TW201348331A - Urethane resin composition, coating agent, article and leather-like sheet - Google Patents

Abstract

The purpose, which is desired to be solved, of the present invention is about providing a urethane resin composition. The composition does not generate the problem of the smell and the air pollution caused by said neutralizing agent, has excellent stability of dispersion and may form a membrane having excellent tensile strength. The present invention relates to a urethane resin composition, which is characterized by comprising: urethane resin (A) and aqueous medium (B), and the urethane resin (A) has an alkoxyl polyoxyalkylene structure containing 40 % to 100% by mass of oxyethylene structure (a1) and a structure (a2). Said alkoxyl polyoxyalkylene structure containing 40 % to 100% by mass of oxyethylene structure (a1) presents in the terminal of said urethane resin (A) or the side chain of said urethane resin (A).

Description

Urethane resin composition, coating agent, articles and leather-like pieces

The present invention relates to a urethane resin composition which can be applied to various applications including a coating agent or an adhesive, and which can be used in the production of a leather-like sheet.

The urethane resin composition in which the urethane resin is dispersed in an aqueous medium can reduce the load on the environment as compared with the conventional organic solvent urethane resin composition, and is therefore applicable to, for example, It is used in various applications including coating agents or adhesives.

As the aqueous urethane resin composition, it is generally known that a urethane resin having a hydrophilic group such as an anionic group is dispersed in an aqueous medium, and is known as a urethane resin composition. For example, a compound having at least one active hydrogen-containing group and an anionic group or a cationic group, a compound having at least one active hydrogen-containing group and at least one unsaturated group, a polyol, and/or a polyamine And a urethane resin composition obtained by reacting a polyoxyalkylene having at least one active hydrogen-containing group with a polyvalent isocyanate (for example, see Patent Document 1).

However, as the cationic group or the anionic group of the above hydrophilic group, an acidic compound or an alkalinity is used for the amine group or the carboxyl group. The compound is neutralized, and the odor and air pollution caused by the above acidic compound or basic compound are problems of recent years.

In the urethane resin composition, a urethane resin composition having a nonionic group such as a polyoxyalkylene group having a hydrophilic group is studied (for example, see Patent Document 2). .

However, compared with the urethane resin having a cationic group and an anionic group, the above nonionic urethane resin is inferior in water dispersing property, so that it cannot be stably settled in an aqueous medium for a long period of time. Dispersed situation.

In the method of improving the water dispersibility of the nonionic urethane resin composition, for example, a method of using an external emulsifier such as polyoxyethylene ethyl stilbene phenyl ether is known.

However, the use of the above emulsifier is caused by a significant decrease in the tensile strength of the film formed by using the urethane resin composition, so that when an external force is applied to the film, the film may be split or broken. situation.

In this way, in fact, there has been no problem of causing odor and air pollution caused by the neutralizing agent such as the above-mentioned basic compound, and even if the external emulsifier is not substantially used, the water can be formed. A urethane resin composition of a film having excellent dispersion stability and high strength of a medium.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-248470

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2009-249635

The problem to be solved by the present invention is to provide a urethane resin composition which does not cause odor and air pollution caused by the above neutralizing agent, and which can form a film excellent in dispersion stability and excellent in tensile strength. Things.

The inventors of the present invention have found that in order to solve the above problems, it has been found that the above problem can be solved by using a urethane resin composition which constitutes an amide formic acid. The terminal of the main chain structure of the ester resin or the side chain of the above-mentioned main chain structure has an alkoxy polyoxyalkylene structure (a1) having an oxygen-extended ethyl structure of 40% by mass to 100% by mass, and is constituted The main chain structure of the above urethane resin has a predetermined structure represented by the following formula (1).

That is, the present invention relates to a urethane resin composition characterized by comprising a urethane resin (A) and an aqueous medium (B), and the urethane resin (A) is An alkoxy polyoxyalkylene structure (a1) having an oxygen-extended ethyl group structure of 40% by mass to 100% by mass and a structure (a2) represented by the following formula (1), and the above having 40% by mass The alkoxy polyoxyalkylene structure (a1) to 100% by mass of an oxygen-extended ethyl group is present at the end of the above urethane resin (A) or the side chain of the above urethane resin (A) .

(In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group; m represents an average value of 0 to 20; n represents an average value of 0 to 20; and the sum of m and n represents an average of 1 to 40 value).

The urethane resin composition of the present invention does not cause a problem of odor and air pollution caused by neutralizing a neutralizing agent used as a cationic group or an anionic group of a hydrophilic group, even if substantially When an external emulsifier is not used, a film having excellent dispersion stability and excellent tensile strength can be formed, and therefore it can be used, for example, as a coating agent, particularly a coating agent for forming a surface coating layer. Further, the above urethane resin composition can be used, for example, in the formation of a skin layer constituting a laminate of a leather-like sheet or the like. Further, by impregnating the urethane resin composition with a fibrous base material such as a nonwoven fabric, a leather-like sheet having a soft touch can be produced.

[Formation of the Invention]

The urethane resin composition of the present invention is characterized in that it contains a urethane resin (A) and an aqueous medium (B), and the urethane resin (A) has a content of 40% by mass. The alkoxy polyoxyalkylene structure (a1) to 100% by mass of an oxygen-extended ethyl structure is represented by the following formula (1) In the structure (a2), the alkoxy polyoxyalkylene structure (a1) having an oxygen-extended ethyl group structure of 40% by mass to 100% by mass is present at the end of the above urethane resin (A). Or the side chain of the above urethane resin (A).

(In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group; m represents an average value of 0 to 20; n represents an average value of 0 to 20; and the sum of m and n represents an average of 1 to 40 value).

The urethane resin composition of the present invention is obtained by dispersing or dissolving the urethane resin (A) in the aqueous medium (B), thereby improving workability, coating workability, and the like. good.

First, the urethane resin used in the above urethane resin composition will be described.

The urethane resin (A) used in the present invention has the above alkoxy polyoxyalkylene structure (a1) and the structure (a2) represented by the above formula (1), wherein the alkoxy group described above The polyoxyalkylene group structure (a1) is present at the end of the above urethane resin (A) or the side chain of the above urethane resin (A).

The urethane resin (A) is used in the main chain structure including the urethane bond of the urethane resin (A) using the alkoxy polyoxyalkylene structure (a1). End, or relative to the above amine group The side chain of the main chain structure of the formate resin (A).

Here, when the urethane resin having an alkoxy polyoxyalkylene structure in the main chain structure using a urethane resin is substituted for the above urethane resin (A), there is a case where it is aqueous. The medium cannot maintain a stable dispersion stability. Further, the term "main chain structure" as used in the present invention means, for example, when a diol which is a polyol is reacted with a binary isocyanate which is a polybasic isocyanate to produce a urethane resin, which has a reaction with the above-mentioned hydroxyl group and an isocyanate group. The formed urethane bond is the main structure.

Further, the alkoxy polyoxyalkylene structure (a1) is an oxygen-extended ethyl group having the following formula (2), which is the same as the alkoxy polyoxyalkylene group (a1). The unit is in the range of 40% by mass to 100% by mass.

-CH ₂ CH ₂ O- (2)

Here, when the alkoxy polyoxyalkylene structure (a1) is substituted with the alkoxy polyoxyalkylene structure having 35 mass% of the above-mentioned oxygen-extended ethyl group, the urethane resin may be caused. The dispersion stability in aqueous media is significantly reduced.

