KR20100087132A

KR20100087132A - Aqueous polyurethane resin, coating film, and artificial and synthetic leather

Info

Publication number: KR20100087132A
Application number: KR1020107009225A
Authority: KR
Inventors: 고로 구와무라; 도시히코 나카가와; 사토시 야마사키
Original assignee: 미쓰이 가가쿠 가부시키가이샤
Priority date: 2007-11-16
Filing date: 2008-10-23
Publication date: 2010-08-03
Also published as: JPWO2009063729A1; TW200932776A; CN101821310B; CN101821310A; KR101503098B1; TWI441843B; JP5545954B2; WO2009063729A1

Abstract

The aqueous polyurethane resin is a polyisocyanate containing an isocyanate group of 1,4-bis (isocyanatomethyl) cyclohexane in a proportion of 50 mol% or more with respect to the total moles of isocyanate groups. , A high molecular weight polyol, and an isocyanate group terminal prepolymer obtained by reacting at least an active hydrogen compound containing a hydrophilic group with a chain extender.

Description

Aqueous Polyurethane Resin, Coating, Artificial & Synthetic Leather {AQUEOUS POLYURETHANE RESIN, COATING FILM, AND ARTIFICIAL AND SYNTHETIC LEATHER}

The present invention relates to an aqueous polyurethane resin, a coating film obtained from the aqueous polyurethane resin, and furthermore, to artificial and synthetic leather in which the aqueous polyurethane resin is used.

In recent years, aqueous resins have been widely used in terms of environmental conservation, resource saving, safety, and the like. Among them, aqueous polyurethane resins have been widely used in fields such as paints, adhesives, binders, and coating agents from the viewpoint of excellent durability, chemical resistance, and abrasion resistance. have.

By the way, when the aqueous polyurethane resin is to be coated at a high speed, aggregates may be generated without being able to withstand the shear force generated in the treatment. Therefore, there is a demand for an aqueous polyurethane resin having excellent dispersion stability that can be stably dispersed even under high shear force and can suppress generation of aggregates.

Moreover, in general, the coating film obtained from the aqueous polyurethane resin has a lower water resistance due to aqueous and less heat resistance and durability than the coating film obtained from the solvent-type polyurethane resin. Therefore, further improvement is desired.

With respect to the abovementioned requirements, for example, (A) (i) polyisocyanates, (ii) high molecular weight active hydrogen containing materials; And (iii) a prepolymer comprising a hydrophilic alkylene oxide polyol or polyamine; (B) water; And (C) optionally an aqueous polyurethane dispersion comprising a reaction product of a chain extender and / or a surfactant, an aqueous polyurethane dispersion having an amount of the reaction product in the dispersion of 40 to 60 mass% is proposed. (See Patent Document 1, for example), and as preferred polyisocyanates, 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane Or mixtures thereof are exemplified.

Japanese Patent Publication No. 2006-509863

By the way, even if it is the water-based polyurethane resin of the said patent document 1, the dispersion stability and heat resistance are still inadequate, and further improvement of these is calculated | required. Moreover, the coating film obtained from this aqueous polyurethane resin has the defect that a tack (tackiness) arises.

An object of the present invention is to provide an aqueous polyurethane resin which is excellent in dispersion stability, solvent resistance and heat resistance, and can realize an excellent texture, and a coating film obtained from the aqueous polyurethane resin, and furthermore, the aqueous polyurethane resin is used. It is to provide the artificial and synthetic leather which were made.

In order to achieve the above object, the aqueous polyurethane resin of the present invention is 50 mol% of isocyanate groups of 1,4-bis (isocyanatomethyl) cyclohexane with respect to the total moles of isocyanate groups. It is characterized by being obtained by reaction of the isocyanate group terminal prepolymer obtained by making the polyisocyanate, high molecular weight polyol, and hydrophilic group-containing active hydrogen compound which contain in the above ratio react at least.

Moreover, in the water-based polyurethane resin of this invention, it is suitable that the said chain extender contains the active hydrogen compound containing an alkoxysilyl group.

Moreover, it is suitable that the aqueous polyurethane resin of this invention contains 0.05-1.5 mass% of Si atoms.

Moreover, in the aqueous polyurethane resin of this invention, it is suitable that the said chain extender is a compound represented by following formula (1).

(Wherein R ¹ and R ² are the same or different and represent an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁴ are the same or different and represent an alkylene group having 1 to 4 carbon atoms. M is an integer of 1 to 3) Is displayed.)

In the aqueous polyurethane resin of the present invention, the 1,4-bis (isocyanatomethyl) cyclohexane contains 50% by mass or more of trans-1,4-bis (isocyanatomethyl) cyclohexane. It is appropriate.

Moreover, the coating film of this invention is obtained from the said water-based polyurethane resin, It is characterized by the above-mentioned.

Furthermore, the artificial and synthetic leathers of the present invention are characterized in that the above water-based polyurethane resin is used.

According to the water-based polyurethane resin of this invention, dispersion stability, solvent resistance, and heat resistance can be improved, and also the outstanding texture can be realized. Therefore, the coating film, artificial, and synthetic leather of this invention which utilized these characteristics can be provided.

The aqueous polyurethane resin of this invention is obtained by reaction of the isocyanate group terminal prepolymer and a chain extender.

The isocyanate group terminal prepolymer is obtained by at least reacting an active hydrogen compound containing a polyisocyanate, a high molecular weight polyol, and a hydrophilic group.

In the present invention, the polyisocyanate is at least 50 mol% of an isocyanate group of 1,4-bis (isocyanatomethyl) cyclohexane relative to the total moles of the isocyanate group. Is contained in a proportion of 70 mol% or more, more preferably 80 mol% or more, particularly preferably 90 mol%. Most preferably, 100 mol% is contained.

1,4-bis (isocyanatomethyl) cyclohexane includes cis-1,4-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as cis 1,4 body), trans-1, There is a stereoisomer of 4-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as trans 1,4 body), and in the present invention, 1,4-bis (isocyanatomethyl) cyclohexane is The trans 1,4 body is preferably 50 mass% or more, more preferably 70 mass%, particularly preferably 80 mass% or more. Most preferably, 90 mass% is contained.

The 1,4-bis (isocyanatomethyl) cyclohexane is, for example, the cold heat two-stage method (direct method) or the salting method described in JP-A-7-309827, or JP-A-2004-244349 It can manufacture by the method which does not use the phosgene as described in Unexamined-Japanese-Patent No. 2003-212835, etc., and the like.

Moreover, in the said polyisocyanate, it is a polyisocyanate which can be used together with 1, 4-bis (isocyanatomethyl) cyclohexane, For example, 1, 3- cyclopentane diisocyanate , 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate , 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3 -Bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatoethyl) cyclohexane, 1,4-bis (isocyanatoethyl) cyclohexane, 2,5- or Alicyclic dies such as 2,6-bis (isocyanatomethyl) norbornene and mixtures thereof Ah between isobutane it can be Nate. Also, for example, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2- Butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4- or 2,2,4-trimethyl hexamethylene dia And aliphatic diisocyanates such as isocyanate and 2,6-diisocyanate methyl caproate. Moreover, the isocyanurate, allophanate, biuret, oxadiazide trione, and uretdione modified body of these polyisocyanate can also be used together in the range which does not impair the film-forming property of an aqueous polyurethane resin.

Furthermore, monoisocyanate can also be used together in the range which does not impair the dispersion stability, solvent resistance, heat resistance, and a touch of an aqueous polyurethane resin. Examples of monoisocyanates include methyl isocyanate, ethyl isocyanate, n-hexyl isocyanate, cyclohexyl isocyanate, 2-ethylhexyl isocyanate, phenyl isocyanate, Benzyl isocyanate, and the like.

