WO2021172485A1

WO2021172485A1 - Polyurethane resin aqueous dispersion

Info

Publication number: WO2021172485A1
Application number: PCT/JP2021/007240
Authority: WO
Inventors: 拓紀牧野; 増美山根; 将浩渡辺
Original assignee: 三洋化成工業株式会社
Priority date: 2020-02-28
Filing date: 2021-02-26
Publication date: 2021-09-02
Also published as: JPWO2021172485A1

Abstract

The present invention addresses the problem of providing a polyurethane resin aqueous dispersion that has excellent storage stability and washability when being used in a paint gun and that can provide a coating having excellent post-painting appearance, water-resistant adhesiveness, and hot water-resistant adhesiveness.　A polyurethane resin aqueous dispersion (Q) according to the present invention contains: an aqueous medium; and a polyurethane resin (U) having an acidic group and including, as an essential structural monomer, an active hydrogen component (A) and an organic polyisocyanate component (B), and/or a polyurethane resin (U1) obtained by neutralizing the acidic group included in the polyurethane resin (U). The polyurethane resin (U) has a hydroxyl group. The acid value of the polyurethane resin (U) is 5-18 mgKOH/g. The viscosity of the polyurethane resin (U) at 25°C as measured using a rheometer at a shear rate of 0.1/s is 100-1,000,000 Pa·s.

Description

Polyurethane resin aqueous dispersion

The present invention relates to a polyurethane resin aqueous dispersion.

Polyurethane resin aqueous dispersions are used as highly functional aqueous dispersions in paints, adhesives, fiber processing agents, paper processing agents, inks, etc. because they have excellent film properties obtained by drying. However, it is expected to become more and more important from the viewpoints of environmental protection, resource saving and safety. Conventionally, solvent-based urethane dissolved in an organic solvent has been used in these applications, but due to the drawbacks of organic solvent toxicity, fire risk, environmental pollution, etc., in recent years, solvent-based urethane to polyurethane resin water-based Switching to dispersion is accelerating.

When the polyurethane resin aqueous dispersion is used for painting purposes, the painting is applied to the base material by a painting gun or the like. When a paint containing a polyurethane resin aqueous dispersion, which generally has strong cohesiveness and is easy to form a film, is painted with a painting gun, the paint containing the polyurethane resin aqueous dispersion remaining in the painting gun after using the painting gun is washed and removed. It could be difficult to do.
Further, when a paint containing an aqueous dispersion of polyurethane resin is spray-painted with a painting gun or the like, there is a problem that the uniformity of the coating film (surface smoothness) is low at the time of coating and the appearance of the coating film is deteriorated. rice field.
The problems of detergency and appearance after using this coating gun can be improved by using an aqueous dispersion of a low molecular weight polyurethane resin in which a terminal isocyanate group is reacted with a blocking agent as in Patent Document 1. can. However, the aqueous dispersion of the polyurethane resin of Patent Document 1 has a problem that it thickens when stored for a long period of time and has poor storage stability.

In addition, since articles coated with paint may be used outdoors, water resistance of the coated film to the substrate is also required, and the polyurethane resin aqueous dispersion is used after the above-mentioned coating gun is used. In addition to the detergency, appearance and storage stability of the above, it has been required to have both water-resistant and heat-resistant water adhesion.

International Publication No. 2010/098318

An object of the present invention is to provide a polyurethane resin aqueous dispersion which is excellent in storage stability and detergency after using a coating gun, and can obtain a film having excellent appearance after coating, water resistance and water adhesion. There is.

As a result of diligent studies, the present inventors have found a polyurethane resin aqueous dispersion that can solve the above-mentioned problems. That is, in the present invention, the polyurethane resin (U) having an acidic group containing the active hydrogen component (A) and the organic polyisocyanate component (B) as essential constituent monomers and / or the acidic group contained in the polyurethane resin (U). A polyurethane resin aqueous dispersion containing a polyurethane resin (U1) obtained by neutralizing the above and an aqueous medium.
The polyurethane resin (U) has a hydroxyl group and has
The polyurethane resin (U) has an acid value of 5 to 18 mgKOH / g.
In a polyurethane resin aqueous dispersion (Q) having a viscosity of the polyurethane resin (U) of 100 to 1,000,000 Pa · s at 25 ° C. measured at a shear rate of 0.1 / s using a rheometer. be.

The polyurethane resin aqueous dispersion of the present invention is excellent in storage stability and detergency after using a painting gun, and can obtain a film having excellent appearance after painting, water resistance and water resistance.

The polyurethane resin aqueous dispersion (Q) of the present invention is a polyurethane resin (U) having an acidic group containing an active hydrogen component (A) and an organic polyisocyanate component (B) as essential constituent monomers, and / or the polyurethane resin. It contains a polyurethane resin (U1) obtained by neutralizing the acidic group of (U) and an aqueous medium.
Further, the polyurethane resin (U) has a hydroxyl group.
The acid value of the polyurethane resin (U) is 5 to 18 mgKOH / g.
The viscosity of the polyurethane resin (U) at 25 ° C. measured at a shear rate of 0.1 / s using a rheometer is 100 to 1,000,000 Pa · s.

<Polyurethane resin (U)>
First, regarding the polyurethane resin (U) having the above-mentioned properties, a mode to be satisfied by the polyurethane resin (U) and a preferable mode of the polyurethane resin (U) will be described.
When the polyurethane resin aqueous dispersion (Q) of the present invention does not contain the polyurethane resin (U) but contains the polyurethane resin (U1), the polyurethane resin (U) which is a precursor of the polyurethane resin (U1) However, it suffices that the following aspects of the polyurethane resin (U) to be satisfied (preferably the preferred aspects of the polyurethane resin (U)) are satisfied.
When the polyurethane resin aqueous dispersion (Q) of the present invention contains the polyurethane resin (U) and the polyurethane resin (U1), the polyurethane resin (U) or the polyurethane resin (U1) which is a precursor of the polyurethane resin (U1) ( It suffices that at least one of U) satisfies the mode to be satisfied by the following polyurethane resin (U) (preferably the preferred mode of the polyurethane resin (U)), and is a precursor of the polyurethane resin (U) and the polyurethane resin (U1). It is preferable that both of the polyurethane resin (U), which is the body, satisfy the aspects to be satisfied by the following polyurethane resin (U) (preferably the preferred embodiment of the polyurethane resin (U)).
The polyurethane resin (U) may be used alone or in combination of two or more. The polyurethane resin (U1) may be used alone or in combination of two or more. At least one kind of polyurethane resin (U) and at least one kind of polyurethane resin (U1) may be used in combination.

As described above, the polyurethane resin (U) is a resin containing the active hydrogen component (A) and the organic polyisocyanate component (B) as essential constituent monomers.
Each component will be described below.

<Active hydrogen component (A)>
The active hydrogen component (A) is a compound containing an active hydrogen-containing group. In the present invention, the active hydrogen-containing group means a group having an active hydrogen atom. The active hydrogen atom means a hydrogen atom that is bonded to an oxygen atom, a nitrogen atom, a sulfur atom, etc. and has a high reactivity with an isocyanate group, and as a group having this active hydrogen atom (active hydrogen-containing group), Examples thereof include a hydroxyl group, a primary amino group, a secondary amino group and a thiol group.
In the present invention, the carboxyl group and the sulfo group are not included in the active hydrogen-containing group.

The active hydrogen component (A) includes a high molecular weight polyol (A1), a low molecular weight polyol (A2), a compound having a hydrophilic group and an active hydrogen atom (A3), a chain extender (A4), and a reaction terminator (A4). A5) and the like can be mentioned.

Examples of the polymer polyol (A1) include polymer polyols having a number average molecular weight of 300 or more.
The number average molecular weight of the polymer polyol (A1) is preferably 500 or more, and more preferably 500 to 2,000.

In the present specification, the number average molecular weight (hereinafter, may be abbreviated as Mn) and the weight average molecular weight (hereinafter, may be abbreviated as Mw) are gel permeation chromatography (GPC) using polystyrene as a standard. ) Is measured.
Mw and Mn are measured by the following measuring methods.
(Measuring method of Mw and Mn)
A sample (high molecular weight polystyrene, polyurethane resin or aqueous polyurethane dispersion) is added to DMF so that the solid content is 0.125% by weight, and the mixture is stirred and dissolved at room temperature for 1 hour, and then filtered through a filter having a pore size of 0.3 μm. After filtration, the components Mw and Mn contained in the obtained filtrate are measured by GPC using DMF as a solvent and polystyrene as a molecular weight standard.
The GPC measurement conditions are as follows.
Equipment: "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: "Guardcolumn α" + "TSKgel α-M" [both manufactured by Tosoh Corporation]
Sample solution: 0.125 wt% dimethylformamide solution Eluent: Dimethylformamide solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) [manufactured by Tosoh Corporation]

Examples of the polymer polyol (A1) include polyether polyols, polyester polyols, polycarbonate polyols and the like.

Examples of the polyether polyol include an aliphatic polyether polyol and an aromatic ring-containing polyether polyol.
The polyether polyol does not include the polyester polyol and the polycarbonate polyol described later.

Examples of the aliphatic polyether polyol include an alkylene oxide adduct having 2 to 4 carbon atoms to an aliphatic polyhydric alcohol having 2 to 20 carbon atoms (ethylene glycol, propylene glycol, butanediol, dodecanediol, glycerin, etc.). Be done.
Specific examples thereof include polyoxyethylene polyol [polyethylene glycol (hereinafter abbreviated as PEG) and the like], polyoxypropylene polyol [polypropylene glycol and the like], polyoxyethylene / propylene polyol, polytetramethylene ether glycol and the like.

Commercially available aliphatic polyether polyols include PTMG650 [Mn = 650 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.], PTMG1000 [Mn = 1,000 polytetramethylene ether glycol, Mitsubishi Chemical Co., Ltd.]. , PTMG1300 [Mn = 1,300 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.], PTMG1500 [Mn = 1,500 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.], PTMG1800 [Mn] = 1,800 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.], PTMG2000 [Mn = 2,000 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.], PTMG3000 [Mn = 3,000 poly Tetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.], PTMG4000 [Mn = 4,000 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.], PTGL3000 [Mn = 3,000 modified PTMG, Hodoya Chemical Industry Co., Ltd.] Manufactured by Sanyo Kasei Kogyo Co., Ltd.] and Sanniks Diol GP-3000 [Mn = 3,000 polypropylene ether triol, manufactured by Sanyo Kasei Kogyo Co., Ltd.] and the like.
Among these, a combination of polytetramethylene ether glycol having a Mn of 300 to 1300 and polytetramethylene ether glycol having an Mn of 1500 to 4000 is preferable from the viewpoint of water adhesion and heat resistant water adhesion.