The above alkoxy polyoxyalkylene structure (a1) is used in the range of 50% by mass to 100% by mass based on the above-mentioned oxygen-extended ethyl group in relation to the above alkoxy polyoxyalkylene structure (a1). Further, it is preferable to have both good dispersion stability and an increase in tensile strength of the formed film, and it is more preferable to use a range of from 85% by mass to 100% by mass.

The alkoxy polyoxyalkylene structure (a1) may, for example, be an alkoxy polyoxyethylene structure. Further, the above alkoxy polyoxyalkylene The structure (a1) may be, for example, an alkoxy group (polyoxy-extension ethyl-polyoxypropyl propyl) structure composed of an oxygen-extended ethyl unit and another oxygen-extended alkyl unit; an alkoxy group (polyoxygen) a block structure of an ethyl-polyoxybutylene structure or the like; or a random structure composed of the above-mentioned oxygen-extended ethyl unit and an oxygen-extended propyl structure; and the above-mentioned oxygen-extended ethyl unit and oxygen-extended butyl group The random structure formed by the structure.

In the above alkoxy polyoxyalkylene structure (a1), a random structure composed of the above-mentioned oxygen-extended ethyl unit and an oxygen-extended propyl unit is used, and the above-mentioned oxygen-extended ethyl unit and oxygen-extension are used. It is preferable that the random structure composed of the base unit can further improve the dispersion stability of the urethane resin (A) in the aqueous medium (B).

Further, an alkoxy group constituting the terminal of the alkoxy polyoxyalkylene group (a1) is preferably a methyl group, an ethyl group, a butyl group or the like.

The above alkoxy polyoxyalkylene structure (a1) is preferably one having a number average molecular weight of from 500 to 10,000, more preferably from a number average molecular weight of from 500 to 5,000.

The alkoxy polyoxyalkylene structure (a1) may be present at one end of the urethane resin (A) or at the end of the urethane resin (A). More than one. Further, the alkoxy polyoxyalkylene group structure (a1) may be present in one or two or more at both ends of the urethane resin (A).

When the urethane resin (A) has a multi-branched structure, specifically, the polyol and the polyisocyanate used in the production of the urethane resin (A) have a triol or a triisocyanate. Alkoxy group having three or more hydroxyl groups and having three or more isocyanates The polyoxyalkylene group structure (a1) may be present one or two or more at each end of the obtained urethane resin (A).

The alkoxy polyoxyalkylene structure (a1) is mainly composed of the above polyol and a polyvalent isocyanate, and may be present in the side chain thereof with respect to the main chain structure of the urethane resin (A).

The alkoxy polyoxyalkylene structure (a1) is present in the urethane resin (A) in a range of 1% by mass to 25% based on the total of the urethane resin (A). % is preferable, and in the range of 1% by mass to 10% by mass, not only the urethane resin (A) can be imparted with more excellent water dispersion stability, but also a film having more excellent tensile strength can be formed. Therefore it is better.

Further, the urethane resin (A) may be used not only in the alkoxy polyoxyalkylene structure (a1) but also in the alkoxy polyoxyalkylene structure (a1). The structure (a2) represented by the following general formula (1).

(In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group; m represents an average value of 0 to 20; n represents an average value of 0 to 20; and the sum of m and n represents an average of 1 to 40 value).

Here, the urethane resin having the above alkoxy polyoxyalkylene structure (a1) and having the structure (a2) represented by the above formula (1) is used. When the urethane resin (A) is replaced by the above, there is a case where a film having excellent tensile strength cannot be formed.

R ¹ and R ² in the above formula (1) each independently represent a hydrogen atom or an alkyl group, and R ¹ and R ² are each preferably a hydrogen atom or an alkyl group.

m and n in the above formula (1) represent the average addition molar number of the oxygen-extended ethyl unit, each of which is in the range of 0 to 20 on average, preferably in the range of 1 to 20 on average, and an average of 1 to 5 The range is better.

The sum of m and n above is in the range of 1 to 40 on average, preferably in the range of 1 to 20 on average, more preferably in the range of 1 to 10 on average, and particularly preferably in the range of 1 to 5 on average.

By using the urethane resin (A) having the above formula (1), good dispersion stability can be maintained, and a film having excellent tensile strength can be formed.

The structure (a2) represented by the above formula (1) is preferably contained in an amount of 0.1% by mass to 25% by mass based on the total amount of the urethane resin (A), and is contained in an amount of 1% by mass. A range of 20% by mass is more preferable, and a range of from 1% by mass to 15% by mass can be imparted to more excellent dispersion stability.

The urethane resin (A) having the above alkoxy polyoxyalkylene structure (a1) and the structure (a2) represented by the above formula (1) is formed to have more excellent tensile strength. The film is preferably one having a weight average molecular weight of from 10,000 to 1,000,000, and more preferably a weight average molecular weight having a range of from 30,000 to 500,000.

The above urethane resin (A) can be produced, for example, by reacting a polyol (a'-1) with a polyvalent isocyanate (a'-2) to produce a terminal or side chain. A urethane resin (A') having an isocyanate group, followed by polyoxygenation by blocking the above-mentioned urethane resin (A') with a hydroxyl group of the polyoxyalkylene glycol via an alkyl alcohol It is produced by reacting an alkyl monoalkyl ether.

In the above polyol (a'-1), for example, the structure (a2) represented by the above formula (1) can be introduced into the above urethane resin (A), and the bisphenol compound is added with ethylene oxide. A polyether polyol, and a polyether ester polyol obtained by reacting the above polyether polyol with a polyvalent carboxylic acid.

As the bisphenol compound which can be added to the above ethylene oxide, for example, bisphenol A, bisphenol F or the like can be used.

The above ethylene oxide is preferably in the range of from 1 to 10 in terms of addition to one hydroxyl group of the bisphenol compound, and more preferably in the range of from 1 to 5.

The polycarboxylic acid which can be reacted with the polyether polyol to which ethylene oxide is added in the above bisphenol compound can be, for example, succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid or bisphenol. An aliphatic polycarboxylic acid such as an acid, azelaic acid, sebacic acid or dodecane dicarboxylic acid; or an aromatic polycarboxylic acid such as phthalic acid, isophthalic acid or terephthalic acid.

When the above polyether polyol and the above polyether ester polyol are further improved in the tensile strength of the film, it is preferred to use an average molecular weight of 500 to 5,000. .

Further, the polyether polyol and the polyether ester polyol are used in the range of the total amount of the polyol (a'-1) used in the production of the urethane resin (A). A total of 0.1% by mass to 25% by mass is preferred.

Further, the above polyol (a'-1) is in addition to the above polyether polyol and In addition to the above polyether ester polyol, other polyols may be appropriately used in combination as necessary.

As the above other polyol, for example, a polyether polyol or a polyether ester polyol having no structure (a2) represented by the above formula (1), a polyester polyol, a polycarbonate polyol, and the like may be used. The polyether polyol or the polycarbonate polyol of the structure (a2) represented by the above formula (1) can further increase the tensile strength of the formed film, and thus is preferable.

In the polyether polyol which does not have the structure (a2) represented by the above-mentioned general formula (1), for example, one or two or more kinds of compounds having two or more active hydrogen atoms can be used as a starting agent to form an alkylene oxide. Addition aggregator.

As the above initiator, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6- can be used. Hexanediol, glycerol, trimethylolethane, trimethylolpropane, and the like.

As the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran or the like can be used.

A polyether polyol which does not have the structure (a2) represented by the above formula (1), specifically, polyoxybutylene butyl glycol or the like can be used.