Polyisocyanate that can be used in combination with 1,4-bis (isocyanatomethyl) cyclohexane, preferably 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate Anate (alias isophorone diisocyanate (IPDI)), 4,4'-methylenebis (cyclohexyl isocyanate), 1,4-cyclohexane diisocyanate, 1,3- Bis (isocyanatomethyl) cyclohexane, 2,5- or 2,6-bis (isocyanatomethyl) norbornene and mixtures thereof, hexamethylene diisocyanate, and these polyiso And a modified product of cyanate.

Meanwhile, 1,3-bis (isocyanatomethyl) cyclohexane includes cis-1,3-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as cis1,3), and trans- There is a stereoisomer of 1,3-bis (isocyanatomethyl) cyclohexane (hereinafter referred to as trans 1,3 body), and 1,3-bis (isocyanatomethyl) cyclohexane is 1,3- When used together with 4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane is preferably at least 50% by mass, more than 1% by mass Preferably it is 70 mass%, Especially preferably, it contains 90 mass% or more.

In the present invention, the high molecular weight polyol is a compound having a number average molecular weight of 400 or more having two or more hydroxyl groups, and examples thereof include polyether polyols, polyester polyols, and polycarbonate polyols.

The number average molecular weight of the high molecular weight polyol is for example 400 to 5,000, preferably 1,400 to 3,000, more preferably 1,500 to 2,500, and the hydroxyl value thereof is 10 to 125 mgKOH / g, for example.

As a polyether polyol, polypropylene glycol, polytetramethylene ether glycol, etc. are mentioned, for example. As polypropylene glycol, Preferably, polyoxyalkylene polyol with a small amount of monool by-products which uses the phosphazeneium compound of Unexamined-Japanese-Patent No. 3905638 as a catalyst is mentioned.

Polypropylene glycols are mainly addition polymers of propylene oxide, for example with low molecular weight polyols or low molecular weight polyamines, and ethylene oxide is used in combination (i.e. random and / or block copolymers of propylene oxide and ethylene oxide). It includes).

On the other hand, low molecular weight polyols are compounds having a number average molecular weight of 60 to less than 400 having two or more hydroxyl groups, and are ethylene glycol, propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2 -Butylene glycol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, alkanes (C7-22) diols, diethylene glycol, triethylene glycol, di Propylene glycol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,4-cyclohexanediol, alkanes-1,2-diol (C17-20), hydrogenated bisphenol A, Dihydric alcohols such as 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, such as triglycerides such as glycerin and trimethylolpropane Alcohols such as tetramethylol methane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, D-mannnit and the like have four or more hydroxyl groups Approach may include alcohol.

Moreover, as a low molecular weight polyamine, aliphatic diamines, such as ethylenediamine, For example, aromatic diamines, such as tolylene diamine, etc. are mentioned.

As polytetramethylene ether glycol, the ring-opened polymer obtained by the cation polymerization of tetrahydrofuran, the amorphous polytetramethylene ether glycol etc. which copolymerized said dihydric alcohol to the polymerization unit of tetrahydrofuran etc. are mentioned, for example.

As a polyester polyol, the polycondensate obtained by making the said polyhydric alcohol and polybasic acid react on well-known conditions, for example is mentioned.

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethyl glutaric acid , Azelaic acid, sebacic acid, other aliphatic dicarboxylic acids (11 to 13 carbon atoms), suberic acid, undecane diacid, dodecane diacid, tridecane diacid, tetradecane diacid, pentade Kane diacid, octadecane diacid, nonadecane diacid, eicosane diacid, methylhexane diacid, citraconic acid, hydrogenated dimer acid, maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid And carboxylic acids such as toluene dicarboxylic acid, dimer acid, hetic acid and pimelic acid, and acid anhydrides derived from these carboxylic acids, acid halides, ricinoleic acid, and 12-hydroxystearic acid.

As the polyester polyol, for example, polycaprolactone polyols, polyvalerolactone polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone, using the above-mentioned dihydric alcohol as an initiator, Furthermore, the lactone polyol etc. which copolymerized the above-mentioned dihydric alcohol are mentioned.

Examples of the polycarbonate polyols include ring-opening polymers of ethylene carbonate having the above-mentioned dihydric alcohol as initiators, for example, 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol. And amorphous polycarbonate polyols obtained by copolymerizing dihydric alcohols such as 1,6-hexanediol and a ring-opening polymer.

These high molecular weight polyols can be used alone or in combination of two or more. Moreover, among these, polycarbonate polyol is mentioned preferably, More preferably, polycarbonate diol is mentioned, Especially preferably, an amorphous (normal temperature liquid) polycarbonate diol is mentioned. .

In the present invention, the active hydrogen compound containing a hydrophilic group is a compound having both a hydrophilic group and an active hydrogen group, and examples of the hydrophilic group include anionic groups, cationic groups and nonionic groups. As an active hydrogen group, a hydroxyl group, an amino group, a carboxyl group, an epoxy group etc. are mentioned as group which reacts with an isocyanate group. Specific examples of the active hydrogen compound containing a hydrophilic group include carboxylic acid group-containing active hydrogen compounds, sulfonic acid group-containing active hydrogen compounds, hydroxyl group-containing active hydrogen compounds, hydrophilic group-containing polybasic acids, and polyoxyethylene group-containing active hydrogen compounds.

Examples of the carboxylic acid group-containing active hydrogen compound include 2,2-dimethylol acetic acid, 2,2-dimethylolactic acid, 2,2-dimethylolpropionic acid (hereinafter abbreviated as DMPA), 2,2-dimethyl Dihydroxycarboxylic acids such as olebutane acid (hereinafter abbreviated as DMBA), 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid, such as diaminocarboxylic acids such as lysine and arginine, or their Metal salts, ammonium salts, etc. are mentioned. Preferably, 2, 2- dimethylol propionic acid (DMPA) and 2, 2- dimethylol butyrate (DMBA) are mentioned.

Examples of the sulfonic acid group-containing active hydrogen compound include dihydroxybutanesulfonic acid and dihydroxypropanesulfonic acid obtained by, for example, the synthesis reaction of an epoxy group-containing compound and an acid sulfite. Further, for example, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, N, N-bis (2-hydroxyethyl) -2-aminobutanesulfonic acid, 1,3-phenylene Diamine-4,6-disulfonic acid, diaminobutanesulfonic acid, diaminopropanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,4-diamino-5-toluenesulfonic acid , N- (2-aminoethyl) -2-aminoethanesulfonic acid, 2-aminoethanesulfonic acid, N- (2-aminoethyl) -2-aminobutanesulfonic acid, or metal or ammonium salts of these sulfonic acids And the like.

As a hydroxyl-containing active hydrogen compound, N- (2-aminoethyl) ethanolamine is mentioned, for example.

Examples of the hydrophilic group-containing polybasic acid include, for example, a polybasic acid containing sulfonic acid, more specifically 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (p-sulfophenoxy) isophthalic acid, and 5- (sulfopropoxy Isophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, sulfopropylmalonic acid, sulfosuccinic acid, 2-sulfobenzoic acid, 2,3-sulfobenzoic acid, 5-sulfosalicylic acid, and alkyl esters of these carboxylic acids, further Examples thereof include metal salts and ammonium salts of these sulfonic acids. Preferably, the sodium salt of 5-sulfoisophthalic acid and the sodium salt of 5-sulfoisophthalic acid dimethyl are mentioned.

A polyoxyethylene group containing active hydrogen compound is a compound which contains a polyoxyethylene group in a principal chain or a side chain, and has two or more active hydrogen groups.

Examples of the polyoxyethylene group-containing compound include polyethylene glycol (for example, number average molecular weights 200 to 6,000, preferably 300 to 3,000), and polyoxyethylene side chain-containing polyols.

A polyoxyethylene side chain containing polyol is a compound which contains a polyoxyethylene group in a side chain, has 2 or more active hydrogen groups, and can be synthesize | combined as follows.