As a specific method for producing an aliphatic polyether polyol, taking polytetramethylene ether glycol (PTMG), which is a polyether polyol, as an example, a method for producing an aliphatic polyether polyol by ring-opening polymerization of tetrahydrofuran (THF), which is a general production method. And so on.

Examples of the aromatic ring-containing polyether polyol include an alkylene oxide adduct having 2 to 4 carbon atoms added to an aromatic ring and a compound having 6 to 20 carbon atoms (bisphenol, resorcin, etc.) having two or more hydroxyl groups.
Specifically, bisphenol A ethylene oxide (hereinafter abbreviated as EO) adduct [bisphenol A EO 2 mol adduct, bisphenol A EO 4 mol adduct, bisphenol A EO 6 mol adduct, bisphenol A EO 8 mol adduct. Bisphenol A EO 10 mol adduct, bisphenol A EO 20 mol adduct, etc.] and bisphenol A propylene oxide (hereinafter abbreviated as PO) adduct [bisphenol A PO 2 mol adduct, bisphenol A PO 3 mol adduct, etc. , PO5 molar adduct of bisphenol A, etc.] and the like, and EO or PO adduct of resorcin and the like having a bisphenol skeleton.
Examples of commercially available aromatic ring-containing polyether polyols include New Pole BPE-20T: [Mn = 321 and ethylene oxide adduct of bisphenol A having a hydroxyl value of 349 mgKOH / g, manufactured by Sanyo Kasei Kogyo Co., Ltd.]. ..

The number average molecular weight of the polyether polyol contained in the active hydrogen component (A) is preferably 500 or more, and more preferably 500 to 2,000.

Examples of the polyester polyol include condensed polyester polyol, polylactone polyol, castor oil-based polyol and the like.
The polyester polyol does not include the polycarbonate polyol described later.

The condensed polyester polyol is a polyester polyol obtained by a low molecular weight (less than Mn300) polyhydric alcohol and a polyvalent carboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof.
Low molecular weight polyhydric alcohols include aliphatic polyhydric alcohols of less than Mn300 and divalent to octavalent or higher, and alkylene oxides of phenols of less than Mn300 of divalent to 8 or higher (EO, PO, 1, 2). -, 1,3-, 2,3- or 1,4-butylene oxide, etc., hereinafter abbreviated as AO) Low molecular weight adducts can be used.
Of the low molecular weight polyhydric alcohols that can be used in condensed polyester polyols, preferred are ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexaneglycol, and EO or PO low molars of bisphenol A. Additives and combinations thereof.

Examples of polyvalent carboxylic acids having 2 to 10 carbon atoms or ester-forming derivatives thereof that can be used in condensed polyester polyols are aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.). , Alicyclic dicarboxylic acid (dimeric acid, etc.), aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, phthalic acid, etc.), trivalent or higher polycarboxylic acid (trimellitic acid, pyromellitic acid, etc.), these Anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), their acid halides (dichloroide adipic acid, etc.), and these low molecular weight alkyl esters (dimethyl succinate, dimethyl phthalate, etc.) In addition, the combined use of these can be mentioned.

Specific examples of the condensed polyester polyol include polyethylene adipatediol, polybutylene adipatediol, polyhexamethylene adipatediol, polyhexamethyleneisophthalatediol, polyneopentyl adipatediol, polyethylenepropylene adipatediol, polyethylenebutylene adipatediol, and polybutylene. Hexamethylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene ceva Examples thereof include catediol and polyneopentyl terephthalate diol.

Commercially available products of the condensed polyester polyol include Clare polyol P-1010 [Mn = 1,000 poly (3-methylpentylene adipate) diol, manufactured by Kurare Co., Ltd.], Clare polyol P-1010 [Mn = 2, 000 poly (3-methylpentylene adipate) diol, manufactured by Clare Co., Ltd.], Clare polyol P-3010 [Mn = 3,000 poly (3-methylpentylene adipate) diol, manufactured by Clare Co., Ltd.], Claret Polyester P-4010 [Mn = 4,000 poly (3-methylpentylene adipate) diol, manufactured by Claret Co., Ltd.], Sun Esther 2610 [Mn = 1,000 polyethylene adipate diol, Sanyo Kasei Kogyo Co., Ltd. ], Sun Esther 4620 [Mn = 2,000 polytetramethylene adipate diol], Sun Esther 2620 [Mn = 2,000 polyethylene adipate diol, manufactured by Sanyo Kasei Kogyo Co., Ltd.] and the like.

The polylactone polyol is a heavy adduct of a lactone to the low molecular weight polyhydric alcohol, and examples of the lactone include lactones having 4 to 12 carbon atoms (γ-butyrolactone, γ-valerolactone, ε-caprolactone, etc.). Be done.
Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, polycaprolactone triol and the like.

Castor oil-based polyol includes castor oil and modified castor oil modified with polyol or AO. Modified castor oil can be produced by transesterification of castor oil and polyol and / or addition of AO. Examples of castor oil-based polyols include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, and EO (4 to 30 mol) adducts of castor oil.

Examples of the polycarbonate polyol include the low molecular weight polyhydric alcohol, a low molecular weight carbonate compound (for example, a dialkyl carbonate having an alkyl group having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, and a polycarbonate polyol having 6 to 9 carbon atoms. Examples thereof include a polycarbonate polyol produced by condensing a diaryl carbonate having an aryl group of (1) with a dealcohol reaction. Two or more kinds of low molecular weight polyhydric alcohols and alkylene carbonates may be used in combination.

Specific examples of the polycarbonate polyol include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol and poly (tetramethylene / hexamethylene) carbonate diol (for example, 1,4-butanediol and 1,6-hexane). Diol) and the like obtained by condensing a diol while dealcoholizing it with a dialkyl carbonate.

Commercially available polycarbonate polyols include Nipponolane 980R [Mn = 2,000 polyhexamethylene carbonate diol, manufactured by Nippon Polyurethane Industry Co., Ltd.] and Clare polyol C-1090 [Mn = 1,000 poly (3-methyl-). 5-Pentanediol / Hexamethylene) carbonate diol, manufactured by Kuraray Co., Ltd.], Kurare polyol C-2090 [Mn = 2,000 poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol, Kuraray Co., Ltd. ), Claret polyol C-3090 [Mn = 3,000 poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol, Claret Co., Ltd.], Claret polyol C-4090 [Mn = 4, 000 poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol, manufactured by Claret Co., Ltd.], and T4672 [Mn = 2,000 poly (tetramethylene / hexamethylene) carbonate diol, Asahi Kasei Chemicals Co., Ltd. ) Made] and the like.

The active hydrogen component (A) is a polytetramethylene ether which is a high molecular weight polyol (A1) from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the range described in detail later and from the viewpoint of water adhesion and heat resistance. It is preferable that glycol is contained as an essential constituent monomer.
The Mn of the polytetramethylene ether glycol is preferably 500 to 2,000 from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the range described in detail later.

Examples of the small molecule polyol (A2) include small molecule polyols having a number average molecular weight (hereinafter abbreviated as Mn) of less than 300.
The Mn of the small molecule polyol is a calculated value from the chemical formula.

Examples of the low molecular weight polyol (A2) having a Mn of less than 300 include aliphatic dihydric alcohols, aliphatic trihydric alcohols, and tetrahydric or higher aliphatic alcohols. Among the low molecular weight polyols (A2) having a Mn of less than 300, a dihydric aliphatic alcohol is preferable from the viewpoint of water resistance and heat-resistant yellowing, and the aliphatic dihydric alcohol includes ethylene glycol and propylene glycol. 1,4-Butanediol, neopentyl glycol and 1,6-hexanediol are particularly preferable, and trimethylolpropane is particularly preferable as the aliphatic trihydric alcohol.

In the present invention, examples of the hydrophilic group of the compound (A3) having a hydrophilic group and an active hydrogen atom include a carboxyl group, a carboxylate group, a sulfo group and a sulfonat group.
Further, as described above, the active hydrogen atom does not include a hydrogen atom derived from a carboxyl group and a sulfo group.
Examples of the compound (A3) having a hydrophilic group and an active hydrogen atom include a compound having a carboxyl group and having 2 to 10 carbon atoms [dialkylol alkanoic acid (2,2-dimethylolpropionic acid, 2,2-dimethylol). Butanoic acid, 2,2-dimethylol heptanic acid and 2,2-dimethylol octanoic acid, etc.), tartrate and amino acids (glycine, alanine, valine, etc.), etc.], compounds with sulfo groups and 2 to 16 carbon atoms [ 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and sulfoisophthalic acid di (ethylene glycol) ester, etc.], compounds having a sulfamic acid group and having 2 to 10 carbon atoms [N, N-bis (2) -Hydrethyl) sulfamic acid, etc.] and the like.
Of these, compounds having a carboxyl group or a carboxylate group are preferable, and 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are more preferable.

The active hydrogen component (A) may contain a compound (A31) having an acidic group (carboxyl group, etc.) as an essential constituent monomer among the compounds (A3) having a hydrophilic group and an active hydrogen atom. preferable. By using the compound (A31), an acidic group can be introduced into the polyurethane resin (U).
The compound (A31) is used in an amount that allows the acid value of the polyurethane resin (U) to be within the range described in detail later.

Examples of the chain extender (A4) include compounds having two or more active hydrogen atoms other than (A1) to (A3), and specific examples thereof include water and diamines having 2 to 10 carbon atoms (ethylenediamine, propylene). Diamine, hexamethylenediamine, isophoronediamine, toluenediamine, piperazine, etc.), polyalkylene polyamines having 2 to 10 carbon atoms (diethylenetriamine, triethylenetetramine, etc.), hydrazine or a derivative thereof (dibasic acid dihydrazide, for example, adipic acid dihydrazide, etc.) ) And amino alcohols having 2 to 10 carbon atoms (ethanolamine, diethanolamine, 2-amino-2-methylpropanol, triethanolamine, etc.) and the like.