Further, the polyether ester polyol which does not have the structure (a2) represented by the above formula (1) can be a polyether polyol and a polycarboxylic acid which do not have the structure (a2) represented by the above formula (1). The reaction comes. As the polyvalent carboxylic acid, for example, an aliphatic polycarboxylic acid such as succinic acid, maleic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid or dodecanedicarboxylic acid can be used. Acid; phthalic acid, isophthalic acid, terephthalic acid, etc. Aromatic polycarboxylic acid.

Further, as the polycarbonate polyol which can be used in the above other polyol, for example, a carbonate or carbonium chloride can be reacted with a polyol.

As the above carbonate, methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclic carbonate, diphenyl carbonate or the like can be used.

As the polyol reactive with the above carbonate, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol can be used. , 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1 ,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-nonanediol, 1,11-undecanediol, 1 ,12-dodecanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-hexanediol, 2-methyl-1,3-propanediol, 2-methyl -1,8-octanediol, 2-butyl-2-ethylpropanediol, 2-methyl-1,8-octanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4 - lower molecular weight dihydroxy compounds such as cyclohexanedimethanol, hydroquinone, resorcinol, bisphenol A, bisphenol F, 4,4'-bisphenol, polyethylene glycol, polypropylene glycol, poly A polyester polyol such as polyether polyol such as oxytetramethylene glycol, polyhexamethylene adipate, polyhexamethylene succinate or polycaprolactone.

The polyester polyol which can be used for the above other polyols can be subjected to ring-opening polymerization using, for example, a cyclic ester compound of a low molecular weight polyol and a polycarboxylic acid obtained by esterification reaction, ε-caprolactone or the like. The obtained polyester, the copolymerized polyester, and the like.

The above low molecular weight polyol can use, for example, a molecular weight Aliphatic pluralism of about 50 to 300 ethylene glycol or propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3-butanediol, etc. An alcohol, a polyhydric alcohol having an aliphatic cyclic structure such as cyclohexanedimethanol, or a polyhydric alcohol having an aromatic structure such as bisphenol A.

As the polyvalent carboxylic acid which can be used in the production of the above polyester polyol, for example, an aliphatic polycarboxylic acid such as succinic acid, adipic acid, sebacic acid or dodecanedicarboxylic acid; An aromatic polycarboxylic acid such as phthalic acid, phthalic acid or naphthalene dicarboxylic acid, and an acid anhydride or esterified product thereof.

The other polyols described above may be used in a number average molecular weight having a range of from 500 to 5,000.

The other polyol described above is preferably used in the range of 30% by mass to 95% by mass based on the total amount of the above polyol (a'-1), and is used in the range of 50% by mass to 95% by mass. It is preferred that the tensile strength of the formed film can be further improved.

The polyisocyanate (a'-2) which can be reacted with the above polyol (a'-1) can be, for example, phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, poly Aromatic polyisocyanate such as methyl polyphenyl polyisocyanate or carbodiimide diphenylmethane polyisocyanate, hexamethylene diisocyanate, diazonic acid diisocyanate, cyclohexane diisocyanate, isophorone II Isocyanate, dicyclohexylmethane diisocyanate, benzodimethyl diisocyanate, tetramethyl dimethyl diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, etc. having an aliphatic or aliphatic cyclic structure Isocyanate or the like is used singly or in combination of two or more. among them. It is preferred to use a polyisocyanate having an aliphatic cyclic structure, and it is more preferable to use isophorone diisocyanate or dicyclohexylmethane diisocyanate. Further, in order to obtain excellent durability such as a formed film, it is preferred to use an aromatic polyisocyanate such as diphenylmethane diisocyanate.

The reaction of the above polyol (a'-1) with the above polyisocyanate (a'-2) can be carried out, for example, without a solvent or under an organic solvent.

The reaction of the above polyol (a'-1) with the above polyisocyanate (a'-2) is carried out by the hydroxyl group of the above polyol (a'-1) and the isocyanate of the above polyisocyanate (a'-2). The equivalent ratio of the base [isocyanate group / hydroxyl group] is preferably in the range of 1.05 to 2.5, more preferably in the range of 1.1 to 2.

The organic solvent used in the production of the above urethane resin (A') may be, for example, a ketone such as acetone or methyl ethyl ketone; tetrahydrofuran or An ether such as an alkyl group; an acetate such as ethyl acetate or butyl acetate; a nitrile such as acetonitrile; a guanamine such as dimethylformamide or N-methylpyrrolidone; or a combination of two or more of them.

In the production of the above urethane resin (A'), a chain extender may be used as necessary. Specifically, the above polyol (a'-1) is mixed with the above polybasic isocyanate (a'-2) in the absence of a solvent or an organic solvent, and is allowed to react at 50 ° C to 100 ° C for about 3 hours to 10 hours. To the left and right, a urethane prepolymer having an isocyanate group at the end is produced, and then, by reacting the urethane prepolymer with a chain extender, a higher molecular weight amine group having a urea bond can be produced. Formate resin.

The chain extender may be, for example, a polyamine or a hydrazine compound. a compound, a compound having other active hydrogen atoms, and the like.

As the above polyamine, for example, ethylenediamine, 1,2-propylenediamine, 1,6-hexamethylenediamine, and piperazine can be used. 2,5-Dimethyl pipe , isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine Isoamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N-methylaminopropylamine, etc. a diamine having one primary amine group and one secondary amine group; a polyamine such as diethylenetriamine, dipropylenetriamine or triethylenetetramine.

The above ruthenium compound may be, for example, ruthenium, N,N'-dimethylhydrazine, 1,6-hexamethylenebiguanide, diacetyl, hexamethylene, pentane, ruthenium, M-xylylene hydrazide, β-aminourea propylene dioxime, 3-aminourea-propyl-carbamate, Aminourea-3-aminoureamethyl-3,5,5- Trimethylcyclohexane and the like.

As the compound having other active hydrogen, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, or the like can be used. Hexamethylene glycol, sucrose, methylene glycol, glycerol, sorbitol, bisphenol A, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'- Dihydroxydiphenylhydrazine, hydrogenated bisphenol A, hydroquinone, water, and the like.

The chain extender introduces a urea bond into the formed film, and as a result, from the viewpoint of further improving the durability of the film, the total amount of the raw materials used in the production of the urethane resin (A') is A range of from 1% by mass to 10% by mass is preferred, and a range of from 1% by mass to 5% by mass is more preferred.

The above urethane resin (A) may be alkyl-blocked by a urethane resin (A') having an isocyanate group at the terminal or side chain obtained above and a hydroxyl group of the polyoxyalkylene glycol. It is produced by reacting a polyoxyalkylene monoalkyl ether. The above reaction is carried out, for example, in the absence of a solvent or in the presence of an organic solvent, and the mixture is allowed to react at about 50 ° C to 100 ° C for about 3 hours to 10 hours.

The polyoxyalkylene glycol monoalkyl ether used in the above reaction may be one in which one of the two hydroxyl groups of the polyoxyalkylene glycol is blocked with an alkyl group.

Specifically, the above polyoxyalkylene glycol monoalkyl ether can be used: polyoxyethylene glycol monomethyl ether, polyoxyethylene ethyl propylene glycol monomethyl ether, dihydroxy polyoxyethylene ethyl ether Monomethyl ether and the like. Among them, the use of polyoxyethylene glycol monomethyl ether is preferable because it can form a film having more excellent dispersion stability and more excellent tensile strength.

The above polyoxyalkylene glycol monoalkyl ether is preferably one having an average molecular weight of from 500 to 10,000, more preferably one having an average molecular weight of from 500 to 5,000.