Namely, first, the above-mentioned diisocyanate and single-ended blocked polyoxyethylene glycol (eg, alkoxyethylene glycol single-ended sealed with an alkyl group having 1 to 4 carbon atoms, number average molecular weight 200 to 6,000, preferably Preferably, 300 to 3,000) is urethane-reacted in the ratio which the isocyanate group of diisocyanate becomes excessive with respect to the hydroxyl group of single-ended blocked polyoxyethylene glycol, and unreacted diisocyanate as needed. By removing the polyoxyethylene chain-containing monoisocyanate is obtained.

Subsequently, polyoxyethylene chain-containing monoisocyanate and dialkananamine (such as diethanolamine, etc.) are used as isocyanates of polyoxyethylene group-containing monoisocyanate with respect to the secondary amino group of dialkanolamine. The urea reaction is carried out at a ratio at which the groups are almost equivalent.

As diisocyanate for obtaining a polyoxyethylene side chain containing polyol, Preferably, aliphatic diisocyanate, such as hexamethylene diisocyanate (HDI), 1, 3- or 1, 4-bis (iso) Cyanatomethyl) cyclohexane (H ₆ XDI) or mixtures thereof, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (aka: isophorone diisocyanate ( IPDI)), 4,4'-methylenebis (cyclohexyl isocyanate) (H ₁₂ MDI), 2,5- or 2,6-bis (isocyanatomethyl) norbornene (NBDI) or their Alicyclic diisocyanate, such as a mixture, is mentioned. More preferably, HDI can be mentioned.

On the other hand, when a polyoxyethylene group containing compound is mix | blended, the content of the polyoxyethylene group in the water-based polyurethane resin (solid content) is 0.9-30 mass%, Preferably it is 2-20 mass%, More preferably, It is 2-10 mass%.

The active hydrogen compound containing these hydrophilic groups can be used alone or in combination of two or more. Moreover, among these, Preferably a carboxylic acid group containing active hydrogen compound and a polyoxyethylene group containing active hydrogen compound are mentioned.

And in order to obtain an isocyanate group terminal prepolymer, the active hydrogen compound containing polyisocyanate, a high molecular weight polyol, and a hydrophilic group is made to react by well-known polymerization methods, such as bulk polymerization and solution polymerization.

On the other hand, when an active hydrogen compound containing a hydrophilic group is contained in a high molecular weight polyol, the high molecular weight polyol and polyisocyanate can be reacted to obtain an isocyanate group terminal prepolymer.

For example, in the synthesis of the aforementioned polyester polyol, the high molecular weight polyol can contain an active hydrogen compound containing a hydrophilic group by blending the active hydrogen compound containing the hydrophilic group as a polyhydric alcohol.

In addition, for example, in the synthesis of the polyester polyol, the high molecular weight polyol may contain an active hydrogen compound containing a hydrophilic group by blending a hydrophilic group-containing polybasic acid as the polybasic acid.

Further, in the synthesis of, for example, polyester polyols, polyether polyols, polycarbonate polyols, and epoxy polyols obtained by ring-opening polymerization, a high molecular weight polyol is formulated by blending an active hydrogen compound containing a hydrophilic group as an initiator or copolymerization component. It is also possible to contain an active hydrogen compound containing a hydrophilic group.

Furthermore, by reacting an active hydrogen compound containing a hydrophilic group with a high molecular weight polyol such as polyether polyol (preferably polytetramethylene ether glycol), an active hydrogen compound containing a hydrophilic group is added to the high molecular weight polyol. It can also be contained.

And each said component contains the active hydrogen group (hydroxyl group, amino group etc.) of the active hydrogen compound containing a high molecular weight polyol and a hydrophilic group (when mix | blending the low molecular weight polyol mentioned later, it contains the hydroxyl group of the low molecular weight polyol) The equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group of the polyisocyanate to is, for example, from 1.1 to 2.5, preferably from 1.2 to 2.3, more preferably from 1.2 to 2. Prescribe (mix) to be. When the equivalent ratio of the isocyanate group is in this range, the dispersion stability of the aqueous polyurethane resin can be improved. Therefore, the coating film, artificial leather, and synthetic leather which are excellent in a texture can be obtained using this aqueous polyurethane resin.

In bulk polymerization, for example, stirring the polyisocyanate under a stream of nitrogen, an active hydrogen compound containing a high molecular weight polyol and a hydrophilic group is added thereto, and the reaction temperature is from 3 to 15 at 50 to 130 ° C, more preferably at 50 to 80 ° C. Let it react for about an hour.

In solution polymerization, an active hydrogen compound containing a polyisocyanate, a high molecular weight polyol, and a hydrophilic group is added to an organic solvent and reacted for about 3 to 15 hours at a reaction temperature of 50 to 120 ° C, more preferably 50 to 80 ° C. .

As the organic solvent, ketones such as acetone and methyl ethyl ketone, such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and methyl cellosolve acetate which are inert to isocyanate groups and are rich in hydrophilicity and are easy to remove , Cellosolve acetates such as ethyl cellosolve acetate, for example, carbitol acetates such as methyl carbitol acetate, ethyl carbitol acetate, nitriles such as acetonitrile, esters such as ethyl acetate, butyl acetate, and the like. Can be.

In addition, in the said polymerization reaction, you may mix | blend said low molecular weight polyol suitably according to the objective and use.

Furthermore, in the said polymerization reaction, you may add well-known urethanization catalysts, such as an amine type, tin type, lead type, bismuth type, etc. as needed, and are free from the obtained isocyanate group terminal prepolymer (unreacted). The polyisocyanate may be removed by a known removal means such as distillation or extraction.

And in the obtained isocyanate group terminal prepolymer, when anionic group or cationic group is contained as a hydrophilic group, neutralizing agent is added preferably, and the salt of anionic group or cationic group is formed.

For example, when an anionic group is contained, a neutralizing agent is a conventional base such as an organic base [eg, tri C1-4 alkylamines such as tertiary amines (trimethylamine, triethylamine, dimethylethanolamine, methyl). Alkanolamines such as diethanolamine, triethanolamine, triisopropanolamine, heterocyclic amines such as morpholine)], inorganic bases [ammonia, alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali Earth metal hydroxides (magnesium hydroxide, calcium hydroxide, etc.), alkali metal carbonates (sodium carbonate, potassium carbonate, etc.)]. These bases can be used alone or in combination of two or more.

The neutralizing agent is added at a ratio of 0.4 to 1.2 equivalents, preferably 0.6 to 1 equivalent, per equivalent of anionic group.

The isocyanate group terminal prepolymer thus obtained is a polyurethane prepolymer having two or more free isocyanate groups at its molecular ends, and the content (isocyanate group content) of the isocyanate group is, for example, 0.3 to 10 mass%, Preferably it is 0.5-6 mass%, More preferably, it is 1.0-5.0 mass%. In addition, the average number of functional groups of the isocyanate group is, for example, 1.5 to 3.0, preferably 1.9 to 2.5. The number average molecular weight (number average molecular weight by GPC measurement using standard polystyrene as a calibration curve) is, for example, 1,000 to 30,000, preferably 1,500 to 20,000. Further, the hydrophilic group concentration of the isocyanate group terminal prepolymer is, for example, 0.1 to 1.0 mmol / g, preferably 0.2 to 0.7 mmol / g, more preferably 0.2 to 0.6 mmol / g.

In order to obtain the aqueous polyurethane resin of this invention, the isocyanate group terminal prepolymer obtained above is made to react with a chain extender.

In the present invention, examples of the chain extender include low molecular weight polyols, polyamines, amino alcohols, and the like.

As a low molecular weight polyol, the low molecular weight polyol mentioned above is mentioned, for example.