Examples of the reaction terminator (A5) include monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.) and monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, mono). Mono or dialkylamines such as butylamines, dibutylamines and monooctylamines; mono- or dialkanolamines such as monoethanolamines, diethanolamines, propanolamines and diisopropanolamines) and the like.
Specific examples thereof include 2-aminoethanol, 2,2'-iminodiethanol, 1-amino-2-propanol, 3-amino-1-propanol and the like.
From the viewpoint of water resistance and heat resistance, it is preferable that the active hydrogen component (A) contains a reaction terminator (A5).

Since the chain extender (A4) and the reaction terminator (A5) affect the urea group content described later and also the viscosity of the polyurethane resin (U), they are used in an amount within a range that does not impair the effects of the present invention. There is a need to. Specifically, it is necessary to use the amount in the range in which the viscosity of the polyurethane resin (U) becomes a value described in detail later.
Therefore, it is preferable to use the chain extender (A4) and the reaction terminator (A5) in an amount such that the urea group content in the polyurethane resin (U) becomes a value described later.

The active hydrogen component (A) may be used alone or in combination of two or more.

<Organic polyisocyanate component (B)>
The organic polyisocyanate component (B), which is an essential constituent monomer of the polyurethane resin (U), is a compound having 2 to 3 or more isocyanate groups, and those conventionally used in polyurethane resin production and the like are used. Can be used.
The organic polyisocyanate component (B) includes an aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms, an alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms, and an aromatic aliphatic polyisocyanate having 10 to 17 carbon atoms. (B3), aromatic polyisocyanates (b4) having 8 to 22 carbon atoms and derivatives of (b1) to (b4) (for example, isocyanurates) and the like can be mentioned.

Examples of the aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2-. Isocyanatoethyl-2,6-diisocyanatohexanoate and the like can be mentioned.

Examples of the alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane 4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate (hydrogenated TDI). , Bis (2-isosianatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornene diisocyanate and the like.

Examples of the aromatic aliphatic polyisocyanate (b3) having 10 to 17 carbon atoms include m- and / or p-xylene diisocyanate (XDI), α, α, α', α'-tetramethylxylene diisocyanate (TMXDI) and the like. Can be mentioned.

Examples of the aromatic polyisocyanate (b4) having 8 to 22 carbon atoms include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-or. 2,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 4,4', 4 ″ -triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, crude MDI and the like. Be done.

Among the organic polyisocyanate components (B), (b1) and (b2) are preferable from the viewpoint of mechanical properties and weather resistance of the obtained film, and (b2) is more preferable, and (b2) is particularly preferable. IPDI and hydrogenated MDI.
The organic polyisocyanate component (B) may be used alone or in combination of two or more. Among them, the organic polyisocyanate component (B) preferably contains a chain aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms and / or an alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms.

Since the type of the organic polyisocyanate component (B) affects the urethane group content described later and also affects the viscosity of the polyurethane resin (U) described in detail later, it is necessary to use the organic polyisocyanate component (B) within a range that does not impair the effects of the present invention. There is. Specifically, it is necessary to use the polyurethane resin (U) in a range in which the viscosity becomes a value described later.
Therefore, as the type of the organic polyisocyanate component (B), it is preferable to use an amount in which the urethane group content in the polyurethane resin (U) becomes a value described later.

The polyurethane resin (U) may have a constituent monomer other than the active hydrogen component (A) and the organic polyisocyanate component (B).
Examples of the constituent monomers other than the active hydrogen component (A) and the organic polyisocyanate component (B) include polyepoxy compounds having 2 to 30 carbon atoms (1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, etc.). ) Etc. can be mentioned.

For the polyurethane resin (U), the viscosity of the polyurethane resin (U) at 25 ° C. measured at a shear rate of 0.1 / s using a rheometer is 100 to 1,000,000 Pa · s.
The viscosity of the polyurethane resin (U) at 25 ° C. measured at a shear rate of 0.1 / s using a rheometer is 100 to 150,000 Pa from the viewpoint of cleanability and appearance after using a painting gun. -It is preferably s. Further, from the viewpoint of water resistance and heat resistant water adhesion, it is more preferably 3,500 to 13,000 Pa · s, further preferably 3,500 to 9,000 Pa · s, and 3,500 to 3,500 to s. It is particularly preferably 4,500 Pa · s.
The viscosity using a rheometer can be measured under the following conditions using, for example, "MCR-302" manufactured by AntonioPaar.
(Measurement condition)
Measuring jig: Parallel plate "PP-08" (diameter 8 mm)
Distance between plates: 0.5 mm
Measurement temperature: 25 ° C
Measurement mode: Rotational shear rate: 0.1 / sec

In order to keep the viscosity of the polyurethane resin (U) within the above range, as described above, polytetramethylene ether glycol, which is a high molecular weight polyol (A1), is used as the active hydrogen component (A), and the urethane group content and The urethane group content is set to a preferable value described later, and the equivalent ratio of isocyanate groups / active hydrogen atoms is set to a preferable value described later for the active hydrogen component (A) and the organic polyisocyanate component (B) constituting the polyurethane resin (U). 0.6 to 0.95), a method in which the molecular weight of the polyurethane resin (U) is set to a preferable value described later, and the acid value is set to a value described later, and the like can be mentioned.
For example, when the viscosity of the polyurethane resin (U) is low, the molecular weight of the polyurethane resin (U) can be increased by increasing the equivalent ratio of isocyanate groups / active hydrogen atoms within a preferable range described later to increase the molecular weight of the polyurethane resin (U). The viscosity of can be increased. Further, the viscosity of the polyurethane resin (U) can be increased by increasing the urethane group content, the urea group content, and the acid value within the range of the values described later.
Further, for example, when the viscosity of the polyurethane resin (U) is high, the molecular weight of the polyurethane resin (U) can be lowered by reducing the equivalent ratio of isocyanate groups / active hydrogen atoms within a preferable range described later, and the polyurethane resin (U) can be reduced. The viscosity of U) can be reduced. Further, the viscosity of the polyurethane resin (U) can be reduced by lowering the urethane group content, the urea group content, and the acid value within the range of the values described later.

As a method for obtaining the polyurethane resin (U) [including the polyurethane resin (U) which is a precursor of the polyurethane resin (U1)] for measuring the viscosity from the polyurethane resin aqueous dispersion (Q), the following methods and the like are used. Can be mentioned.
When the component other than the polyurethane resin (U) contained in the polyurethane resin aqueous dispersion (Q) [including the neutralizing agent of the polyurethane resin (U) described later] is a volatile component, the polyurethane resin (containing a neutralizing agent for the polyurethane resin (U) described later) is heated or the like. Polyurethane resin (U) can be obtained by volatilizing components other than U).
When the polyurethane resin aqueous dispersion (Q) contains a non-volatile component, the polyurethane resin (U) is purified by known chromatography using a volatile solvent as a mobile phase, and then heated or the like. The polyurethane resin (U) can be obtained by removing the volatile solvent and the like.
When the neutralizing agent for the polyurethane resin (U) described later is non-volatile, the components other than the polyurethane resin (U) are removed by the above method after performing a salt exchange reaction with a volatile base. Then, the polyurethane resin (U) can be obtained.

The urethane group content of the polyurethane resin (U) is 1.0 to 3.5 mmol / g based on the weight of the polyurethane resin (U) from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the above-mentioned viscosity. It is preferably 1.0 to 1.5 mmol / g, more preferably 1.0 to 1.2 mmol / g, and particularly preferably 1.1 to 1.2 mmol / g. preferable.
The urea group content of the polyurethane resin (U) is preferably 0.8 mmol / g or less based on the weight of the polyurethane resin (U) from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the above-mentioned viscosity. .. From the viewpoint of water adhesion and heat resistance, the urea group content is preferably 0.05 mmol / g or more, preferably 0.5 mmol / g or more, based on the weight of the polyurethane resin (U). It is more preferable to have.
The ratio of the urea group content to the urethane group content [urea group content / urethane group content] is preferably 0.45 or more from the viewpoint of water adhesion and heat resistant water adhesion, and is preferably 0. It is more preferably 47 to 0.80. The ratio of the urea group to the urethane group content can be quantified by ^{1 1 H-NMR.}

In order to make the urethane group content of the polyurethane resin (U) within a desired range, the amounts of the active hydrogen component (A) and the organic polyisocyanate component (B) may be appropriately adjusted.
The urethane group content can be calculated from the N atom content quantified by the nitrogen analyzer, the ratio of the urea group to the urethane group content, and the alohanate group and burette group content. First, the total amount of N atoms derived from "urethane group" and "urea group" is calculated by subtracting the amount of N atoms derived from "alohaneate group" and "buret group" from "N atom content". do. Next, the amounts of N atoms derived from the "urethane group" and the "urea group" are calculated from the ratio of the urethane group and the urea group, respectively. From this value, the urethane group concentration is calculated.

In order to make the urea group content in the polyurethane resin (U) within a desired range, the amino group content, the water content and the isocyanate group content in the raw material of the polyurethane resin (U) may be appropriately adjusted.
The urea group content can be calculated from the N atom content quantified by a nitrogen analyzer, the ratio of the urea group to urethane group contents, and the alohanate group and burette group contents. First, the total amount of N atoms derived from "urethane group" and "urea group" is calculated by subtracting the amount of N atoms derived from "alohaneate group" and "buret group" from "N atom content". do. Next, the amounts of N atoms derived from the "urethane group" and the "urea group" are calculated from the ratio of the urethane group and the urea group, respectively. From this value, the urea group concentration is calculated.

In the present invention, the total content of the alohanate group and the burette group in the polyurethane resin (U) is 0 based on the weight of the polyurethane resin (U) from the viewpoint of film forming property and water resistance of the obtained film. It is preferably 0.1 mmol / g or less, more preferably 0.03 mmol / g or less, particularly preferably 0.01 mmol / g or less, particularly preferably 0.003 mmol / g or less, and most preferably 0.001 mmol / g or less. Is.

In order to make the total value of the alohanate group and burette group content of the polyurethane resin (U) within the desired range, the amino group content in the raw material of the polyurethane resin (U) and the isocyanate group with respect to the equivalent of the hydroxyl group and the amino group The ratio of the equivalent amounts of the above, the urethanization reaction temperature, and the like may be appropriately adjusted. In particular, the reaction temperature can be set to 120 ° C. or lower or 180 ° C. or higher to suppress the formation of alohanate groups and burette groups.
The content of alohanate group and burette group is measured by gas chromatography.