The method for producing a urethane resin composition by mixing the urethane resin (A) obtained by the above production method with an aqueous medium (B) is, for example, a urethane obtained by the above method. The resin (A) or an organic solvent solution thereof can be produced by mixing and stirring with an aqueous medium (B). The organic solvent contained at this time may be removed by distillation or the like as needed. When the urethane resin (A) and the aqueous medium (B) are mixed, a machine such as a homogenizer can be used as needed.

The urethane resin obtained by the above production method can be obtained (A) The aqueous medium (B) which is dispersed or dissolved may, for example, be water, an organic solvent mixed with water, and a mixture thereof. Examples of the organic solvent to be mixed with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; and polyalkylenes such as ethylene glycol, diethylene glycol and propylene glycol. a diol; an alkyl ether of a polyalkylene glycol; an indoleamine such as N-methyl-2-pyrrolidone or the like. In the present invention, water may be used alone, or a mixture of water and an organic solvent mixed with water may be used, or only an organic solvent mixed with water may be used. From the point of safety and environmental load, it is better to use only water, or a mixture of water and organic solvent mixed with water, and it is better for water alone.

The urethane resin composition of the present invention obtained by the above method, the urethane resin (A) is contained in an amount of 15% by mass to 60% by mass based on the total amount of the urethane resin composition. The range of % is preferable, and it is more preferably in the range of 20% by mass to 60% by mass, and more preferably in the range of 30% by mass to 55% by mass, because the coating workability can be improved.

Further, the aqueous medium (B) is preferably contained in the range of 30% by mass to 80% by mass based on the total amount of the urethane resin composition, and more preferably in the range of 40% by mass to 80% by mass. In the range of 45% by mass to 70% by mass, it is more preferable because the coating workability can be improved.

The above urethane resin composition is often used in combination with an emulsifier from the viewpoint of further improving the dispersion stability. However, the use of the above emulsifier is one of the causes of poor appearance and water resistance of the resulting film.

Since the urethane resin composition of the present invention can maintain good dispersion stability without using the above emulsifier, it is possible to form a film having excellent appearance and excellent water resistance. Specifically, the urethane resin composition of the present invention may contain an emulsifier in a range of 0% by mass to 5% by mass based on the total amount of the urethane resin composition, and may also contain 0. The range of mass % to 0.5% is better in the case of no emulsifier.

The urethane resin composition of the present invention may contain various additives as necessary. For example, an associative thickener, an alkali soluble thickener, a crosslinking agent, a urethane catalyst, a decane coupling agent, a filler, a thixotropic agent, a tackifier, a wax, and a heat Additives such as stabilizers, light stabilizers, fluorescent brighteners, foaming agents, etc.; thermoplastic resins, thermosetting resins, pigments, dyes, conductive additives, antistatic agents, moisture permeability improving agents, water repellents, Oil-repellent agent, hollow foam, compound containing crystal water, flame retardant, water absorbing agent, moisture absorbent, deodorant, foam stabilizer, defoaming agent, anti-fungal agent, preservative, algaecide, pigment Dispersant, anti-caking agent, anti-hydrolysis agent.

As the above-mentioned associative thickener, for example, a cellulose derivative such as hydroxyethylcellulose, methylcellulose or carboxymethylcellulose, or a polyacrylate, a polyvinylpyrrolidone or a urethane can be used. Thickener, polyether thickener, etc. Among them, a polyacrylate-containing thickener having a high thickening effect on the above urethane resin (A) is preferred. The above-mentioned associative thickener is preferably used in the range of 0.5% by mass to 5% by mass based on the total amount of the above urethane resin (A).

The above urethane resin composition can form a high-strength film, and thus can be applied to a coating agent applied to various substrate surfaces, preferably. A coating agent for forming a coating layer is used.

As the substrate, for example, a fibrous substrate such as a woven fabric or a non-woven fabric, a plated steel sheet such as a galvanized steel sheet or an aluminized-zinc alloy steel sheet, or an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate or a stainless steel plate can be used. Metal substrate; polycarbonate substrate, polyester substrate, acrylonitrile-butadiene-styrene substrate, polyacrylic substrate, polystyrene substrate, polyurethane substrate, epoxy resin A plastic substrate such as a substrate, a polyvinyl chloride substrate, or a polyamide substrate; a glass substrate or a leather-like sheet. Among them, as the base material, the use of the synthetic leather such as the synthetic leather and the processed leather used for the processing of the shoe and the bag is used by bonding other members or applying a putty to the surface of the leather-like sheet by using an adhesive. It is preferable to be able to efficiently produce a leather piece which is excellent in design.

The coating agent of the present invention can be formed by, for example, directly coating the surface of the substrate, followed by drying and hardening to form a film. Further, the coating agent of the present invention is applied onto the surface of the release paper to be dried and cured, and then a film may be formed on the substrate in the coating area. Further, when the crosslinking agent is used, the coating agent is applied to the surface of the substrate, and the urethane resin (A) or the like is mixed with the crosslinking agent to maintain good coating workability. good.

The method of applying the coating agent to the above-mentioned substrate may, for example, be a spray coating method, a curtain coating method, a shower coating method, a roll coating method, a brush coating method, or a dipping method.

The above drying and hardening method may be a method of curing at a normal temperature from about 1 day to about 10 days, and it is preferred to heat at a temperature of from 50 ° C to 250 ° C for from about 1 second to about 600 seconds from the viewpoint of rapid curing. and When a plastic substrate which is easily deformed or discolored at a relatively high temperature is used, it is preferably cured at a relatively low temperature of about 30 ° C to 100 ° C.

The film thickness of the film formed by using the coating agent of the present invention can be appropriately adjusted depending on the intended use of the article containing the film, and is generally preferably from about 0.5 μm to about 100 μm.

When the urethane resin composition of the present invention is used as a coating agent for forming an overcoat layer, an intermediate layer such as an undercoat layer may be provided on the surface of the substrate. The undercoat layer may, for example, be a coating containing a conventional acrylic resin, a coating containing a polyester resin, a coating containing an alkyd resin, a coating containing an epoxy resin, or a coating containing a fatty acid-modified epoxy resin. A coating containing a silicone resin, a coating containing a polyurethane resin, and the like.

As described above, the article including the above-mentioned substrate and the film formed using the coating agent of the present invention can be used, for example, in automobile parts and various home electric appliances such as automobile interior and exterior materials represented by mobile phones, home electric appliances, and OA equipment. Parts, building materials, etc.

Further, the urethane resin composition of the present invention can be used as a material for forming the skin layer of the above-mentioned leather-like sheet. The leather-like sheet is generally formed by laminating an intermediate layer such as a porous layer on the surface of the fibrous substrate impregnated with the resin as needed, and layering the skin layer on the intermediate layer. The urethane resin composition of the present invention is used.

As the fibrous base material, a nonwoven fabric, a woven fabric, a knitted fabric or the like can be used. As the substrate constituting the above, for example, polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber can be used. Dimensions, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, blended fibers of these, and the like.

The surface of the substrate may be subjected to anti-electric processing, release processing, water-repellent processing, water absorption processing, antibacterial and deodorizing processing, bacteriostatic processing, and ultraviolet-resistant processing as necessary.

a leather-like sheet in which a surface layer of the fibrous substrate is directly laminated with a skin layer, for example, by coating and drying the urethane resin composition on a sheet subjected to release treatment to form a skin layer, followed by The fibrous substrate can be produced by laminating the fibrous substrate by using an adhesive or the like. Examples of the method of applying the above urethane resin composition on the sheet include a gravure coating method, a knife coating method, a tube coating method, and a comma coating method. Further, a method of drying and hardening the urethane resin composition coated by the above method may be, for example, at a normal temperature for about 1 to 10 days, or at a temperature of 50 to 250 ° C. Heating for about 1 second to 600 seconds.