Examples of the polyamine include aromatic polyamines such as 4,4'-diphenylmethanediamine, for example, aliphatic polyamines such as 1,3- or 1,4-xylylenediamine or mixtures thereof, such as 3-aminomethyl-3 , 5,5-trimethylcyclohexylamine (common name: isophoronediamine), 4,4'-dicyclohexyl methanediamine, 2,5 (2,6) -bis (aminomethyl) bicyclo [2.2 .1] alicyclic polyamines such as heptane, 1,3- or 1,4-bis (aminomethyl) cyclohexane or mixtures thereof, 1,3- or 1,4-cyclohexanediamine or mixtures thereof; Ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, hydrazine (including hydrates), diethylenetriamine, triethylenetetraamine, Aliphatic polyamines, such as tetraethylene pentaamine, etc. are mentioned.

Moreover, as amino alcohol, N- (2-aminoethyl) ethanolamine etc. are mentioned, for example.

Moreover, as a chain extender, the active hydrogen compound containing an alkoxy silyl group is mentioned, for example. The active hydrogen compound containing an alkoxysilyl group is a compound which uses an alkoxy silyl group and an active hydrogen group together.

In the alkoxysilyl group, examples of the alkoxy group bonded to the Si atom include alkoxy groups having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group and isobutoxy group. Preferably, a methoxy group and an ethoxy group are mentioned. Further, the number of bonds to the Si atom of the alkoxy group is usually 1 to 3, preferably 1 to 2 pieces.

As an active hydrogen group, as an active hydrogen group which reacts with an isocyanate group, an amino group, a hydroxyl group, etc. are mentioned, for example, Amino group is mentioned preferably.

The active hydrogen compound containing such an alkoxysilyl group is represented by following General formula (1), for example.

[Formula 1]

In said Formula (1), as R <^1> and R <^2> , C1-C4 alkyl groups, such as a methyl group, an ethyl group, a propyl group, a butyl group, are mentioned, for example. Moreover, as R <^3> and R <^4> , C1-C4 alkylene groups, such as a methylene group, ethylene group, a propylene group, butylene group, are mentioned, for example.

As an active hydrogen compound containing an alkoxysilyl group, More specifically, N- (beta)-(aminoethyl)-(gamma) -aminopropylmethyl dimethoxysilane, N- (beta)-(aminoethyl)-(gamma) -aminopropyl tri Methoxysilane, γ- (2-aminoethyl) aminopropyl triethoxysilane, γ- (2-aminoethyl) aminopropyl dimethoxysilane, γ- (2-aminoethyl) aminopropyl diethoxy Silane, γ-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl dimethoxysilane, γ-aminopropyl diethoxysilane, N, N'-bis [ (gamma)-(trimethoxysilyl) propyl] ethylenediamine, etc. are mentioned. Preferably, N- (beta)-(aminoethyl)-(gamma) -aminopropylmethyl dimethoxysilane is mentioned.

The concentration of the active hydrogen group contained in the chain extender is preferably 250 to 800 mgKOH / g, more preferably 350 to 600 mgKOH / g. When the concentration of the active hydrogen group is in this range, an aqueous polyurethane resin excellent in durability can be obtained.

These chain extenders can be used alone or in combination of two or more. Moreover, among these, Preferably together, the use of the active hydrogen compound containing a polyamine and the alkoxy silyl group is mentioned.

And in order to obtain the aqueous polyurethane resin of this invention, the isocyanate group terminal prepolymer obtained above is made to react and disperse | distribute in chain extension agent in water. Thereby, the aqueous polyurethane resin in which the isocyanate group terminal prepolymer is extended by the chain extender can be obtained as an aqueous dispersion (dispersion).

In order to react the isocyanate group terminal prepolymer and the chain extender in water, for example, first, an isocyanate group terminal prepolymer is added to water to disperse the isocyanate group terminal prepolymer. Subsequently, a chain extender is added thereto to chain extend the isocyanate group terminal prepolymer.

In order to disperse the isocyanate group terminal prepolymer, the isocyanate group terminal prepolymer is slowly added to water under stirring. Water is added with respect to 100 mass parts of isocyanate group terminal prepolymers, Preferably it is a ratio of 60-1,000 mass parts.

And an equivalent ratio of the active hydrogen groups (such as hydroxyl groups and amino groups) of the chain extender to the isocyanate group of the isocyanate group terminal prepolymer, under stirring, with a chain extender in the isocyanate group terminal prepolymer dispersed in water ( Active hydrogen group / isocyanate group) is added at a ratio of, for example, 0.5 to 1.1, preferably 0.7 to 1.

When a diamine (including a diamine containing an alkoxysilyl group) is used as the chain extender, the amino group has high reactivity with the isocyanate group of the isocyanate group terminal prepolymer and is produced by the reaction. Since the resulting urea bonds have a very high intermolecular cohesion, it is necessary to reduce the local reaction of the chain extender and the isocyanate monomer. Therefore, the chain extender is preferably blended as an aqueous solution or a solution. At least 20 mass% is preferable, and, as for the density | concentration of the diamine in aqueous solution or a solution, More preferably, it is at least 50 mass%. In addition, the chain extender is preferably added at a temperature of 40 ° C. or lower, and after completion of the addition, the reaction is completed while stirring further, for example, at room temperature.

On the other hand, when the isocyanate group terminal prepolymer is obtained by solution polymerization, after completion | finish of reaction of an isocyanate group terminal prepolymer, an organic solvent is removed by heating at appropriate temperature, for example under reduced pressure.

The aqueous dispersion of the aqueous polyurethane resin thus obtained is prepared such that its solid content is, for example, 10 to 70 mass%, preferably 20 to 50 mass%.

The aqueous polyurethane resin has a number average molecular weight (number average molecular weight obtained by GPC measurement using standard polystyrene as a calibration curve), for example, from 3,000 to 100,000, preferably from 5,000 to 80,000. The aqueous polyurethane resin (solid content) preferably has a loading ratio of the urethane group to the urea group, for example, 0.05 to 1.2, more preferably 0.1 to 0.8.

Moreover, when an active hydrogen compound containing an alkoxysilyl group is used as a chain extender, this aqueous polyurethane resin has content of the Si atom, for example, 0.05-1.5 mass%, Preferably it is 0.05-1.2 mass%, More Preferably it is 0.07-0.8 mass%. If the content of Si atoms is in the above range, the polyisocyanate contains an isocyanate group of 1,4-bis (isocyanatomethyl) cyclohexane in a proportion of 50 mol% or more with respect to the total number of moles of isocyanate groups. There exist advantages, such as the improvement of the mechanical stability of the water-based polyurethane resin which consists of cyanates, and the coating film which the solvent resistance and softening temperature rose.

As a method of measuring content of Si atom, the water contained in an aqueous polyurethane resin is distilled off, for example, after producing the film in which the aqueous polyurethane resin is used, the method of measuring solid-state high-resolution NMR of a film, organic of a film After the component is completely decomposed by the wet ashing method (described later in [Examples]), a method of measuring by atomic absorption method, ICP emission method, fluorescence X-ray method or the like can be mentioned. Among these, ICP emission spectrometry is mentioned preferably.

In addition, the aqueous polyurethane resin has a mechanical stability of, for example, 200 μg / g or less, preferably 180 μg / g or less, and more preferably 160 μg / g or less by a Maron test (to be described later in [Examples] below).

And when forming the aqueous polyurethane resin of this invention, the coating film excellent in dispersion stability, solvent resistance, and heat resistance, and also a touch can be obtained. Therefore, the aqueous polyurethane resin of this invention can be used suitably for artificial leather, synthetic leather, etc. which utilized the said characteristic.

On the other hand, film-forming is apply | coated an aqueous polyurethane resin to a base material by well-known coating methods, such as the gravure coating method, the reverse coating method, the roll coating method, the bar coating method, the spray coating method, the air knife coating method, the dipping method, Then, it heats and dries.