The Mn of the polyurethane resin (U) is preferably 1,500 to 8,000, more preferably 2,000 to 7,500, particularly 2,000 to 7,500, from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the above-mentioned viscosity. It is preferably 2,000 to 6,000, particularly preferably 2,000 to 5,500, and most preferably 2,000 to 5,000.
By appropriately adjusting the amounts of the active hydrogen component (A) and the organic polyisocyanate component (B), the Mn of the polyurethane resin (U) can be set in a desired range.

The Mw of the polyurethane resin (U) is preferably 4,000 to 20,000, more preferably 5,000 to 18,000, and even more preferably 5,000 to 18,000, from the viewpoint of adjusting the viscosity of (U) to the above-mentioned viscosity. It is 6,500 to 15,000, particularly preferably 7,000 to 9,800, and most preferably 7,000 to 7,600.

Mn and Mw are values measured by the above-mentioned gel permeation chromatography (GPC).
In the GPC measurement, when the polyurethane resin (U) is dissolved in DMF so that the solubility of the polyurethane resin (U) in the solvent used for the measurement is less than 90% by weight [0.125% by weight of the solid content concentration], the sample actually dissolved is 0. If it is less than 1125% by weight (= 0.125 × 0.90)], the measurement accuracy of GPC is lowered. In that case, since it is difficult to accurately measure the molecular weight, the molecular weight of the polyurethane resin is defined as infinite.

As described above, the polyurethane resin (U) has a hydroxyl group.
The hydroxyl value of the polyurethane resin (U) is preferably 15 to 100 mgKOH / g from the viewpoint of paint gun detergency and appearance.
Examples of the hydroxyl group of the polyurethane resin (U) include a hydroxyl group derived from the active hydrogen component (A), and the hydroxyl value can be adjusted by adjusting the amounts of the active hydrogen component (A) and the organic polyisocyanate component (B). Can be adjusted to the above-mentioned preferable range.
The hydroxyl value of the polyurethane resin (U) is a value measured according to JIS K0070 (1992).

As described above, the polyurethane resin (U) has an acidic group.
The acid value of the polyurethane resin (U) is 5 to 18 mgKOH / g, preferably 5 to 15 mgKOH / g, and more preferably 5 to 10 mgKOH / g from the viewpoint of water resistance and adhesion.
Examples of the acidic group contained in the polyurethane resin (U) include an acidic group derived from the compound (A31) having an acidic group, and a carboxyl group and a sulfo group. The acid value can be adjusted to the above-mentioned preferable range by adjusting the amount of the compound (A31) having an acidic group or the like.
The acid value of the polyurethane resin (U) is a value measured according to JIS K0070 (1992).

The weight ratio of the insoluble component generated when the polyurethane resin (U) and acetone (such as 25 ° C. acetone) having a weight 10 times that of the polyurethane resin (U) are stirred at 80 ° C. for 180 minutes in a sealed state is used for painting gun cleaning. From the viewpoint of properties, it is preferably 5% by weight or less based on the weight of the added polyurethane resin (U).
The following method can be used as a method for measuring the weight ratio of the insoluble component.
(Measuring method of weight ratio of insoluble components)
Wg of polyurethane resin (U) is placed in a pressure-resistant airtight container with an inner diameter of 6 cm and a depth of 12 cm together with a stirrer chip having a length of 3 cm. (Acetone at ° C., etc.) is added, and the mixture is stirred at 80 ° C. for 180 minutes in a hermetically sealed manner to obtain a mixed solution.
The obtained mixed solution is filtered through a SUS mesh (opening 75 μm) whose weight (W1) has been measured in advance, and then filtered with acetone (the same weight as acetone charged in a pressure-resistant airtight container such as 25 ° C. acetone). To wash. The filtration residue and the SUS mesh are dried at 105 ° C. for 30 minutes, and then the total weight (W2) is measured. The weight ratio of the insoluble component is calculated by the following formula.
Weight ratio of insoluble component (%) = {(W2-W1) / W} x 100
As a method for obtaining the polyurethane resin (U) for measuring the weight ratio of the insoluble component from the polyurethane resin aqueous dispersion (Q), the above-mentioned "polyurethane resin (U) for measuring the viscosity" is used. A method of obtaining from the polyurethane resin aqueous dispersion (Q) ”and the like can be used.

In order to set the weight ratio of the insoluble component to the above-mentioned preferable value, polytetramethylene ether glycol, which is a high molecular weight polyol (A1), is used as the active hydrogen component (A), and the urethane group content and the urea group are contained. The amount is set to the above-mentioned preferable value, and the equivalent ratio of the isocyanate group / active hydrogen atom is set to the above-mentioned preferable value (0.6) with respect to the active hydrogen component (A) and the organic polyisocyanate component (B) constituting the polyurethane resin (U). ~ 0.95), the molecular weight of the urethane resin (U) is set to the above-mentioned preferable value, and the acid value is set to the above-mentioned value.
For example, when the weight ratio of the insoluble component of the polyurethane resin (U) is high, the molecular weight of the polyurethane resin (U) can be lowered by reducing the equivalent ratio of the isocyanate group / active hydrogen atom within a preferable range described later. The weight ratio of the insoluble component can be reduced. Further, by lowering the urethane group content, the urea group content, and the acid value within the above-mentioned range, the weight ratio of the insoluble component can be reduced.

<Polyurethane resin (U1)>
The polyurethane resin (U1) in the present invention is a polyurethane resin obtained by neutralizing the acidic group of the polyurethane resin (U). Here, the acidic group of the polyurethane resin (U) is preferably an acidic group derived from the compound (A31) having an acidic group (carboxyl group or the like).

Examples of the neutralizing agent used for neutralizing the acidic group derived from the compound (A31) include ammonia, amine compounds having 1 to 20 carbon atoms, and hydroxides of alkali metals (sodium, potassium, lithium, etc.). ..

Examples of amine compounds having 1 to 20 carbon atoms include primary amines (monomethylamine, monoethylamine, monobutylamine, monoethanolamine, 2-amino-2-methyl-1-propanol, etc.) and secondary amines (dimethylamine, diethylamine). , Dibutylamine, diethanolamine, N-methyldiethanolamine, etc.) and tertiary amines (trimethylamine, triethylamine, dimethylethylamine, N, N-dimethylaminoethanol, triethanolamine, etc.) and the like.

Of these, amine compounds having a low vapor pressure at 25 ° C. are preferable from the viewpoint of the odor of the aqueous dispersion and the water resistance of the obtained film, and more preferable are triethylamine, monoethanolamine, diethanolamine and N-methyl. Diethanolamine, N, N-dimethylaminoethanol.

<Polyurethane resin aqueous dispersion (Q)>
The aqueous dispersion (Q) of the polyurethane resin (U) in the present invention can be produced by dispersing the polyurethane resin (U) and / or the polyurethane resin (U1) in water.

The polyurethane resin aqueous dispersion (Q) of the present invention, together with the polyurethane resin (U) and / or the polyurethane resin (U1), may be used as an antioxidant, an antioxidant, a weathering stabilizer, a plasticizer, a mold release agent, etc., if necessary. Additives can be included. The amount of these additives used is preferably 10% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less, based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1). ..

The polyurethane resin aqueous dispersion (Q) of the present invention is produced by producing the polyurethane resin (U) and / or the polyurethane resin (U1) by the following methods (1), (2), (3) or (4). It can be manufactured with.
(1) A method in which an active hydrogen component (A) and an organic polyisocyanate component (B) are collectively mixed, and after a urethanization reaction, the above-mentioned neutralizing agent is mixed if necessary and dispersed in an aqueous medium.
(2) A method in which the active hydrogen component (A) and the organic polyisocyanate component (B) are collectively mixed, the mixture is dispersed in water, a urethanization reaction is carried out, and the above-mentioned neutralizing agent is mixed if necessary.
(3) The urethane prepolymer (P) having an isocyanate group at the terminal obtained by reacting the active hydrogen component (A) [(A1) to (A3), etc.] with the organic polyisocyanate component (B), and the above-mentioned A method in which a neutralizing agent is mixed at a predetermined weight ratio, dispersed in water, and then (P) is extended with a chain extender (A4), and if necessary, a stop reaction is carried out with a reaction terminator (A5).
(4) A urethane prepolymer (P) having an isocyanate group at the terminal obtained by reacting an active hydrogen component (A) [(A1) to (A3), etc.] with an organic polyisocyanate component (B) is produced. Then, if necessary, an extension reaction is carried out with a chain extender (A4), and then a stop reaction is carried out with a reaction terminator (A5). Then, if necessary, the neutralizing agent is mixed in a predetermined weight ratio and dispersed in an aqueous medium.
Examples of the aqueous medium include water (pure water and the like) and a mixture of water and an organic solvent described later.

From the viewpoint of dispersibility of the polyurethane resin (U) and the polyurethane resin (U1) in water, it is preferable that the active hydrogen component (A) contains a compound (A3) containing a hydrophilic group and an active hydrogen atom. ..
The polyurethane resin aqueous dispersion (Q) in the present invention includes, if necessary, a urethane prepolymer (P) and a polyurethane resin from the viewpoint of dispersibility of the polyurethane resin (U) and the polyurethane resin (U1) and the stability of the aqueous dispersion. (U) and / or the polyurethane resin (U1) may be dispersed in water in the presence of the dispersant (g).

Dispersants (g) include nonionic surfactants (g1), anionic surfactants (g2), cationic surfactants (g3), amphoteric surfactants (g4) and other emulsified surfactants (g5). ). The dispersant (g) may be used alone or in combination of two or more.

Examples of the nonionic surfactant (g1) include an AO-added nonionic surfactant and a polyhydric alcohol-based nonionic surfactant. The AO addition type includes EO addition of an aliphatic alcohol having 10 to 20 carbon atoms, EO addition of phenol, EO addition of nonylphenol, EO addition of alkylamine having 8 to 22 carbon atoms, and EO addition of polypropylene glycol. Examples of the polyhydric alcohol type include fatty acid (8 to 24 carbon atoms) esters of polyhydric (3 to 8 or higher) alcohols (2 to 30 carbon atoms) (for example, glycerin monostearate and glycerin). Monooleate, sorbitan monolaurate, sorbitan monooleate, etc.) and alkyl (4 to 24 carbon atoms) poly (polymerization degree 1 to 10) glycoside and the like can be mentioned.