Further, in the above-mentioned leather-like sheet, an intermediate layer such as a porous layer is provided between the fibrous base material and the skin layer, and the urethane resin composition is applied, for example, to a sheet subjected to release treatment. Coating and drying to form a skin layer, and then coating and hardening the resin composition for forming a porous layer which is foamed by a conventional mechanical foaming method or a water foaming method to form a porous layer. Next, a conventional fibrous binder can be laminated on the porous layer by using a conventionally known adhesive.

Further, the urethane resin composition of the present invention can be used in a leather-like sheet comprising an impregnated substrate obtained by impregnating a fibrous substrate. Used in manufacturing.

As the fiber base material, a nonwoven fabric, a woven fabric, a knitted fabric or the like can be used. As the fiber substrate, for example, polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, ray fiber, polylactic acid fiber, cotton, hemp, silk, wool can be used. , such blended fibers, and the like.

The method of impregnating the above-mentioned urethane resin with the above-mentioned urethane resin is exemplified by directly immersing the above-mentioned fiber base material in a tank in which the urethane resin composition is stored, such as a rolling mill or the like. A method of twisting excess urethane resin.

Next, the fibrous substrate impregnated with the urethane resin composition is heated to a temperature above the sensitization temperature of the urethane resin (about 50 ° C to 80 ° C), except for the above amine group In addition to solidification of the acid ester resin, the aqueous medium (B) contained in the above urethane resin composition is evaporated. Thereby, a substrate in which the fibrous substrate is impregnated with the urethane resin (A) can be produced.

The leather-like sheet obtained by the above method may be, for example, a furniture member such as a shoe, a bag, a cloth, a chair or a sofa; a vehicle interior material such as a vehicle seat and a steering wheel; a waterproof and breathable material, a synthetic leather, an artificial leather, or the like. Imitation leather sheet; used in abrasive materials, core materials such as microphones, etc.

As described above, the urethane resin composition of the present invention can be used in a resin composition for forming a skin layer containing various coating agents and various laminates, and is particularly suitable for use in the production of a leather-like sheet.

[Examples]

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

[Example 1] Modification of urethane resin composition (X1)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, a polyoxybutylene butyl diol (number average molecular weight: 2,000) of 600 g and bisphenol A were added to a compound having 2 mol of ethylene oxide ( In the formula (1), R ¹ and R ² are a methyl group, and the sum of m and n is a compound of 2) 65 g, polyoxyethylene glycol monomethyl ether (number average molecular weight: 4,000), 75 g, cyclohexane 70 g of methanol and 360 g of dicyclohexylmethane diisocyanate were reacted at 70 ° C until the NCO% reached 1.3% by mass, thereby obtaining a methyl ethyl group of a urethane prepolymer (X1') having an isocyanate group at the end. Ketone solution. Further, the above NCO% represents the mass ratio of the isocyanate groups to the total amount of the methyl ethyl ketone solution of the above urethane polymer (X1').

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (X1') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 270 g of a 27 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (X1) having a nonvolatile content of 40% by mass.

[Example 2] Modulation of urethane resin composition (X2)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, 325 g of polyoxybutylene butyl diol (quantitative molecular weight 2,000) and bisphenol A were added to a compound having 2 mol of ethylene oxide ( In the formula (1), R ¹ and R ² are a methyl group, and the sum of m and n is a compound of 2) 65 g, polyoxyethylene glycol monomethyl ether (number average molecular weight: 4,000), 350 g, cyclohexane 70 g of methanol and 360 g of dicyclohexylmethane diisocyanate were reacted at 70 ° C until NCO% reached 1.7% by mass, thereby obtaining a methyl ethyl group of a urethane prepolymer (X2') having an isocyanate group at the end. Ketone solution.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (X2') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 370 g of a 37 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (X2) having a nonvolatile content of 30% by mass.

[Example 3] Modulation of urethane resin composition (X3)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, 415 g of polyoxybutylene butyl diol (quantitative molecular weight 2,000) and bisphenol A were added to a compound having 2 mol of ethylene oxide ( In the formula (1), R ¹ and R ² are a methyl group, and the sum of m and n is a compound of 2) 250 g, polyoxyethylene glycol monomethyl ether (number average molecular weight: 4,000), 75 g, and dicyclohexylmethane 360 g of the diisocyanate was reacted at 70 ° C until the NCO% reached 1.2% by mass, whereby a methyl ethyl ketone solution of a urethane prepolymer (X3') having an isocyanate group at the end was obtained.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (X3') was mixed with 2340 g of pure water, and emulsified by phase inversion emulsification. liquid.

Supplying the obtained emulsion in the obtained emulsion 250 g of an aqueous solution of a chain extender of 25 g was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (X3) having a nonvolatile content of 40% by mass.

[Example 4] Modification of urethane resin composition (X4)

A compound of polyoxybutylene butyl diol (number average molecular weight: 2,000) of 600 g and bisphenol A was added with 2 mol of ethylene oxide in the presence of methyl 11-glycolone and 0.1 g of stannous octoate ( a compound of the formula (1) wherein R ¹ and R ² are a methyl group and the sum of m and n is 2) 65 g, and a polyol having a methoxy polyoxyethylene structure in the side chain (YMER N120; Perstorp Co., Ltd. 15 g, 70 g of cyclohexanedimethanol, and 360 g of dicyclohexylmethane diisocyanate were reacted at 70 ° C until the NCO% reached 1.3% by mass, thereby obtaining a urethane prepolymer having an isocyanate group at the molecular terminal ( X4') methyl ethyl ketone solution.

2,220 g of a methyl ethyl ketone solution having a urethane prepolymer (X4') having an isocyanate group at the molecular terminal and 2,220 g of pure water were mixed, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 27 g of an aqueous chain extender solution of 270 g was mixed to cause chain elongation reaction.

Then, methyl ethyl ketone was distilled off from the above reaction mixture to obtain a urethane resin composition (X4) having a nonvolatile content of 40% by mass.

[Example 5] Modification of urethane resin composition (X5)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, a compound of polyoxybutylene butyl diol (number average molecular weight: 2,000) of 600 g and bisphenol A was added to have 10 mol of ethylene oxide ( In the formula (1), R ¹ and R ² are a methyl group, and the sum of m and n is 10 compounds) 65 g, polyoxyethylene glycol monomethyl ether (number average molecular weight: 4,000), 75 g, cyclohexane 70 g of methanol and 360 g of dicyclohexylmethane diisocyanate were reacted at 70 ° C until the NCO% reached 1.3% by mass, thereby obtaining a methyl ethyl group of a urethane prepolymer (X5') having an isocyanate group at the end. Ketone solution.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (X5') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 270 g of a 27 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (X5) having a nonvolatile content of 40% by mass.

[Example 6] Modification of urethane resin composition (X6)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, a polyoxybutylene butyl diol (number average molecular weight: 2,000) of 600 g and bisphenol A were added to a compound having 2 mol of ethylene oxide ( a compound of the formula (1) wherein R ¹ and R ² are a methyl group, and the sum of m and n is 2) 65 g of a polyoxyethylene methyl polyoxyalkylene random copolymer monobutyl ether (oxygen) The mass ratio of the ethyl group structure to the oxygen propyl structure is 75/25; the number average molecular weight is 3,400), 75 g, cyclohexane dimethanol 70 g, and dicyclohexylmethane diisocyanate 360 g, so that the NCO% reaches 1.3% by mass. The reaction was carried out at ° C, whereby a methyl ethyl ketone solution of a urethane prepolymer (X6') having an isocyanate group at the end was obtained.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (X6') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 270 g of a 27 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (X6) having a nonvolatile content of 40% by mass.