When using the aqueous polyurethane resin of this invention for manufacture of artificial leather and synthetic leather, it can use as a raw material of a wet method and a dry method, for example.

On the other hand, the aqueous polyurethane resin of the present invention is not limited to the artificial leather and synthetic leather as described above, for example, various uses such as automobiles, electronic devices, clothing materials, medical care, building materials, paints, adhesives, etc. Can also be used.

[Examples]

Next, although this invention is demonstrated based on a manufacture example, a synthesis example, an Example, and a comparative example, this invention is not limited by the following Example. In addition, in the following description, "part" and "%" are mass references | standards unless there is particular notice. In addition, the measuring method used for a synthesis example, etc. is shown below.

(Hydrophilic group concentration / unit of isocyanate group terminal prepolymer: mmol / g)

The hydrophilic group concentration of the isocyanate group terminal prepolymer was determined by neutralization titration using a potentiometric titration device (manufactured by Hiranuma Industries, Inc., Model: COM-980).

More specifically, about 1.5 g of the prepolymer solution before adding TEA was weighed out and dissolved in a 40 ml toluene / ethanol mixed solvent (volume ratio of toluene / ethanol was 2/1) prepared in advance. Subsequently, potentiometric titration using 0.1 mol / L of ethanol potassium hydroxide (a titration reagent having a titer) was performed to measure the hydrophilic group concentration.

On the other hand, in the hydrophilic group concentration, the hydrophilic group corresponds to the carboxyl group in the isocyanate group terminal prepolymer.

On the other hand, since the sample measured was the acetonitrile solution of the prepolymer, it was corrected by the mass of the prepolymer based on the amount of the solvent added, and the hydrophilic group concentration of the prepolymer was calculated from the measured value.

(Oxyethylene Group Concentration / Unit: Mass% of Isocyanate Group Terminal Prepolymer)

To 0.5 g of isocyanate terminal prepolymer, a certain amount of tetrachloroethane dissolved in deuterated chloroform as an internal standard was added, and deuterated chloroform was further added to make the total volume 5mL. The oxyethylene group concentration was calculated | required by ¹ H-NMR (made by JEOL, JNM-AL400) measurement of this solution.

(Isocyanate group content / unit: mass% contained in the isocyanate group terminal prepolymer solution)

The isocyanate group content of the isocyanate group terminal prepolymer solution was measured by the n-dibutylamine method based on JISK-1556 using the potentiometric titration apparatus.

Preparation Example 1 (Method for producing 1,4-bis (isocyanatomethyl) cyclohexane)

^A cold-heated two-stage phosgenation method was carried out at atmospheric pressure using 1,4-bis (aminomethyl) cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.) having a trans / cis ratio of 93/7 by ¹³ C-NMR measurement as a raw material.

That is, a stirring rod, a thermometer, a phosgene inlet tube, a dropping funnel and a cooling tube were attached to the flask, and 400 parts by mass of orthodichlorobenzene was added to the flask. While cooling the flask with cold water, the temperature in the flask was 10 ° C or lower, and 280 parts by mass of phosgene was introduced from the phosgene introduction tube. Into the dropping funnel, a mixture of 100 parts by mass of 1,4-bis (aminomethyl) cyclohexane and 500 parts by mass of orthodichlorobenzene were added, and the mixture was added to the flask over 30 minutes. In the meantime, the temperature in the flask was kept at 30 degrees C or less. After the addition was completed, the flask became a white slurry liquid. The reaction temperature was raised to 150 ° C while introducing phosgene again, and the reaction was continued at 150 ° C for 5 hours. The reaction liquid in the flask became a pale brown clear liquid.

After completion | finish of reaction, the nitrogen gas was vented at 10 L / h at 100-150 degreeC, and degassed.

Orthodichlorobenzene which is a solvent was distilled off under reduced pressure, and the oil content of boiling point 138-140 degreeC / 0.7 kPa was further collected by distillation under reduced pressure.

This obtained 123 mass parts (yield 90%) of 1, 4-bis (isocyanatomethyl) cyclohexane as a colorless transparent liquid.

1,4-bis (iso between annatto methyl), purity according to gas chromatography measurement of the cyclohexane thus obtained trans / cis ratio of the color due to 99.9%, APHA measurement is 5, ¹³ C-NMR measurement is 93 / It was seven.

Preparation Example 2 (Synthesis of Polyoxyethylene Side Chain Containing Diol)

In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, 1,000 parts by mass of methoxy polyethylene glycol having a number average molecular weight of 1,000 (manufactured by Toho Chemical Co., Ltd.) and 1,6-hexamethylene diisocyanate ( Product name: Takean 700, Mitsui Chemical Polyurethane Co., Ltd.) 1,682 parts by mass was added, and the mixture was reacted at 90 ° C. for 9 hours under a nitrogen atmosphere. The obtained reaction liquid was thin-film distilled, the unreacted 1, 6- hexamethylene diisocyanate was removed, and the polyoxyethylene group containing monoisocyanate was obtained. Subsequently, 82.5 parts by mass of diethanolamine was added to a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, and 917.5 parts by mass of the polyoxyethylene group-containing monoisocyanate was cooled with air under a nitrogen atmosphere. It was dripped slowly so that it might not exceed 70 degreeC. After completion of the dropwise addition, the mixture was stirred at 70 ° C. under a nitrogen atmosphere for about 1 hour to confirm that the isocyanate group was lost, thereby obtaining a polyoxyethylene side chain-containing diol.

The oxyethylene group concentration in the polyoxyethylene side chain containing diol was 76 mass% as a result of actual measurement by ¹ H-NMR.

Synthesis Example 1 (Synthesis of Hydrophilic Group-Containing Prepolymer Solution (A))

In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 1,4-bis (isocyanatomethyl) cyclohexane (hereinafter, abbreviated as 1,4-BIC) in Production Example 1 was used. 780 parts by mass of 3,000 parts by mass of an amorphous polycarbonate diol (trade name: T-5652, manufactured by Asahi Kasei Chemicals Co., Ltd.) having a number average molecular weight of 2,000, which was heated to 110 ° C. in advance and dried under reduced pressure to an acetonitrile (hereinafter referred to as AN). 220 parts by mass of dimethylolpropionic acid (hereinafter, abbreviated as DMPA) was dried by heating in the same manner as 1,000 parts by mass and amorphous polycarbonate diol, and then reacted at 75 ° C. under nitrogen atmosphere for 8 hours. . This obtained the solution of the isoisocyanate group terminal prepolymer (henceforth abbreviated as prepolymer) whose isocyanate group content is 1.40 mass%.

Subsequently, this reaction liquid was cooled to 20 degreeC, and 158 mass parts of triethylamine (it abbreviates as TEA hereafter) were added. That is, TEA was added so that it was 0.95 equivalent with respect to the hydrophilic group (carboxyl group) in an isocyanate group terminal prepolymer.

Thereafter, by stirring and mixing at the same temperature for 30 minutes, a hydrophilic group-containing isocyanate group terminal prepolymer (hereinafter, abbreviated to hydrophilic group-containing prepolymer) in which carboxylic acid was neutralized by TEA was obtained. Table 1 shows the details and properties of the synthesis conditions of the obtained hydrophilic group-containing prepolymer solution (A).

In addition, in Table 1, the "equivalent ratio of isocyanate group" has shown the equivalence ratio of the isocyanate group of polyisocyanate with respect to the hydroxyl group of the active hydrogen compound containing a high molecular weight polyol and a hydrophilic group.