Examples of the anionic surfactant (g2) include ether carboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof [lauryl ether sodium acetate and (poly) oxyethylene (additional molars 1 to 100) lauryl ether. Sodium acetate, etc.]; Sulfate or ether sulfate having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof [sodium lauryl sulfate, (poly) oxyethylene (additional moles 1 to 100) sodium lauryl sulfate, (poly) ) Oxyethylene (additional moles 1 to 100) triethanolamine lauryl sulfate and (poly) oxyethylene (additional moles 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.]; Hydrocarbon groups having 8 to 24 carbon atoms Sulfate having (sodium dodecylbenzene sulfonate, etc.); sulfosuccinate having one or two hydrocarbon groups having 8 to 24 carbon atoms; phosphate ester or ether having a hydrocarbon group having 8 to 24 carbon atoms. Phosphate esters and their salts [sodium lauryl phosphate and (poly) oxyethylene (additional moles 1 to 100) sodium lauryl ether phosphate, etc.]; fatty acid salts having hydrocarbon groups with 8 to 24 carbon atoms [lauric acid] Sodium and triethanolamine laurate, etc.]; and acylated amino acid salts having a hydrocarbon group having 8 to 24 carbon atoms [sodium coconut oil fatty acid methyl taurine, sodium coconut oil fatty acid sarcosin sodium, coconut oil fatty acid sarcosin triethanolamine, N- Palm oil fatty acid acyl-L-glutamate triethanolamine, N-coconut oil fatty acid acyl-L-sodium glutamate, sodium lauroylmethyl-β-alanine, etc.] can be mentioned.

Examples of the cationic surfactant (g3) include quaternary ammonium salt type [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride and lanolin fatty acid ethyl sulfate aminopropylethyldimethylammonium, etc.] and amine salt type. [Diethylaminoethylamide stearate, dilaurylamine hydrochloride, oleylamine hydrochloride, etc.] can be mentioned.

Examples of the amphoteric tenside agent (g4) include betaine-type amphoteric tenside agents [coconut oil fatty acid amidopropyldimethylaminoacetate betaine, lauryldimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium. Betaine, laurylhydroxysulfobetaine, lauroylamide ethylhydroxyethylcarboxymethylbetaine sodium hydroxypropyl phosphate, etc.] and amino acid amphoteric tenside [β-laurylaminopropionate, etc.] can be mentioned.

Other emulsifying dispersants (g5) include, for example, polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, carboxyl group-containing (co) polymers such as sodium polyacrylate, and US Patent No. Examples thereof include the emulsion dispersant having a urethane group or an ester group described in 5906704 (for example, a polycaprolactone polyol and a polyether diol linked with a polyisocyanate).

The dispersant (g) may be used before the urethanization reaction of the polyurethane resin (U), during the urethanization reaction, after the urethanization reaction, before the water dispersion step of the polyurethane resin (U), during the water dispersion step, or after the water dispersion. Although it may be added at the appropriate time, it is preferable to add it before the water dispersion step or during the water dispersion step from the viewpoint of the dispersibility of the polyurethane resin (U) and the stability of the aqueous dispersion.

The content of the dispersant (g) is preferably 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, particularly preferably 0.01 to 10% by weight, based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1). Is 0.1 to 5% by weight.
The total weight of the constituent unit derived from the compound (A3) and the dispersant (g) in the polyurethane resin (U) and the polyurethane resin (U1) is based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1). It is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight, and particularly preferably 0.6 to 10% by weight.

The polyurethane resin aqueous dispersion (Q) in the present invention is an organic solvent [ketone solvent (eg acetone and methyl ethyl ketone), ester solvent (eg ethyl acetate), ether solvent (eg tetrahydrofuran), amide solvent (eg N, N-dimethylformamide and N-methylpyrrolidone), alcohol solvents (eg isopropyl alcohol) and aromatic hydrocarbon solvents (eg toluene)] may be included.

In the present invention, the polyurethane resin (U) and the urethane prepolymer (P) are obtained by heating the active hydrogen component (A) and the organic polyisocyanate component (B) in a heatable facility and reacting them. For example, a method in which a raw material of polyurethane resin (U) or urethane prepolymer (P) is charged in a container, uniformly stirred, and then heated in a heating dryer or a heating furnace without stirring, or a simple pressurizing reaction device (autoclave). , Kolben, a uniaxial or biaxial kneader, a plastic mill, a universal kneader, or the like, and a method of heating and reacting while stirring or kneading can be mentioned. Among them, the method of heating and reacting while stirring or kneading increases the homogeneity of the obtained polyurethane resin (U), and the mechanical properties, durability, chemical resistance, abrasion resistance, etc. of the obtained film are increased. Is preferred because it tends to be better.

The polyurethane resin (U) is preferably reacted at a ratio of an isocyanate group / active hydrogen atom equivalent ratio of 0.6 to 0.95.
Further, when the polyurethane resin (U) is produced by reacting the active hydrogen component (A) and the organic polyisocyanate component (B), the weight ratio of water in the reaction system is such that the urea group content is the above-mentioned preferable value. From the viewpoint of adjusting to 1.45% by weight or less based on the weight of the polyurethane resin (U), it is preferable.

The reaction temperature at the time of producing the polyurethane resin (U) and the urethane prepolymer (P) is 60 to 120 ° C. or 180 to 250 ° C. from the viewpoint of the content of the alohanate group and the burette group of the polyurethane resin (U). It is preferable, more preferably 60 to 110 ° C. or 180 to 240 ° C., and most preferably 60 to 100 ° C. or 180 to 230 ° C.
The time for producing the polyurethane resin (U) and the urethane prepolymer (P) can be appropriately selected depending on the equipment used, but is preferably 1 minute to 100 hours, more preferably 3 minutes to 30 hours. It is particularly preferably 5 minutes to 20 hours. Within this range, a polyurethane resin (U) capable of fully exerting the effects of the present invention can be obtained.

In order to control the urethanization reaction rate, known reaction catalysts (tin octylate, bismuth octylate, etc.), reaction retarders (phosphoric acid, etc.) and the like can be used. The amount of these catalysts or reaction retardants added is preferably 0.001 to 3% by weight, more preferably 0.005 to 2% by weight, and particularly preferably 0.01 to, based on the weight of the polyurethane resin (U). 1% by weight.

As a device for dispersing the polyurethane resin (U) or the urethane prepolymer (P) in water, any device having a dispersing ability can be used, but temperature control, supply of granular or block-shaped resin, dispersion ability, etc. From the viewpoint, it is preferable to use a rotary dispersion / mixing device, an ultrasonic dispersion / kneader, and a rotary dispersion / mixing device having a particularly excellent dispersion ability is more preferable.

The main dispersion principle of the rotary dispersion mixing device is that a shearing force is applied to the processed material from the outside by the rotation of the drive unit or the like to make the processed material into fine particles and disperse the particles. In addition, the rotary dispersion mixing device can be operated under normal pressure, reduced pressure or pressurization.

Examples of the rotary dispersion mixer include a mixer having general stirring blades such as Max Blend and helical blades, TK homomixer [manufactured by Primix Corporation], Clairemix [manufactured by M-Technique Co., Ltd.], and fill mix. [Primix Corporation], Ultra Turlux [IKA Co., Ltd.], Ebara Milder [Ebara Corporation], Cavitron (Eurotech Co., Ltd.) and Biomixer [Nippon Seiki Co., Ltd.], etc. Is exemplified.

From the viewpoint of dispersion capacity, the number of rotations when the polyurethane resin (U) or urethane prepolymer (P) is dispersed using the rotary dispersion mixing device is preferably 10 to 30,000 rpm, more preferably 20,000 to 20,000 rpm, and particularly. It is preferably 30 to 10000 rpm.

The main dispersion principle of the ultrasonic dispersion device is to apply energy from the outside to the processed material by the vibration of the drive unit to make it fine particles and disperse it. In addition, the ultrasonic disperser can be operated under normal pressure, reduced pressure or pressurization.

As the ultrasonic disperser, an ultrasonic disperser commercially available from Ikemoto Rika Kogyo Co., Ltd., Cosmo Bio Co., Ltd., Ginsen Co., Ltd., etc. can be used.

The frequency at which the polyurethane resin (U) or urethane prepolymer (P) is dispersed using the ultrasonic disperser is preferably 1 to 100 kHz, more preferably 3 to 60 kHz, particularly from the viewpoint of dispersion ability. It is preferably 10 to 30 kHz.

The main dispersion principle of the kneader is to knead the processed material in the rotating part of the kneader to give energy to make it into fine particles and disperse it. Further, the kneader can be operated under normal pressure, reduced pressure or pressurization.

As the kneading machine, a twin-screw extruder [PCM-30 manufactured by Ikegai Corp.], a kneader [KRC kneader manufactured by Kurimoto, Ltd., etc.], a universal mixer [Hibismix manufactured by Primix Corporation, etc.] and Plast mills [Lab plast mills manufactured by Toyo Seiki Seisakusho Co., Ltd., etc.] are exemplified.

From the viewpoint of dispersion capacity, the number of rotations when the polyurethane resin (U) or urethane prepolymer (P) is dispersed using a kneader is preferably 1 to 1000 rpm, more preferably 3 to 500 rpm, and particularly preferably 10. ~ 200 rpm.

The weight ratio of the polyurethane resin (U) or urethane prepolymer (P) supplied to the disperser to water is appropriately selected depending on the resin component content of the target aqueous dispersion, but is preferably [(U). Or (P)] / water = 10/2 to 10/100, more preferably 10/5 to 10/50.

The time for treating the polyurethane resin (U) or urethane prepolymer (P) and water in the disperser is preferably 10 seconds to 10 hours, more preferably 1 minute to 3 hours, most preferably from the viewpoint of dispersibility. Is 10 to 60 minutes.

When dispersing with a disperser, one kind of additive selected from pH adjusters, defoamers, antifoaming agents, antioxidants, anticoloring agents, plasticizers, mold release agents, etc. is used as necessary. The above can be added. Further, if necessary, solvent removal, concentration, dilution and the like may be performed after dispersion.

As a method of neutralizing the polyurethane resin (U) or urethane prepolymer (P) produced by the above reaction with the above-mentioned neutralizing agent to obtain a precursor of the polyurethane resin (U1) or the polyurethane resin (U1). , The above-mentioned neutralizing agent is added to a solution containing the polyurethane resin (U) or the urethane prepolymer (P), and the mixture is stirred at 10 to 50 ° C. for 10 to 180 minutes to obtain the polyurethane resin (U) or the urethane prepolymer (P). Examples thereof include a method of neutralizing the acidic group of P).