[Example 7] Modulation of urethane resin composition (X7)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, polycarbonate diol (manufactured by Nippon Polyurethane Industrial Co., Ltd.; Nipporan N980R; number average molecular weight: 2,000) 600 g, bisphenol A Addition of a compound having 2 moles of ethylene oxide (the compound of the formula (1) wherein R ¹ and R ² are a methyl group, and the sum of m and n is 2) 65 g, polyoxyethylene glycol monomethyl 75 g of a group (quantitative molecular weight: 4,000), 70 g of cyclohexanedimethanol, and 360 g of dicyclohexylmethane diisocyanate, and reacted at 70 ° C until NCO% reached 1.3% by mass, thereby obtaining an amine group having an isocyanate group at the terminal. A solution of the ester prepolymer (X7') in methyl ethyl ketone. Further, the above NCO% represents the mass ratio of the isocyanate groups to the total amount of the methyl ethyl ketone solution of the above urethane polymer (X7').

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (X7') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 270 g of a 27 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (X7) having a nonvolatile content of 40% by mass.

[Example 8] Modulation of urethane resin composition (X8)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, polycarbonate diol (manufactured by Nippon Polyurethane Co., Ltd.; Nipporan N980R; number average molecular weight: 2,000) 415 g, bisphenol A Addition of a compound having 2 moles of ethylene oxide (the compound of the formula (1) wherein R ¹ and R ² are a methyl group, and the sum of m and n is 2) 250 g, polyoxyethylene glycol monomethyl 75 g of a group (the number average molecular weight: 4,000) and 360 g of dicyclohexylmethane diisocyanate were reacted at 70 ° C until the NCO% reached 1.2% by mass, thereby obtaining a urethane prepolymer having an isocyanate group at the end (X8). ') methyl ethyl ketone solution.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (X8') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 250 g of an aqueous chain extender solution of 25 g, which was subjected to a chain elongation reaction by mixing, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (X8) having a nonvolatile content of 40% by mass.

[Example 9] Modulation of urethane resin composition (X9)

Polycarbonate diol (manufactured by Nippon Polyurethane Industry Co., Ltd.; Nipporan N980R; number average molecular weight: 2,000) 600 g, bisphenol A in the presence of methyl 11-glycolone and 0.1 g of stannous octoate Addition of a compound having 2 moles of ethylene oxide (the compound of the formula (1) wherein R ¹ and R ² are a methyl group, and the sum of m and n is 2) 65 g, and the side chain has a methoxy group 15 g of an oxygen-extended ethyl structure (YMER N120; Perstorp), 360 g of cyclohexanedimethanol, and 360 g of dicyclohexylmethane diisocyanate, and reacted at 70 ° C until the NCO% reached 1.3% by mass, thereby obtaining an end. A methyl ethyl ketone solution of a urethane prepolymer (X9') having an isocyanate group.

2220 g of a methyl ethyl ketone solution of the urethane prepolymer (X9') having an isocyanate group at the end thereof was mixed with 2,220 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 27 g of an aqueous chain extender solution of 270 g was mixed to cause chain elongation reaction.

Then, methyl ethyl ketone was distilled off from the above reaction mixture to obtain a urethane resin composition (X9) having a nonvolatile content of 40% by mass.

[Example 10] Modification of urethane resin composition (X10)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, polycarbonate diol (manufactured by Nippon Polyurethane Industrial Co., Ltd.; Nipporan N980R; number average molecular weight: 2,000) 600 g, bisphenol A Addition of a compound having 10 moles of ethylene oxide (the compound of the formula (1) wherein R ¹ and R ² are a methyl group, and the sum of m and n is 10) 65 g, polyoxyethylene glycol monomethyl 75 g of a group (quantitative molecular weight: 4,000), 70 g of cyclohexanedimethanol, and 360 g of dicyclohexylmethane diisocyanate, and reacted at 70 ° C until NCO% reached 1.3% by mass, thereby obtaining an amine group having an isocyanate group at the terminal. A solution of the ester prepolymer (X10') in methyl ethyl ketone.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (X10') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 270 g of a 27 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (X10) having a nonvolatile content of 40% by mass.

[Example 11] Modulation of urethane resin composition (X11)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, polycarbonate diol (manufactured by Nippon Polyurethane Industrial Co., Ltd.; Nipporan N980R; number average molecular weight: 2,000) 600 g, bisphenol A Addition of a compound having 2 moles of ethylene oxide (the compound of the formula (1) wherein R ¹ and R ² are a methyl group, and the sum of m and n is 2) 65 g, polyoxyalkylene polyoxyl Monobutyl ether of a propyl random copolymer (mass ratio of oxygen-extended ethyl structure/oxypropyl propyl structure: 75/25; number average molecular weight: 3,400), 75 g, cyclohexane dimethanol 70 g, and dicyclohexylmethane 360 g of the diisocyanate was reacted at 70 ° C until the NGO % reached 1.3% by mass, whereby a methyl ethyl ketone solution of the urethane prepolymer (X11') having an isocyanate group at the end was obtained.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (X11') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 270 g of a 27 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (X11) having a nonvolatile content of 40% by mass.

[Comparative Example 1] Preparation of urethane resin composition (Y1)

In the presence of 1,170 g of methyl ethyl ketone and 0.1 g of stannous octoate, 665 g of polyoxyalkylene butyl diol (quantitative molecular weight: 2,000) and polyoxyethylene glycol monomethyl ether (number average molecular weight: 4,000) of 75 g were used. 70 g of cyclohexanedimethanol and 360 g of dicyclohexylmethane diisocyanate were reacted at 70 ° C until NCO% reached 1.8% by mass, whereby a urethane prepolymer (Y1') having an isocyanate group at the terminal was obtained. Methyl ethyl ketone solution.

1650 g of a methyl ethyl ketone solution of the above urethane prepolymer (Y1') was mixed with 1650 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 40 g of an aqueous chain extender solution of 40 g was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (Y1) having a nonvolatile content of 40% by mass.

[Comparative Example 2] Preparation of urethane resin composition (Y2)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, 675 g of polyoxyalkylene butyl diol (quantitative molecular weight 2,000) and bisphenol A were added to a compound having 2 mol of ethylene oxide ( In the formula (1), R ¹ and R ² are a methyl group, and the sum of m and n is a compound of 2) 65 g, cyclohexane dimethanol 70 g, and dicyclohexylmethane diisocyanate 360 g, so that the NCO% reaches 1.3 mass. The reaction was carried out at 70 ° C to obtain a methyl ethyl ketone solution of a urethane prepolymer (Y2') having an isocyanate group at the end.

2340 g of a methyl ethyl ketone solution of the urethane prepolymer (Y2') having an isocyanate group at the end and 2340 g of pure water were mixed, and although phase inversion emulsification was carried out, a stable emulsion could not be obtained, and the result could not be obtained. A urethane resin composition (Y2) was obtained.

[Comparative Example 3] Modulation of urethane resin composition (Y3)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, a polyoxybutylene butyl diol (quantitative molecular weight: 2,000) of 600 g and bisphenol A were added to a compound of 2 mol of ethylene oxide. 75 g of polyoxyethylene glycol monomethyl ether (number average molecular weight: 4,000), 70 g of cyclohexane dimethanol, and 360 g of dicyclohexylmethane diisocyanate, and reacted at 70 ° C until NCO% reached 1.3% by mass. A solution of a methyl ethyl ketone of a urethane prepolymer (Y3') having an isocyanate group at the end.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (Y3') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 270 g of a 27 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (Y3) having a nonvolatile content of 40% by mass.