Synthesis Example 2 (Synthesis of Hydrophilic Group-Containing Prepolymer Solution (B))

The isocyanate group content was 2.65% by mass in the same manner as in Synthesis Example 1, except that 950 parts by mass of 1,4-BIC, 1,045 parts by mass of AN, 230 parts by mass of DMPA, and 165 parts by mass of TEA were used. A hydrophilic group-containing prepolymer solution (B) was obtained. Table 1 shows the details and properties of the synthesis conditions of the obtained hydrophilic group-containing prepolymer solution (B).

Synthesis Example 3 (Synthesis of Hydrophilic Group-Containing Prepolymer Solution (C))

The isocyanate group content was 4.23 mass% by operation similar to the synthesis example 1 except having used 1,200 mass parts of 1, 4-BIC, 1,111 mass parts of AN, 244 mass parts of DMPA, and 175 mass parts of TEA. A hydrophilic group-containing prepolymer solution (C) was obtained. Table 1 shows the details and properties of the synthesis conditions of the obtained hydrophilic group-containing prepolymer solution (C).

Synthesis Example 4 (Synthesis of Hydrophilic Group-Containing Prepolymer Solution (D))

The isocyanate group content was 5.96 mass% by the same operation as Synthesis Example 1, except 1,500 parts by mass of 1,4-BIC, 1,190 parts by mass of AN, 260 parts by mass of DMPA, and 186 parts by mass of TEA. A hydrophilic group-containing prepolymer solution (D) was obtained. Table 1 shows the details and properties of the synthesis conditions of the obtained hydrophilic group-containing prepolymer solution (D).

Synthesis Example 5 (Synthesis of Hydrophilic Group-Containing Prepolymer Solution (E))

950 parts by mass of 1,3-bis (isocyanatomethyl) cyclohexane (trade name: Takenate T-600, manufactured by Mitsui Chemical Polyurethane Co., Ltd.) (hereinafter abbreviated as 1,3-BIC) and AN of 1,045 A hydrophilic group-containing prepolymer solution (E) having an isocyanate group content of 2.62% by mass was obtained by the same operation as in Synthesis Example 1, except that 230 parts by mass and 165 parts by mass of TEPA were used. Table 1 shows the details and properties of the synthesis conditions of the obtained hydrophilic group-containing prepolymer solution (E).

Synthesis Example 6 (Synthesis of Hydrophilic Group-Containing Prepolymer Solution (F))

By the same operation as in Synthesis Example 1, except that 428 parts by mass of 1,3-BIC and 523 parts by mass of 1,4-BIC, 1,045 parts by mass of AN, 230 parts by mass of DMPA, and 165 parts by mass of TEA were used. A hydrophilic group-containing prepolymer solution (F) having a cyanate group content of 2.69 mass% was obtained. Table 1 shows the details and properties of the synthesis conditions of the obtained hydrophilic group-containing prepolymer solution (F).

Synthesis Example 7 (Synthesis of Hydrophilic Group-Containing Prepolymer Solution (G))

Same as Synthesis Example 1 except that 1,160 parts by mass of isophorone diisocyanate (IPDI, trade name: VESTANAT IPDI, manufactured by Degussa), 1,105 parts by mass of AN, 260 parts by mass of DMPA, and 186 parts by mass of TEA were used. By operation, the hydrophilic group-containing prepolymer solution (G) having an isocyanate group content of 2.68% by mass was obtained. Table 1 shows the details and properties of the synthesis conditions of the obtained hydrophilic group-containing prepolymer solution (G).

Synthesis Example 8 (Synthesis of Hydrophilic Group-Containing Prepolymer Solution (H))

1,370 parts by mass of 4,4'-methylenebis (cyclohexyl isocyanate) (trade name: VESTANAT H ₁₂ MDI, manufactured by Degussa) (hereinafter abbreviated to H ₁₂ MDI), AN of 1,158 parts by mass, and DMPA A hydrophilic group-containing prepolymer solution (H) having an isocyanate group content of 2.54 mass% was obtained by the same operation as in Synthesis Example 1 except that 260 parts by mass and 186 parts by mass of TEA were used. Table 1 shows the details and properties of the synthesis conditions of the obtained hydrophilic group-containing prepolymer solution (H).

Synthesis Example 9 (Synthesis of Hydrophilic Group-Containing Prepolymer Solution (I))

In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 129 parts by mass of 4,4'-methylenebis (cyclohexyl isocyanate) (H ₁₂ MDI) and an amorphous polycarbonate diol ( Product name: T-5652) 3,000 parts by mass, AN, 1,054 parts by mass, DMPA 232 parts by mass, after reacting for 3 hours at 75 ℃ in a nitrogen atmosphere, 856 parts by mass of 1,4-BIC was added, The reaction was carried out at the furnace temperature for 6 hours. This obtained the prepolymer solution whose isocyanate group content is 2.65 mass%.

Subsequently, this reaction liquid was cooled to 20 degreeC and 166 mass parts of TEA was added. That is, TEA was added so that it was 0.95 equivalent with respect to the hydrophilic group (carboxyl group) in an isocyanate group terminal prepolymer. Thereafter, the mixture was stirred and mixed at the same temperature for 30 minutes to obtain a hydrophilic group-containing prepolymer solution (I) in which carboxylic acid was neutralized by TEA. Table 1 shows the synthesis conditions and properties of the obtained hydrophilic group-containing prepolymer solution (I).

Synthesis Example 10 (Synthesis of Prepolymer Solution (J))

In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen inlet tube, 447 parts by mass of 1,4-BIC was heated to 110 ° C in advance, and then dried under reduced pressure to obtain an amorphous polycarbonate diol having a molecular weight of 2,000 (product name: T-5652, manufactured by Asahi Kasei Chemicals Co., Ltd.), 389 parts of polyoxyethylene side chain-containing diol dried under reduced pressure by heating in the same manner as 3,000 parts by mass, 1,452 parts by mass of AN, 1,815 parts by mass of acetone, and amorphous polycarbonate diol. Charged by mass and reacted at 75 ° C. for 7 hours under a nitrogen atmosphere. This obtained the prepolymer solution (J) whose isocyanate group content is 0.57 mass%. Table 1 shows the details and properties of the synthesis conditions of the obtained prepolymer solution (J).

Synthesis Example 11 (Synthesis of Prepolymer Solution (K))

An isocyanate group was produced by the same operation as in Synthesis Example 10, except that 496 parts by mass of 1,4-BIC was used, 1,473 parts by mass of AN, 1,841 parts by mass of acetone, and 394 parts by mass of polyoxyethylene side chain-containing diol. A prepolymer solution (K) having a content of 0.81 mass% was obtained. Table 1 shows the details and properties of the synthesis conditions of the obtained prepolymer solution (K).

Synthesis Example 12 (Synthesis of Prepolymer Solution (L))

Isocyanate group by the same operation as Synthesis Example 10 except having used 799 parts by mass of 1,4-BIC, 1,600 parts by mass of AN, 2,001 parts by mass of acetone, and 428 parts by mass of polyoxyethylene side chain-containing diol. A prepolymer solution (L) having a content of 2.35 mass% was obtained. Table 1 shows the details and properties of the synthesis conditions of the obtained prepolymer solution (L).

Synthesis Example 13 (Synthesis of Prepolymer Solution (M))

The isocyanate group content was the same as in Synthesis Example 10 except that 676 parts by mass of H ₁₂ MDI, 1,548 parts by mass of AN, 1,936 parts by mass of acetone, and 414 parts by mass of polyoxyethylene side chain-containing diol were used. The prepolymer solution (M) which is 0.8 mass% was obtained. Table 1 shows the details and properties of the synthesis conditions of the obtained prepolymer solution (M).

Example 1 (synthesis of aqueous polyurethane resin (A))

1,000 parts by mass of ion-exchanged water previously adjusted to 10 ° C. was placed in a stainless steel container having a volume of 3 L, and was previously stirred under 2,000 rpm using a homo disper (trade name: TK Homo Disper, manufactured by Primix). 500 parts by mass of the hydrophilic group-containing prepolymer solution (A) adjusted to 20 ° C was gradually added and dispersed.