The device for reacting the chain extender (A4) and the reaction terminator (A5) after dispersing the urethane prepolymer (P) is not particularly limited, but the reaction is carried out while mixing with the disperser or a static mixer or the like. It is preferable to let it.

The polyurethane resin aqueous dispersion (Q) of the present invention is a polyurethane resin (U') other than the polyurethane resin (U) and the polyurethane resin (U1) as long as the effects of the present invention are not impaired, and a rheometer is used. It may contain a polyurethane resin (U'1) having a viscosity of more than 1,000,000 Pa · s at 25 ° C. measured at a shear rate of 0.1 / s.
From the viewpoint of paint gun cleaning property, the weight ratio of the polyurethane resin (U'1) is preferably 40% by weight or less based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1). It is preferably 10% by weight or less, particularly preferably 5% by weight or less, and most preferably 1% by weight or less.

From the viewpoint of chemical resistance and mechanical properties of the film, the polyurethane resin aqueous dispersion (Q) of the present invention contains a reactive group capable of reacting with an active hydrogen-containing group (hydroxyl group or the like) contained in the polyurethane resin (U). It is preferable to contain a cross-linking agent (C) having two or more of them.
In the polyurethane resin aqueous dispersion (Q) of the present invention, the mixture of the polyurethane resin (U) and the cross-linking agent (C) may form one particle, and the polyurethane resin (U) and the cross-linking agent (C) may be formed. ) May exist in the state of separate particles.
The cross-linking agent (C) can also be cross-linked with the acidic group of the polyurethane resin (U).

The cross-linking agent (C) is selected from the group consisting of a blocked isocyanate compound (c1), a melamine compound (c2), an oxazoline compound (c3), a carbodiimide compound (c4), an aziridine compound (c5) and an epoxy compound (c6). At least one cross-linking agent can be mentioned.

The blocked isocyanate compound (c1) is not particularly limited as long as it has two or more blocked isocyanate groups in the molecule, and for example, the polyisocyanate compound exemplified as the organic polyisocyanate component (B) is known as a blocking agent [ Phenols, secondary or tertiary alcohols, oximes, aliphatic or aromatic secondary amines, phthalate imides, lactams, active methylene compounds (malonic acid dialkyl esters, etc.), pyrazole compounds (Pyrazole and 3,5-dimethylpyrazole, etc.) and acidic sodium sulfite, etc.] and the like are blocked.

Commercially available blocked isocyanate compounds (c1) include Duranate series (Duranate 17B-60P, TPA-B80E, MF-B60B, MF-K60B, SBB-70P, SBN-70D, SBF-" manufactured by Asahi Kasei Chemicals Co., Ltd. 70E, E402-B80B, WM44-L70G, etc.) and the like.

The melamine compound (c2) is not particularly limited as long as it is a methylolated melamine compound or a methoxymethylolated melamine compound having two or more methylol groups or methoxymethylol groups in the molecule, and is, for example, the Uban series manufactured by Mitsui Chemicals Co., Ltd. [Uban 120, 20HS, 2021, 2028, 228, 2860, 22R, etc.], Cymel series manufactured by Nippon Cytec Co., Ltd. (Simel 202, 232, 235, 238, 254, 266, 267, 272, 285, 301, 303, 325, 327, 350, 370, 701, 703, 736, 738, 771, 114, 1156, 1158, etc.) and Sumitomo Chemical Co., Ltd.'s Sumimar series (Sumimar M-30W, M-50W, M- 55, M-66B, 50B, etc.).

The oxazoline compound (c3) is not particularly limited as long as it is a compound having two or more oxazoline groups (oxazoline skeleton) in the molecule, and is, for example, 2,2'-isopropyrinebis (4-phenyl-2-oxazoline) or the like. Compounds with two or more oxazoline groups; (co) polymers of polymerizable oxazoline compounds such as 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline and 2-vinyl-4-methyl-2-oxazoline; The polymerizable oxazoline compound and a copolymerizable monomer that does not react with the oxazoline group [(meth) methyl acrylate, (meth) ethyl acrylate, (meth) hydroxyethyl acrylate, polyethylene glycol (meth) acrylate, etc. Examples thereof include copolymers with (meth) acrylic esters, (meth) acrylic acid amidovinyl acetate, styrene, and α-methylstyrene styrene sulfonate sodium, etc.]. Examples of commercially available products of the oxazoline compound (c3) include "Epocross K-2010E", "Epocross K-2020E" and "Epocross WS-500" manufactured by Nippon Shokubai Co., Ltd.

The carbodiimide compound (c4) is not particularly limited as long as it is a compound having two or more carbodiimide groups in the molecule, for example, the aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms and an alicyclic having 8 to 18 carbon atoms. An aliphatic polycarbodiimide [poly (hexamethylene) obtained by polymerizing a formula polyisocyanate (b2), an aromatic aliphatic polyisocyanate (b3) having 10 to 17 carbon atoms or an aromatic polycarbodiimide (b4) having 8 to 22 carbon atoms. Carbodiimide), etc.], alicyclic polycarbodiimide [poly (4,4'-dicyclohexylmethanecarbodiimide), etc.] and aromatic polycarbodiimide [poly (p-phenylene carbodiimide), poly (4,4'-diphenylmethanecarbodiimide) and poly (Diisopropylphenylcarbodiimide), etc.]. Commercially available products of the carbodiimide compound (c4) include "carbodilite V-01", "carbodilite V02", "carbodilite V-03", "carbodilite V-04", and "carbodilite V-05" manufactured by Nisshinbo Holdings. Examples thereof include "carbodilite V-07", "carbodilite V-09", "carbodilite E-02", "carbodilite E-03A" and "carbodilite E-04".

The aziridine compound (c5) is not particularly limited as long as it is a compound having two or more aziridinyl groups in the molecule, and is, for example, tetramethylolmethanetris (β-aziridinyl propionate) and trimethylolpropane tris (β-azili). Ridinyl propionate).

The epoxy compound (c6) is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule, and is, for example, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and glycerol. Examples thereof include polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, trimethyl propane polyglycidyl ether, pentaerythritol polyglycidyl ether and polypropylene glycol diglycidyl ether.

The cross-linking agent (C) may be used alone or in combination of two or more.

The content of the cross-linking agent (C) in the polyurethane resin aqueous dispersion (Q) is preferably 30% by weight or less, more preferably 0.1 to 25% by weight, based on the solid content weight of the polyurethane resin aqueous dispersion (Q). %.

The solid content concentration [weight ratio of components (solid content) other than volatile components] of the polyurethane resin aqueous dispersion (Q) obtained by the production method of the present invention is preferably from the viewpoint of ease of handling of the aqueous dispersion. It is 20 to 65% by weight, more preferably 25 to 55% by weight. For the solid content concentration, about 1 g of the aqueous dispersion was thinly spread on a Petri dish, weighed precisely, and then heated at 130 ° C. for 45 minutes using a circulating constant temperature dryer, and then weighed and weighed before heating. It can be obtained by calculating the ratio (percentage) of the residual weight after heating to the weight.
Further, the ratio of the total weight of the polyurethane resin (U) contained in the polyurethane resin aqueous dispersion (Q) and the polyurethane resin (U) which is a precursor of the polyurethane resin (U1) is the ratio of the polyurethane resin aqueous dispersion (Q). Based on the weight of the solid content, it is preferably 15 to 100% by weight, more preferably 25 to 100% by weight, particularly preferably 40 to 100% by weight, and 55 to 100% by weight. Is most preferable.
Further, the ratio of the total weight of the polyurethane resin (U) contained in the polyurethane resin aqueous dispersion (Q) and the polyurethane resin (U) which is a precursor of the polyurethane resin (U1) is the ratio of the polyurethane resin aqueous dispersion (Q). Based on the weight obtained by subtracting the weight of the cross-linking agent (C) from the weight of the solid content, it is preferably 20 to 100% by weight, more preferably 30 to 100% by weight, and 45 to 100% by weight. Is particularly preferable, and 60 to 100% by weight is most preferable.

The viscosity of the polyurethane resin aqueous dispersion (Q) obtained by the production method of the present invention is preferably 10 to 100,000 mPa · s, more preferably 10 to 5,000 mPa · s. The viscosity is a value measured at a constant temperature of 25 ° C. using a BL type viscometer.

The pH of the polyurethane resin aqueous dispersion (Q) obtained by the production method of the present invention is preferably 2 to 12, more preferably 4 to 10. The pH is a value measured at 25 ° C. with pH Meter M-12 [manufactured by HORIBA, Ltd.].

<Use>
The polyurethane resin aqueous dispersion (Q) of the present invention is an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (binder composition for pigment printing, a binder composition for non-woven fabric, a bundling agent for reinforcing fibers). Compositions, binder compositions for antibacterial agents, raw material compositions for artificial leather / synthetic leather, etc.), water-based coating compositions (waterproof coating composition, water-repellent coating composition, antifouling coating composition, etc.), water-based paper treatment agents Although it can be used in compositions, water-based ink compositions, etc., it is particularly preferably used as a water-based paint composition, a water-based adhesive composition, and a water-based fiber processing agent composition because of its excellent film-forming property and water resistance. can do.

When used in these applications, if necessary, other additives such as coating resin, cross-linking agent, catalyst, pigment, pigment dispersant, viscosity modifier, defoamer, leveling agent, preservative, deterioration prevention One or more kinds of agents, stabilizers, antifreeze agents and the like can be added.

The preparation of the water-based paint using the polyurethane resin aqueous dispersion (Q) of the present invention will be described below.
In addition to the urethane resin (U) in the polyurethane resin aqueous dispersion (Q) of the present invention, other water-dispersible resins or water-soluble paints are used in the water-based paint, if necessary, for the purpose of assisting the formation of a coating film and improving the binder function. A resin may be used in combination.
Further, the polyurethane resin aqueous dispersion (Q) used for the aqueous coating material preferably contains the above-mentioned cross-linking agent (C).

Examples of other water-dispersible resins or water-soluble resins used in combination with water-based paints include water-dispersible or water-soluble polyurethane resins, polyacrylic resins, polyester resins, etc. other than the polyurethane resin in the present invention. These other resins can be appropriately selected from those commonly used in each application for each application of the water-based coating material.

The solid content of the polyurethane resin aqueous dispersion (Q) of the present invention in the aqueous coating material is preferably 0.1 to 60% by weight, more preferably 1 to 50% by weight, based on the weight of the aqueous coating material.
The content of the other resin in the water-based paint is preferably 60% by weight or less, more preferably 50% by weight or less, based on the weight of the water-based paint.