[Comparative Example 4] Preparation of urethane resin composition (Y4)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, a polyoxybutylene butyl diol (quantitative molecular weight 2,000) of 600 g, comprising a polyoxyalkylene extended polypropylene propylene random copolymer Non-alcohol (mass ratio of oxygen-extended ethyl structure / oxygen-extended propyl structure: 75/25; number average molecular weight: 3,000) 65 g, polyoxyethylene glycol monomethyl ether (quantitative average molecular weight: 4,000), 75 g, cyclohexane 70 g of methanol and 360 g of dicyclohexylmethane diisocyanate were reacted at 70 ° C until NCO% reached 2.0% by mass, thereby obtaining a methyl ethyl group of a urethane prepolymer (Y4') having an isocyanate group at the end. Ketone solution.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (Y4') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 430 g of a chain-stretching agent aqueous solution of 43 g was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (Y4) having a nonvolatile content of 40% by mass.

[Comparative Example 5] Modulation of urethane resin composition (Y5)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, a compound of 635 g of polyoxybutylene butyl diol (quantitative molecular weight: 2,000) and bisphenol A were added to have 2 mol of ethylene oxide ( R ¹ and R ² in the formula (1) are a methyl group, and the sum of m and n is 2, 65 g, dimethylolpropionic acid 40 g, cyclohexane dimethanol 70 g, and dicyclohexylmethane diisocyanate 360 g, and reacted at 70 ° C until the NCO% reached 1.3% by mass, thereby obtaining a methyl ethyl ketone solution of a urethane prepolymer (Y5') having an isocyanate group at the molecular terminal.

In 2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (Y5'), 31 g of triethylamine was mixed, and further mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 60 g of a 6 g chain extender aqueous solution was mixed and subjected to chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (Y5) having a nonvolatile content of 30% by mass.

[Comparative Example 6] Preparation of urethane resin composition (Y6)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, a polyoxybutylene butyl diol (number average molecular weight: 2,000) of 600 g and bisphenol A were added to a compound having 2 mol of ethylene oxide ( a compound of the formula (1) wherein R ¹ and R ² are a methyl group, and the sum of m and n is 2) 65 g of a polyoxy-extension ethyl ethoxy-propyl random copolymer monobutyl ether (oxygen extension) The mass ratio of ethyl/oxypropyl group: 35/65; number average molecular weight 3,700) 75 g, cyclohexane dimethanol 70 g, and dicyclohexylmethane diisocyanate 360 g, and the reaction was carried out at 70 ° C until the NCO% reached 1.3% by mass. Thus, a methyl ethyl ketone solution of a urethane prepolymer (Y6') having an isocyanate group at the end was obtained.

2340 g of the methyl ethyl ketone solution of the above urethane prepolymer (Y6') and 2340 g of pure water were mixed, and although the phase inversion emulsification was carried out, the stable emulsion could not be obtained, and as a result, the urethane was not obtained. Ester resin composition (Y6).

[Comparative Example 7] Preparation of urethane resin composition (Y7)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, polycarbonate diol (manufactured by Nippon Polyurethane Industry Co., Ltd.; Nipporan N980R; number average molecular weight 2,000) 665 g, polyoxyethylene B 75 g of diol monomethyl ether (number average molecular weight: 4,000), 70 g of cyclohexane dimethanol, and 360 g of dicyclohexylmethane diisocyanate were reacted at 70 ° C until NCO% reached 1.8% by mass, whereby an isocyanate group was obtained at the terminal. A solution of the methyl urethane of the urethane prepolymer (Y7').

1650 g of a methyl ethyl ketone solution of the above urethane prepolymer (Y7') was mixed with 1650 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 40 g of an aqueous chain extender solution of 40 g was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (Y7) having a nonvolatile content of 40% by mass.

[Comparative Example 2] Preparation of urethane resin composition (Y8)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, a polycarbonate diol (manufactured by Nippon Polyurethane Co., Ltd.; Nipporan N980R; number average molecular weight: 2,000) 675 g, bisphenol A a compound having 2 moles of ethylene oxide (the compound of the formula (1) wherein R ¹ and R ² are a methyl group, and the sum of m and n is 2) 65 g, cyclohexane dimethanol 70 g, and 360 g of dicyclohexylmethane diisocyanate was reacted at 70 ° C until NCO% reached 1.3% by mass, whereby a methyl ethyl ketone solution of a urethane prepolymer (Y8') having an isocyanate group at the end was obtained.

Precursing a urethane having an isocyanate group at the above end 2340 g of the methyl ethyl ketone solution of the polymer (Y8') and 2340 g of pure water were mixed, and although the phase inversion emulsification was carried out, the stable emulsion was not obtained, and as a result, the urethane resin composition (Y8) could not be obtained.

[Comparative Example 3] Preparation of urethane resin composition (Y9)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, polycarbonate diol (manufactured by Nippon Polyurethane Industrial Co., Ltd.; Nipporan N980R; number average molecular weight: 2,000) 600 g, bisphenol A 65 g of a compound having 2 mol of propylene oxide, 75 g of polyoxyethylene glycol monomethyl ether (quantitative molecular weight 4,000), 70 g of cyclohexane dimethanol, and 360 g of dicyclohexylmethane diisocyanate were added to achieve NCO%. The reaction was carried out at 70 ° C at 1.3% by mass, whereby a methyl ethyl ketone solution of a urethane prepolymer (Y9') having an isocyanate group at the end was obtained.

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (Y9') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 270 g of a 27 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (Y9) having a nonvolatile content of 40% by mass.

[Comparative Example 10] Preparation of urethane resin composition (Y10)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, polycarbonate diol (manufactured by Nippon Polyurethane Co., Ltd.; Nipporan N980R; number average molecular weight: 2,000) 600 g, including poly Oxygen extended ethyl polyoxypropyl propylene random copolymer diol (oxygen extension ethyl structure / oxygen propylene structure mass ratio: 75 / 25; number average molecular weight 3,000) 65g, polyoxyethylene glycol single 75 g of methyl ether (number average molecular weight: 4,000), 70 g of cyclohexanedimethanol, and 360 g of dicyclohexylmethane diisocyanate were reacted at 70 ° C until NCO% reached 2.0% by mass, whereby an amino group having an isocyanate group at the terminal was obtained. A methyl ethyl ketone solution of the formate prepolymer (Y10').

2340 g of a methyl ethyl ketone solution of the above urethane prepolymer (Y10') was mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 430 g of a chain-stretching agent aqueous solution of 43 g was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (Y10) having a nonvolatile content of 40% by mass.

[Comparative Example 11] Preparation of urethane resin composition (Y11)

A compound of polycarbonate diol (Nipporan N980R; number average molecular weight: 2,000) 635 g and bisphenol A was added to have 2 moles of ethylene oxide in the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate. (In the formula (1), R ¹ and R ² are a methyl group, and the sum of m and n is a compound of 2) 65 g, dimethylolpropionic acid 40 g, cyclohexane dimethanol 70 g, and dicyclohexylmethane 360 g of the isocyanate was reacted at 70 ° C until the NCO% reached 1.3% by mass, whereby a methyl ethyl ketone solution of a urethane prepolymer (Y11') having an isocyanate group at the end was obtained.

Methyl ethyl group in the above urethane prepolymer (Y11') To 2340 g of the ketone solution, 31 g of triethylamine was mixed, and further mixed with 2340 g of pure water, and an emulsion was obtained by phase inversion emulsification.