Subsequently, 19.2 mass parts of the chain extender liquid prepared by 3.85 mass parts of hydrazine in 20 mass% aqueous solution was added gradually, paying attention to heat generation. In addition, the equivalence ratio of the amino group in the chain extender to the isocyanate group in the prepolymer (hereinafter, abbreviated as equivalent ratio of the chain extender) was 0.95.

In addition, hydrazine used hydrazine monohydrate (made by Wako Pure Chemical Industries, Ltd.), and the mass part of hydrazine is equivalent to hydrazine monohydrate (the equivalent ratio of the chain extender and the amount of hydrazine used in Examples and Comparative Examples below). The same applies to the description thereof).

After the addition of the chain extender solution, the mixture was stirred at 10 to 25 ° C for 2 hours to carry out a chain extension reaction. Furthermore, AN was distilled off under reduced pressure and the aqueous dispersion of the aqueous polyurethane resin (A) of 35 mass% of solid content was obtained. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (A).

Example 2 (synthesis of aqueous polyurethane resin (B))

5.82 parts by mass of hydrazine and N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane (trade name: KBM602, manufactured by Shin-Etsu Chemical Co., Ltd.), using a hydrophilic group-containing prepolymer solution (B) as a chain extender. Si atom content 13.6 mass%) The aqueous dispersion of aqueous polyurethane resin (B) was obtained by the same conditions and operation as Example 1 except having used 59.1 mass parts of chain extending | stretching agents prepared from 6.00 mass parts in 20 mass% aqueous solution. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (B).

Example 3 (Synthesis of Aqueous Polyurethane Resin (C))

Aqueous polyurethane resin under the same conditions and operation as in Example 1, except that 36.4 parts by mass of the chain extender solution prepared by using a hydrophilic group-containing prepolymer solution (B) and 7.27 parts by mass of hydrazine in an aqueous solution of 20% by mass as a chain extender. The aqueous dispersion of (C) was obtained. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (C).

Example 4 (Synthesis of Aqueous Polyurethane Resin (D))

As a chain extender, using a hydrophilic group-containing prepolymer solution (B), 30.0 parts by weight of N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane (KBM602) was prepared in a 20% by mass aqueous solution. A water dispersion of the aqueous polyurethane resin (D) was obtained under the same conditions and operation as in Example 1 except that 149.9 parts by mass was used. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (D).

Example 5 (Synthesis of Aqueous Polyurethane Resin (E))

Aqueous polyurethane resin under the same conditions and operation as in Example 1, except that 58.0 parts by mass of the chain extender solution prepared by using a hydrophilic group-containing prepolymer solution (C) as a chain extender was prepared using 11.6 parts by mass of hydrazine in a 20% by mass aqueous solution. The aqueous dispersion of (E) was obtained. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (E).

Example 6 (Synthesis of Aqueous Polyurethane Resin (F))

4.91 parts by mass of hydrazine and 47.2 parts by mass of N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane (KBM602) were used as a chain extender using a hydrophilic group-containing prepolymer solution (D) in a 20 mass% aqueous solution. A water dispersion of the aqueous polyurethane resin (F) was obtained under the same conditions and operation as in Example 1 except that 260.5 parts by mass of the prepared chain elongation solution was used. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (F).

Example 7 (Synthesis of Aqueous Polyurethane Resin (G))

Aqueous polyurethane resin under the same conditions and operation as in Example 1, except that 81.8 parts by mass of the chain extender solution prepared by using a hydrophilic group-containing prepolymer solution (D) and prepared as a chain extender using 16.4 parts by mass of hydrazine in a 20% by mass aqueous solution. The aqueous dispersion of (G) was obtained. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (G).

Example 8 (Synthesis of Aqueous Polyurethane Resin (H))

Aqueous polyurethane resin under the same conditions and operation as in Example 1, except that 36.4 parts by mass of the chain extender solution prepared by using a hydrophilic group-containing prepolymer solution (I) and 7.27 parts by mass of hydrazine as a 20% by mass aqueous solution as a chain extender. An aqueous dispersion of (H) was obtained. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (H).

Example 9 (Synthesis of Aqueous Polyurethane Resin (I))

500 g of the prepolymer solution (J) synthesized in Synthesis Example 10 was charged to a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, and heated to 30 ° C. Subsequently, 850 g of ion-exchanged water adjusted to 20 ° C in advance is gradually added to form an aqueous solution, and 0.85 parts by mass of hexamethylenediamine (manufactured by Wako Pure Chemical Industries, Ltd., hereinafter abbreviated as HDA) and N-β- (aminoethyl) 29.6 mass parts of chain extender liquids which prepared 5.06 mass part of-(gamma) -aminopropylmethyl dimethoxysilane (KBM602) with 20 mass% aqueous solution were added, and the chain extension was carried out.

After the addition of the chain extender solution, the mixture was stirred at 10 to 25 ° C for 2 hours to carry out a chain extension reaction. In addition, AN and acetone were distilled off under reduced pressure to obtain an aqueous dispersion of aqueous polyurethane resin (I) having a solid content of 35% by mass. Table 3 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (I).

Example 10 (Synthesis of Aqueous Polyurethane Resin (J))

As a chain extender, using a prepolymer solution (K), 2.4 parts by mass of HDA and 5.09 parts by mass of N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane (KBM602) were prepared in a 20% by mass aqueous solution. A water dispersion of the aqueous polyurethane resin (J) was obtained under the same conditions and operation as in Example 9, except that 37.4 parts by mass of the enteric solution was used. Table 3 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (J).

Example 11 (Synthesis of Aqueous Polyurethane Resin (K))

A prepolymer solution (L) was used to prepare 12.3 parts by mass of HDA and 5.28 parts by mass of N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane (KBM602) as a chain extender in a 20 mass% aqueous solution. Except having used 87.9 mass parts of chain extension liquids, the aqueous dispersion of aqueous polyurethane resin (K) was obtained by the same conditions and operation as Example 9. Table 3 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (K).

Comparative Example 1 (Synthesis of Aqueous Polyurethane Resin (L))

As a chain extender using a hydrophilic group-containing prepolymer solution (E), a 20 mass% aqueous solution of 5.75 parts by mass of hydrazine and 5.93 parts by mass of N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane) (KBM602) The aqueous dispersion of the aqueous polyurethane resin (L) was obtained under the same conditions and operation as in Example 1, except that 58.4 parts by mass of the chain elongation solution prepared in the above was used. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (L).

Comparative Example 2 (Synthesis of Aqueous Polyurethane Resin (M))

Aqueous polyurethane resin under the same conditions and operation as in Example 1, except that 36.9 parts by mass of the chain extender solution prepared by using a hydrophilic group-containing prepolymer solution (F) and 7.38 parts by mass of hydrazine as a 20% by mass aqueous solution as a chain extender. The aqueous dispersion of (M) was obtained. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (M).

Comparative Example 3 (Synthesis of Aqueous Polyurethane Resin (N))

A chain extender solution prepared by using a hydrophilic group-containing prepolymer solution (G) as a chain extender, 30.2 parts by mass of N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane (KBM602) in a 20% by mass aqueous solution A water dispersion of the aqueous polyurethane resin (N) was obtained under the same conditions and operation as in Example 1 except that 151.1 parts by mass was used. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (N).

Comparative Example 4 (Synthesis of Aqueous Polyurethane Resin (O))

The chain extension agent liquid which prepared 28.7 mass parts of N- (beta)-(aminoethyl)-(gamma)-aminopropylmethyl dimethoxysilane (KBM602) with 20 mass% aqueous solution using the hydrophilic group containing prepolymer (H) as a chain extension agent. A water dispersion of the aqueous polyurethane resin (O) was obtained under the same conditions as in Example 1 except for using a mass part. Table 2 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (O).