The amount of the cross-linking agent (C) added to the water-based paint is preferably 30% by weight or less, more preferably 0.1 to 20% by weight, based on the solid content weight of the water-based paint.

The water-based paint can further contain one or more kinds of pigments, pigment dispersants, viscosity modifiers, antifoaming agents, preservatives, deterioration inhibitors, stabilizers, antifreeze agents, water and the like.

Pigments include inorganic pigments having a solubility in water of 1 or less (for example, white pigments, black pigments, gray pigments, red pigments, brown pigments, yellow pigments, green pigments, blue pigments, purple pigments and metallic pigments) and organic pigments (for example, purple pigments and metallic pigments). For example, natural organic pigments, synthetic organic pigments, nitroso pigments, nitro pigments, pigment pigment type azo pigments, azo lakes made from water-soluble dyes, azo lakes made from sparingly soluble dyes, rakes made from basic dyes, rakes made from acidic dyes, and xanthan lakes. , Anthraquinone lake, pigments from bat dyes and phthalocyanine pigments) and the like. The content of the pigment is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of the aqueous paint.
Examples of the pigment dispersant include the above-mentioned dispersant (g), and the content of the pigment dispersant is preferably 20% by weight or less, more preferably 15% by weight or less, based on the weight of the pigment.

Viscosity adjusting agents include thickeners such as inorganic viscosity adjusting agents (sodium silicate, bentonite, etc.), cellulose-based viscosity adjusting agents (methyl cellulose having Mn of 20,000 or more, carboxymethyl cellulose, hydroxymethyl cellulose, etc.), and protein-based viscosity. Adjusters (casein, casein soda, ammonium casein, etc.), acrylics (sodium polyacrylate with Mn of 20,000 or more, ammonium polyacrylate, etc.) and vinyl viscosity adjusters (polyvinyl alcohol with Mn of 20,000 or more) Etc.).
Examples of the defoaming agent include long-chain alcohols (octyl alcohol and the like), sorbitan derivatives (sorbitan monooleate and the like), silicone oils (polymethylsiloxane and polyether-modified silicones and the like) and the like.

Examples of the preservative include an organic nitrogen-sulfur compound-based preservative and an organic sulfur halide-based preservative.
Examples of the deterioration inhibitor and stabilizer (ultraviolet absorber, antioxidant, etc.) include hindered phenol-based, hindered amine-based, hydrazine-based, phosphorus-based, benzophenone-based and benzotriazole-based deterioration inhibitor and stabilizer. ..
Examples of the antifreeze agent include ethylene glycol and propylene glycol.
The contents of the viscosity regulator, antifoaming agent, preservative, deterioration inhibitor, stabilizer and antifreeze agent are preferably 5% by weight or less, more preferably 3% by weight or less, respectively, based on the weight of the water-based paint. be.

A solvent may be further added to the water-based paint for the purpose of improving the appearance of the coating film after drying. Examples of the solvent to be added include monohydric alcohols having 1 to 20 carbon atoms (methanol, ethanol, propanol, etc.), glycols having 1 to 20 carbon atoms (ethylene glycol, propylene glycol, diethylene glycol, etc.), and 3 having 1 to 20 carbon atoms. Alcohols having a value higher than the value (glycerin, etc.) and cellosolves having 1 to 20 carbon atoms (methyl, ethyl cellosolves, etc.) and the like can be used. The content of the solvent to be added is preferably 20% by weight or less, more preferably 15% by weight or less, based on the weight of the aqueous coating material.

The aqueous coating material using the polyurethane resin aqueous dispersion (Q) of the present invention is produced by mixing and stirring the polyurethane resin aqueous dispersion (Q) of the present invention and each of the above-mentioned components. At the time of mixing, all the components may be mixed at the same time, or each component may be added stepwise and mixed.
The solid content concentration of the water-based paint is preferably 10 to 70% by weight, more preferably 15 to 60% by weight.

The aqueous adhesive using the polyurethane resin aqueous dispersion (Q) of the present invention will be described below.
As the resin used for the water-based adhesive, the polyurethane resin (U) and / or the polyurethane resin (U1) in the polyurethane resin aqueous dispersion (Q) of the present invention may be used as it is, but the SBR latex resin or acrylic resin may be used. A water-dispersible or water-soluble resin other than the typical polyurethane resin can be used in combination. When used in combination, the ratio of the total weight of the polyurethane resin (U) and the polyurethane resin (U1) to the total weight of the resin is preferably 1% by weight or more, more preferably 10% by weight or more.

Further, auxiliary materials and additives used in the adhesive, for example, a cross-linking agent, a plasticizer, and a tackifier, as long as the cohesiveness of the adhesive containing the polyurethane resin aqueous dispersion (Q) of the present invention is not impaired. , Fillers, pigments, thickeners, antioxidants, UV absorbers, surfactants, flame retardants and the like can also be used.

The base material (adhesive body) on which the adhesive is used is not particularly limited.
A laminate of adherends obtained using an adhesive is also included in the present invention.

Hereinafter, preparation of an aqueous fiber processing agent using the polyurethane resin aqueous dispersion (Q) of the present invention will be described.
The fiber processing agent containing the polyurethane resin aqueous dispersion (Q) of the present invention includes, if necessary, known defoaming agents, wetting agents, and various resin aqueous dispersions (polyurethane aqueous dispersions other than the present invention, acrylic aqueous dispersions). Body, SBR latex, etc.) and softeners, etc. can be blended. In the case of the aqueous resin dispersion, these blending amounts are preferably 30% by weight or less (more preferably 20% by weight or less) based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1) in terms of solid content. In the case of other additives, the content is preferably 1% by weight or less (more preferably 0.1 to 0.5% by weight).
Further, if necessary, a pH adjuster can be added. Examples of the pH adjuster include salts of alkaline substances such as strong bases (alkali metals and the like) and weak acids (acids having a pKa of more than 2.0, such as carbonic acid and phosphoric acid) (sodium bicarbonate and the like), or acidic substances (acetic acid and the like). Can be mentioned. The amount of the pH adjuster is preferably 0.01 to 0.3% by weight based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1).

The solid content (nonvolatile content) concentration of the aqueous fiber processing agent is not particularly limited, but is preferably 10 to 50% by weight, more preferably 15 to 45% by weight. The viscosity (25 ° C.) is preferably 10 to 100,000 mPa · s.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Hereinafter, the part means a weight part.

<Example 1>
A simple pressurizing reaction device equipped with a stirrer and a heating device is provided with a high molecular weight polyol (A1), a low molecular weight polyol (A2), a compound (A3), and an organic polyisocyanate as the active hydrogen component (A) shown in Table 1. The component (B) and the organic solvent were charged in the weights shown in Table 1 and stirred at 95 ° C. for 15 hours to carry out a urethanization reaction to produce an acetone solution of a polyurethane resin.
While stirring 500 parts of the obtained polyurethane resin acetone solution at 30 ° C., 5.09 parts of triethylamine was added as a neutralizing agent, homogenized at 60 rpm for 30 minutes, kept at 30 ° C., and stirred at 500 rpm. , The emulsification operation was carried out by gradually adding 651.56 parts of ion-exchanged water.
Next, after distilling off acetone at 65 ° C. for 12 hours under reduced pressure, ion-exchanged water was added as necessary, and the solid content concentration of the finally obtained polyurethane resin aqueous dispersion (Q) was 35. A polyurethane resin aqueous dispersion (Q-1) containing a polyurethane resin (U1) was obtained by performing a filtration operation in which the content was adjusted to be% by weight and filtered through a SUS mesh having a mesh size of 100 μm.

<Examples 2 to 11>
In Example 1, the types and weights of the active hydrogen component (A), the organic polyisocyanate component (B), the organic solvent, the neutralizing agent, and the ion-exchanged water were changed to the contents shown in Table 1, but the same as in Example 1. The same procedure was carried out to obtain polyurethane resin aqueous dispersions (Q-2) to (Q-11) containing a polyurethane resin (U1).
In Example 6, a chain extender (A4) as an active hydrogen component (A) was added.

<Example 12>
A simple pressurizing reaction device equipped with a stirrer and a heating device is provided with a high molecular weight polyol (A1), a low molecular weight polyol (A2), a compound (A3), and an organic polyisocyanate as the active hydrogen component (A) shown in Table 1. The component (B) and the organic solvent were charged in the weights shown in Table 1 and stirred at 95 ° C. for 15 hours to carry out a urethanization reaction, and the urethanization reaction was carried out. %) Was manufactured. The above isocyanate group content was measured in accordance with JIS K7301-1995, 6.3 Isocyanate group content.
The reaction terminator (A5) as the active hydrogen component (A) shown in Table 1 was added to the obtained urethane prepolymer acetone solution with stirring at 30 ° C., homogenized at 60 rpm for 60 minutes, and the polyurethane resin acetone solution was added. Manufactured.
While stirring the acetone solution of the obtained polyurethane resin at 30 ° C., 4.49 parts of triethylamine was added as a neutralizing agent, homogenized at 60 rpm for 30 minutes, kept at 30 ° C., and ionized under stirring at 500 rpm. The emulsification operation was carried out by gradually adding 628.83 parts of exchanged water.
Next, after distilling off acetone at 65 ° C. for 12 hours under reduced pressure, ion-exchanged water was added as necessary, and the solid content concentration of the finally obtained polyurethane resin aqueous dispersion (Q) was 35. A polyurethane resin aqueous dispersion (Q-12) containing a polyurethane resin (U1) was obtained by performing a filtration operation in which the content was adjusted to be% by weight and filtered through a SUS mesh having a mesh size of 100 μm.

<Examples 13 to 14 and 16>
In Example 12, except that the types and weights of the active hydrogen component (A), the organic polyisocyanate component (B), the organic solvent, the neutralizing agent and the ion-exchanged water were changed to the contents shown in Table 1, the same as in Example 12. The same procedure was carried out to obtain polyurethane resin aqueous dispersions (Q-13) to (Q-14) and (Q-16) containing a polyurethane resin (U1).