Supplying the obtained emulsion in the obtained emulsion 60 g of a 6 g of an aqueous chain extender solution was mixed to cause chain elongation reaction, and methyl ethyl ketone was distilled off to obtain a urethane resin composition (Y11) having a nonvolatile content of 30% by mass.

[Comparative Example 12] Preparation of urethane resin composition (Y12)

In the presence of 1170 g of methyl ethyl ketone and 0.1 g of stannous octoate, polycarbonate diol (manufactured by Nippon Polyurethane Industrial Co., Ltd.; Nipporan N980R; number average molecular weight: 2,000) 600 g, bisphenol A Addition of a compound having 2 moles of ethylene oxide (the compound of the formula (1) wherein R ¹ and R ² are a methyl group, and the sum of m and n is 2) 65 g, polyoxyethylene oxide extension Monobutyl ether of propyl random copolymer (mass ratio of oxygen extended ethyl/oxypropyl propyl group: 35/65; number average molecular weight 3,700) 75 g, cyclohexane dimethanol 70 g, and dicyclohexylmethane diisocyanate 360 g The reaction was carried out at 70 ° C until the NCO% reached 1.3% by mass, whereby a methyl ethyl ketone solution of a urethane prepolymer (Y12') having an isocyanate group at the end was obtained.

2340 g of the methyl ethyl ketone solution of the above urethane prepolymer (Y12') and 2340 g of pure water were mixed, and although the phase inversion emulsification was carried out, the stable emulsion could not be obtained, and as a result, the urethane was not obtained. Ester resin composition (Y12).

Each of the urethane resin compositions obtained in the above Examples and Comparative Examples was 100 g, TEGO Flow 425 (manufactured by Degussa Co., Ltd.; 矽 leveling agent), 0.2 g, and TEGO Twin 4000 (manufactured by Degussa Co., Ltd.; Foaming agent) 0.2 g and BOCHIGEL ALA (manufactured by Borchers Co., Ltd.; alkali thickening tackifier) 1 g, mixed using a mechanical mixer at 2000 rpm for 2 minutes, followed by defoaming by using a vacuum defoaming machine, Each coating agent was prepared.

100 g of each of the above-mentioned coating agents was applied to a release paper (155T flat manufactured by Dainippon Printing Co., Ltd.) so that the film thickness after coating was 150 μm.

Immediately after the above application, the Werner Mathis dryer was used, pre-dried at 70 ° C for 2 minutes, and then dried at 150 ° C for 2 minutes to form a film.

[Method for evaluating tensile strength] <modulus evaluation>

The film was peeled off from the release paper, and cut into a test piece having a width of 5 mm, a length of 7 cm, and a thickness of 30 μm. The tensile strength of the above test piece was evaluated in accordance with JIS K-7311 by Tensilon (manufactured by Shimadzu Corporation; HEAD SPEED 300 mm/min).

<Extension evaluation>

The film was peeled off from the release paper, and cut into a test piece having a width of 5 mm, a length of 7 cm, and a thickness of 30 μm. The tensile strength of the above test piece was performed using Shimadzu Autograph "AG-1" (manufactured by Shimadzu Corporation; precision universal testing machine autostereoscopic measuring instrument) at a test speed of 300 mm/min, gauge length: 20 mm, and jig spacing: The condition of 40 mm was measured.

<Evaluation of flow start temperature>

The above-mentioned film was peeled off from the above-mentioned release paper, and cut into a size of 5 mm in width, 7 cm in length, and 30 μm in thickness was used as a test piece. The flow initiation temperature of the above test film was Shimadzu CFT-500D-1 (manufactured by Shimadzu Corporation; flow tester) to Dice; 1.0 mm. ×1.0 mm, load: 98 N; holding time: 10 minutes; temperature rising rate: 3 ° C / minute.

[Evaluation method of odor]

100 g of the coating agent containing the urethane resin composition prepared above was applied to a release paper (155T flat manufactured by Dainippon Printing Co., Ltd.) so that the film thickness after coating was 150 μm.

Immediately after the application, the Werner Mathis dryer was used, and when dried at 70 ° C for 2 minutes, it was judged whether or not the odor was detected from the position of the air vent of the dryer at a height of 50 cm.

The urethane resin compositions obtained in Examples 1 and 6 are excellent in water dispersibility, and have no odor due to the neutralizing agent, and can form a film having excellent tensile strength. In the urethane resin composition obtained in Example 2, it was confirmed that the flow initiation temperature was lowered by using excess polyoxyethylene glycol monomethyl ether, and the dispersion stability was excellent and the odor was not obtained. A film with good tensile strength. The urethane resin composition obtained in each of Examples 3 and 8 can also be formed into a film having excellent dispersion stability, no odor, and good tensile strength. The urethane resin compositions obtained in Examples 4 and 9 have an alkoxy polyoxyalkylene structure (a1) in the side chain of the urethane resin, and can be formed to have excellent dispersion stability and no A film with a good odor and good tensile strength.

The urethane resin compositions of Examples 5 and 10 obtained by adding bisphenol to 10 mol of ethylene oxide can also form a film having excellent dispersion stability, no odor, and good tensile strength. .

Single-polyoxyethylene extended propylene random copolymer The urethane resin compositions of Examples 6 and 11 obtained from butyl ether were also excellent in dispersion stability, and it was possible to form a film having a non-odor and having good tensile strength.

The urethane resins of Comparative Examples 1, 3, 4, 7, 9, and 10 having no structure represented by the general formula (1) caused a significant decrease in tensile strength. The urethane resin compositions of Comparative Examples 2 and 8 having no alkoxy polyoxyalkylene structure (a1) having a structure represented by the formula (1) cannot maintain good water dispersion stability and cause aggregation. .

The urethane resin compositions of Comparative Examples 5 and 11 having a carboxylate group formed by neutralizing a carboxyl group as a hydrophilic group have excellent water dispersion stability and can form a film having excellent tensile strength, but There is an odor caused by the neutralizing agent.

Further, the urethane resin compositions of Comparative Examples 6 and 12 having an alkoxy polyoxyalkylene group structure having a mass ratio of oxygen-extended ethyl group of 35% by mass cannot maintain good water dispersion stability. Causes cohesion.

Claims (7)

A urethane resin composition characterized by comprising a urethane resin (A) and an aqueous medium (B), and the urethane resin (A) has a content of 40% by mass to 100% The alkoxy polyoxyalkylene structure of the mass % oxygen-extended ethyl unit (a1) and the structure (a2) represented by the following general formula (1), and the alkoxy polyoxyalkylene structure described above ( A1) is present at the end of the above urethane resin (A) or the side chain of the above urethane resin (A), (In the formula (1), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group; m represents an average value of 0 to 20; n represents an average value of 0 to 20; and the sum of m and n represents an average of 1 to 40 value). The urethane resin composition of claim 1, wherein the urethane resin (A) is alkoxy polyoxyl relative to the urethane resin (A). The alkylene structure (a1) has a range of from 0.1% by mass to 25% by mass. The urethane resin composition of claim 1, wherein the urethane resin (A) is the same as the urethane resin (A), and the above formula (1) The configuration (a2) shown has a range of 0.1% by mass to 25% by mass. A coating agent comprising the urethane resin composition according to any one of claims 1 to 3. An article comprising a film formed using the urethane resin composition according to any one of claims 1 to 3. A leather-like sheet obtained by impregnating a fibrous base material with a urethane resin composition according to any one of claims 1 to 3. A leather-like sheet having at least a layer containing an impregnated base material and a skin obtained by impregnating a fibrous base material with a urethane resin composition according to any one of claims 1 to 3 Floor.