Comparative Example 5 (Synthesis of Aqueous Polyurethane Resin (P))

As a chain extender using a prepolymer solution (M), 2.35 parts by mass of HDA and 5.10 parts by mass of N-β- (aminoethyl) -γ-aminopropylmethyl dimethoxysilane (KBM602) were prepared in 20% by mass aqueous solution. Except having used 37.3 mass parts of enteric solutions, the aqueous dispersion of aqueous polyurethane resin (P) was obtained by the same conditions and operation as Example 9. Table 3 shows the details and properties of the synthetic conditions of the obtained aqueous polyurethane resin (P).

Property evaluation

The concentration, mechanical stability, oleic acid resistance, breaking elongation, softening temperature, texture and feel of the Si atom of the aqueous polyurethane resin (hereinafter, abbreviated to each aqueous polyurethane resin) obtained in each Example and each Comparative Example It was measured by the method. The results are shown in Table 2.

Examples 1 to 8, and Comparative Examples 1 to 4

Each aqueous polyurethane resin was apply | coated using the applicator on the OHP film degreased with acetone, and it dried at 110 degreeC for 1 hour, and obtained the film of about 60 micrometers in thickness. Thereafter, the film was cured for one week in a laboratory at 23 ° C. and a relative humidity of 55%. This produced a test sample.

Examples 9 to 11 and Comparative Example 5

Each water-based polyurethane resin was put into a plastic tray, and it solidified by making 90 degreeC or more saturated water vapor touch for about 1 minute. After standing overnight in a laboratory at 23 ° C. and a relative humidity of 55%, a film having a thickness of about 250 μm was obtained by drying at 110 ° C. for 2 hours. Thereafter, the film was cured for one week in a laboratory at 23 ° C. and a relative humidity of 55%. This produced a test sample.

Test of each aqueous polyurethane by the wet ashing method using nitric acid and sulfuric acid (for example, "Analytical Chemistry Manual", Japanese Analytical Chemistry Society of Japan, issuer Maruzen Co., Ltd., issued November 30, 1991, page 1292). After completely decomposing the organic components of the sample, it was heated to obtain a dried substance.

Subsequently, powdered sodium carbonate was added to the dried product, and further heated to dissolve the dried product in a molten salt of sodium carbonate.

Then, the mixture was cooled and solidified, and then diluted hydrochloric acid was added slowly until it became weakly acidic. Thus, an analytical sample was prepared (for example, "Analytical Chemistry Manual", Japanese Analytical Chemistry Society of Japan, issuer Maruzen Co., 1991). Published November 30, see pages 265 to 266).

Using this analysis sample, the concentration of Si atoms in each aqueous polyurethane resin was measured by an ICP emission spectrometer (ICP-AES, manufactured by Seiko Instool Co., Ltd., Model: VISTA-PRO).

In addition, description of "n.d." in Table 2 means that there is no measured value because Si atom is not contained.

After the test solution of the aqueous dispersion of each aqueous polyurethane resin of 5% by mass of solid content diluted with ion-exchanged water was passed through a wire mesh of # 300 mesh in advance, 100 g of the resin remaining in the wire mesh was weighed into a dedicated cup for a mechanical stability test.

Subsequently, shearing was applied for 20 minutes under conditions of a load of 147 N (15 kgf) and a rotation speed of 1,000 rpm using a Maron mechanical stability tester (manufactured by Science and Engineering Co., Ltd.) (Maron test).

The resin after the test was then filtered through a wire mesh of # 300 mesh, and the wire mesh was dried at 110 ° C. for 1 hour.

The mass of the wire mesh before and after the maron test was measured, and the mass of the resin remaining in the wire mesh was measured. Based on the measured mass, it converted into the amount of residual resin in the wire mesh of solid content of each aqueous polyurethane resin.

A test sample of each aqueous polyurethane resin was cut out to a size of 1 × 10 cm, and the mass of this test sample was measured. Subsequently, it was immersed in oleic acid for 7 days at 23 degreeC. After immersion, the oleic acid adhered to the surface of the test sample was quickly wiped off before the mass measurement of the test sample. And the mass of the test sample after immersion was measured. From the mass of the test sample before and after immersion in oleic acid, the oleic acid resistance (%) was calculated by the following formula.

% Oleic acid resistance = (mass of test sample after immersion-mass of test sample before immersion) / mass of test sample before immersion x 100

Test samples of each aqueous polyurethane resin were punched with dumbbells in the size of 5 mm wide and 50 mm long. Subsequently, the test sample was subjected to a test sample under the conditions of a tensile mode, a length of 25 mm between the marking lines, a heating rate of 5 ° C./min, and a measuring frequency of 10 Hz using a dynamic viscoelasticity measuring device (manufactured by Haiti Metrology Control, Model: DVA-200). The dynamic viscoelasticity of was measured. The intersection point of each tangent of the storage elastic modulus was calculated | required in the area | region where the storage elastic modulus of a rubber | gum or leather flat area | region is inflection | deflected, and this temperature was defined as softening temperature.

Elongation at Break (%)

Test samples of each aqueous polyurethane resin were punched with dumbbells in the size of 1 cm wide and 10 cm long. Next, this test sample was subjected to a tensile test using a tensile compression tester (Model 205N manufactured by Intesco Co., Ltd.) at 23 ° C, a tensile speed of 300 mm / min, and a distance of 50 mm between chucks. Thereby, the breaking elongation (EL) of each aqueous polyurethane resin was measured.

<Feel>

The tack (sticky feeling) and the touch of the test sample of each aqueous polyurethane resin were evaluated by accelerating with the following evaluation criteria, respectively. Based on these results, the texture was further evaluated by the following evaluation criteria.

(Feel)

(Circle): Both a tack and a touch are (circle).

(Triangle | delta): A tack is (circle) and a touch is (triangle | delta).

X: Any one of a tack and a touch is x.

(Evaluation standard of house)

(Circle): A tag is not recognized.

(Triangle | delta): A tag is recognized slightly.

X: A tag is recognized.

(Evaluation standard of the feel)

(Circle): It is a soft touch.

(Triangle | delta): When it is bent, a little stripe remains.

X: When bent, streaks remain clearly.

In addition, although the said description was provided as embodiment of an illustration of this invention, this is only a mere illustration and should not be interpreted limitedly. Modifications of the invention which are apparent to those skilled in the art are included in the appended claims.

Industrial Applicability

The aqueous polyurethane resin of the present invention is suitably used to provide a coating film or artificial and synthetic leather.

Claims

Polyisocyanates, high molecular weight polyols, containing at least 50 mol% of isocyanate groups of 1,4-bis (isocyanatomethyl) cyclohexane relative to the total moles of isocyanate groups; and An isocyanate group terminal prepolymer obtained by reacting at least an active hydrogen compound containing a hydrophilic group with
Extender
It is obtained by reaction of aqueous polyurethane resin.

The method of claim 1,
The chain extender contains an active hydrogen compound containing an alkoxysilyl group, wherein the aqueous polyurethane resin.

The method of claim 1,
0.05-1.5 mass% of Si atoms are contained, The aqueous polyurethane resin characterized by the above-mentioned.

The method of claim 2,
The chain extender is a compound represented by the following formula (1), an aqueous polyurethane resin.
[Formula 1]

The method of claim 1,
An aqueous polyurethane resin, wherein 1,4-bis (isocyanatomethyl) cyclohexane contains 50% by mass or more of trans-1,4-bis (isocyanatomethyl) cyclohexane.

It is obtained from the aqueous polyurethane resin of Claim 1, The coating film characterized by the above-mentioned.

The aqueous polyurethane resin of Claim 1 is used, The artificial and synthetic leather characterized by the above-mentioned.