate was observed in a range of 30% or more with respect to the entire coating surface.

  Further, instead of using gauze impregnated with methyl ethyl ketone, the coating film surface is rubbed in the same manner as described above except that gauze impregnated with ethanol is used, and the surface state after rubbing is visually observed, The evaluation was made according to the same criteria.

[Evaluation method of substrate followability (bending test)]
Formulation obtained by blending 0.5 parts by mass of a photopolymerization initiator (2-hydroxy-2-methyl-1-phenylpropan-1-one) with respect to 100 parts by mass of the aqueous urethane resin composition obtained above. Using a bar coater on the surface of the base material of 0.3 mm x 50 mm x 150 mm with the same material as [8] GL: hot dip galvanized steel sheet, so that the film thickness of the dry film is 2 μm The test plate 5 having a film laminated on the surface of the hot dip galvanized steel sheet is obtained by irradiating with a high pressure mercury lamp at 400 mJ / cm ² after drying for 180 seconds at 80 ° C. using a hot air dryer. It was.
The test plate 5 was used for evaluation based on the JIS K-5600 bending resistance test method (mandrel diameter was 2 mm). The evaluation criteria are as follows.
A: Cracks, wrinkles and whitening are not observed on the surface of the film at the bent portion.
◯: Although wrinkles and whitening were observed on a very small part of the surface of the film at the bent portion, it was at a level that was not a problem for practical use.
Δ: Some cracks are observed in a very small part of the film surface at the bent portion.
X: Generation | occurrence | production of a crack is seen in the whole film | membrane surface of a bending part.

Abbreviations in the table are shown below.
PET: Polyethylene terephthalate, 1.0 mm x 70 mm x 150 mm
PC: Polycarbonate, 1.0mm x 70mm x 150mm
PVC: Vinyl chloride, 2.0mm x 70mm x 150mm
SUS: JIS G4305 SUS304, 0.5 mm x 70 mm x 150 mm
SPC: JIS G3141 SPCC-SB, 0.8 mm x 70 mm x 150 mm
AL: Aluminum, JIS H4000 A1050P, 0.8 mm x 70 mm x 150 mm
Glass: JIS R3202, 2.0 mm x 70 mm x 150 mm
GL: Hot-dip galvanized steel sheet (45% by mass of zinc, 55% by mass of aluminum), 0.8 mm × 70 mm × 150 mm
MEK; methyl ethyl ketone EtOH; ethanol

Claims (10)

Polyol (A), polyisocyanate (B), and hydroxyl group-containing vinyl monomer containing an aliphatic cyclic structure-containing polyol (a1) and a hydrophilic group-containing polyol (a2) other than the aliphatic cyclic structure-containing polyol (a1) A urethane resin (D) having an aliphatic cyclic structure obtained by reacting the body (C), a hydrophilic group and a polymerizable unsaturated double bond, and an aqueous medium (E),
The aliphatic cyclic structure-containing polyol (a1) contains an aliphatic cyclic structure-containing polycarbonate polyol or an aliphatic cyclic structure-containing polyester polyol,
Relative to the total weight of the urethane resin (D), the ratio of aliphatic cyclic structure contained in the urethane resin (D) is Ri range der of 2000mmol / kg~5500mmol / kg, the urethane resin (D) is, the aqueous urethane resin composition characterized der Rukoto those having a weight average molecular weight in the range of 30,000 to 200,000.   The urethane resin (D) has an aliphatic cyclic structure derived from the aliphatic cyclic structure-containing polyol (a1) from 300 mmol / kg to 2000 mmol / kg with respect to the total mass of the urethane resin (D). The aqueous urethane resin composition according to claim 1.   The polyol (A) contains an aliphatic cyclic structure-containing polyol (a1), a hydrophilic group-containing polyol (a2), and another polyol (a3), and the other polyol (a3) is a polycarbonate. The aqueous urethane resin composition according to claim 1, which is a polyol or a polyester polyol. The aqueous urethane resin composition according to claim 1, wherein the urethane resin ( D ) has a polymerizable unsaturated double bond at a molecular end or a molecular side chain. The urethane resin ( D ) includes an aliphatic cyclic structure-containing polyol (a1) and a polyol (A) containing a hydrophilic group-containing polyol (a2), a polyisocyanate (B), a hydroxyl group-containing vinyl monomer (C), , it is obtained by reacting a chain extender, the aqueous urethane resin composition according to claim 1. Furthermore, the water-based urethane resin composition of any one of Claims 1-5 containing a polymerization initiator. The coating agent containing the water-based urethane resin composition of any one of Claims 1-6 . The steel plate surface treating agent containing the water-based urethane resin composition of any one of Claims 1-6 . A cured product obtained by curing the aqueous urethane resin composition according to claim 6 . A laminate in which a film formed using the steel sheet surface treating agent according to claim 8 is laminated on the surface of a metal substrate.