<Example 15>
In Example 12, the weights of the high molecular weight polyol (A1), the low molecular weight polyol (A2), the compound (A3), the organic polyisocyanate component (B), and the organic solvent as the active hydrogen component (A) are shown in Table 1. The same procedure as in Example 12 was carried out except that the contents were changed to produce an acetone solution of urethane prepolymer (isocyanate group content of the solution: 1.25% by weight).
A polyurethane resin aqueous dispersion containing a polyurethane resin (U1) was carried out in the same manner as in Example 12 except that the weights of the active hydrogen component (A5), the neutralizing agent and the ion-exchanged water were changed to the contents shown in Table 1. (Q-15) was obtained.

<Example 17>
A simple pressurizing reaction device equipped with a stirrer and a heating device is provided with a high molecular weight polyol (A1), a low molecular weight polyol (A2), a compound (A3), and an organic polyisocyanate as the active hydrogen component (A) shown in Table 1. The component (B) and the organic solvent were charged in the weights shown in Table 1 and stirred at 95 ° C. for 15 hours to carry out a urethanization reaction, and the urethanization reaction was carried out. %) Was manufactured.
While stirring the obtained urethane prepolymer acetone solution at 30 ° C., 4.72 parts of triethylamine was added as a neutralizing agent, homogenized at 60 rpm for 30 minutes, kept at 30 ° C., and stirred at 500 rpm. An aqueous solution in which 1.19 parts of a chain extender (A4) as an active hydrogen component (A), 8.06 parts of a reaction terminator (A5) as an active hydrogen component (A), and 622.55 parts of ion-exchanged water are mixed in advance. Was gradually added to the urethane prepolymer solution to carry out an emulsification operation.
Next, after distilling off acetone at 65 ° C. for 12 hours under reduced pressure, ion-exchanged water was added as necessary, and the solid content concentration of the finally obtained polyurethane resin aqueous dispersion (Q) was 35. A polyurethane resin aqueous dispersion (Q-17) containing a polyurethane resin (U1) was obtained by performing a filtration operation in which the content was adjusted to be% by weight and filtered through a SUS mesh having a mesh size of 100 μm.

<Example 18>
In Example 17, except that the types and weights of the active hydrogen component (A), the organic polyisocyanate component (B), the organic solvent, the neutralizing agent, and the ion-exchanged water were changed to the contents shown in Table 1, the same as in Example 17. The same procedure was carried out to obtain a polyurethane resin aqueous dispersion (Q-18) containing a polyurethane resin (U1).

<Example 19>
90 parts by weight of the polyurethane resin aqueous dispersion (Q-12) produced in Example 12 and 10 parts by weight of the polyurethane resin aqueous dispersion (Q'-1) produced in Comparative Example 1 below are mixed to obtain a polyurethane resin. A polyurethane resin aqueous dispersion (Q-19) containing (U1) was obtained.

<Comparative example 1>
The active hydrogen component (A), the organic polyisocyanate component (B) and the organic solvent shown in Table 2 were charged into a simple pressurizing reaction device equipped with a stirrer and a heating device at the weights shown in Table 2 at 95 ° C. The urethanization reaction was carried out with stirring for 15 hours to produce an acetone solution of a urethane prepolymer (resin having an isocyanate group at the terminal).
The obtained urethane prepolymer acetone solution was emulsified in the same manner as in Example 1 except that the weights of triethylamine and ion-exchanged water were changed to the weights shown in Table 2.
The obtained emulsion is stirred at 60 ° C. for 10 hours to carry out a chain extension reaction (extension reaction via a reaction between the isocyanate group of the urethane prepolymer and water), and then in the same manner as in Example 1. From the distillation operation of acetone to the filtration operation, a comparative polyurethane resin aqueous dispersion (Q'-1) containing a comparative polyurethane resin (U1') was obtained.

<Comparative Examples 2-3>
In Example 1, the types and weights of the active hydrogen component (A), the organic polyisocyanate component (B), the organic solvent, the neutralizing agent, and the ion-exchanged water were changed to the contents shown in Table 2, except that the contents were changed to those shown in Example 1. The same procedure was carried out to obtain comparative polyurethane resin aqueous dispersions (Q'-2) to (Q'-3) containing a comparative polyurethane resin (U1').

<Comparative example 4>
The active hydrogen component (A) shown in Table 2 was charged into a simple pressurizing reaction device equipped with a stirrer and a heating device at the weight shown in Table 2, and the pressure was reduced (1.3 kPa) at 120 ° C. for 3 hours. It was heated and stirred. After cooling to 25 ° C., the organic polyisocyanate component (B) shown in Table 2 was charged by the weight shown in Table 2 and stirred at 95 ° C. for 15 hours to carry out a urethanization reaction. After cooling to 25 ° C., the weights of acetone shown in Table 2 were added and stirred to prepare an acetone solution of a polyurethane resin.
Then, the emulsification operation was carried out in the same manner as in Example 1 except that triethylamine was not added and the weight of the ion-exchanged water was changed to the weight shown in Table 2.
After that, the steps from the distillation operation of acetone to the filtration operation were carried out in the same manner as in Example 1, and the polyurethane resin aqueous dispersion for comparison (Q'-4) containing the polyurethane resin for comparison (U1') was carried out. Got

The polymer polyols (A1) used in Examples 1 to 19 and Comparative Examples 1 to 4 are as follows.
PTMG650: [Mn = 650, Mw / Mn = 1.1 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation]
PTMG1000: [Mn = 1,000, Mw / Mn = 1.1 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation],
PTMG2000: [Mn = 2,000, Mw / Mn = 1.1 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Corporation]
Nieuport BPE-20T: [Mn = 321 and ethylene oxide adduct of bisphenol A having a hydroxyl value of 349 mgKOH / g, manufactured by Sanyo Chemical Industries, Ltd.]
Sanniks PP-2000: [Mn = 2,000 polyoxypropylene glycol, manufactured by Sanyo Chemical Industries, Ltd.]
PEG-1000: [Mn = 1,000 polyethylene glycol, manufactured by Sanyo Chemical Industries, Ltd.]

Various physical property values of the polyurethane resin aqueous dispersions (Q-1) to (Q-19) and (Q'-1) to (Q'-4) obtained in Examples 1 to 19 and Comparative Examples 1 to 4 and The evaluation results are shown in Tables 1 to 4. The methods for measuring and evaluating various physical property values are as follows.

<Urea group content and urea group content of polyurethane resins (U) and (U')>
The polyurethane resin aqueous dispersion (Q) or (Q') is poured into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, dried at 25 ° C. for 12 hours, and then heated at 105 ° C. for 3 hours in a circulation dryer. By drying, a polyurethane resin (U) or (U') for measurement was obtained.
The urethane group content and urea group content of the polyurethane resins (U) and (U') are quantified by the N atom content quantified by a nitrogen analyzer [ANTEK7000 (manufactured by Antec)] and ¹ H-NMR. It was calculated from the ratio of urethane group to urea group and the content of alohanate group and burette group described later.
^{1 1} H-NMR measurement was carried out by the method described in "Structural Study of Polyurethane Resin by NMR: Takeda Research Institute Bulletin 34 (2), 224-323 (1975)". That is, when ¹ H-NMR is measured and an aliphatic isocyanate is used, the urea group is derived from the ratio of the integrated amount of hydrogen derived from the urea group near the chemical shift of 6 ppm and the integrated amount of hydrogen derived from the urethane group near the chemical shift of 7 ppm. The weight ratio of the urethane group to the urethane group was measured, and the urethane group and urea group contents were calculated from the weight ratio, the N atom content, and the alohanate group and burette group contents. When aromatic isocyanate is used, the weight ratio of urea group to urethane group is calculated from the ratio of the integrated amount of hydrogen derived from the urea group near the chemical shift of 8 ppm and the integrated amount of hydrogen derived from the urethane group near the chemical shift of 9 ppm. The urethane group and urea group contents were calculated from the weight ratio, the N atom content, and the alohanate group and burette group contents.

<Contents of alohanate group and burette group>
The total content of the alohanate group and the burette group of the polyurethane resins (U) and (U') was calculated by a gas chromatograph [Shimadzu GC-9A {manufactured by Shimadzu Corporation}]. A 50 g DMF solution containing 0.01% by weight di-n-butylamine and 0.01% by weight naphthalene (internal standard) was prepared. The sample was measured in a test tube with a stopper, 2 g of the above DMF solution was added, and the test tube was heated in a constant temperature water tank at 90 ° C. for 2 hours. After cooling to room temperature, 10 μl of acetic anhydride was added, and the mixture was shaken and stirred for 10 minutes. Further, 50 μl of di-n-propylamine was added, and the mixture was shaken for 10 minutes, and then gas chromatograph measurement was performed. In parallel, blank measurement was performed, the consumption of amine was determined from the difference from the test value, and the total content of alohanate group and burette group was measured.
(Gas chromatograph conditions)
Equipment: Shimadzu GC-9A
Column: 10% PEG-20M on Chromosorb WAW DMLS 60/80 mesh glass column 3mmφ x 2m
Column temperature: 160 ° C, sample introduction temperature: 200 ° C, carrier gas: nitrogen 40 ml / min Detector: FID, sample injection amount: 2 μl
(Calculation formula for the total content of alohanate group and burette group)
Total content of alohanate group and burette group = {(BA) / B} × 0.00155 / S
A: (Peak area of di-n-butylacetamide / Peak area of naphthalene) of sample
B: Blank (peak area of di-n-butylacetamide / peak area of naphthalene)
S: Polyurethane resin collection amount (g)

<Mw and Mn measurement method>
Polyurethane resin (U) or (U') or high molecular weight polyol is added to DMF so that the solid content is 0.125% by weight, and after stirring and dissolving at room temperature for 1 hour, a filter having a pore size of 0.3 μm is used. After filtration, the components Mw and Mn contained in the obtained filtrate were measured by GPC using DMF as a solvent and polystyrene as a molecular weight standard.
When the sample is dissolved in DMF so that the solubility of the sample in the solvent used for measurement is less than 90% by weight [0.125% by weight of solid content concentration], the sample actually dissolved is 0.1125% by weight (= 0.125% by weight). If it is less than × 0.90)], the measurement accuracy of GPC is lowered. In that case, since it is difficult to accurately measure the molecular weight, the molecular weight of the polyurethane resin is defined as infinite "∞".
(GPC measurement conditions)
Equipment: "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: "Guardcolumn α" + "TSKgel α-M" [both manufactured by Tosoh Corporation]
Sample solution: 0.125 wt% dimethylformamide solution Eluent: Dimethylformamide solution Injection volume: 100 μL
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) [manufactured by Tosoh Corporation]

<Measuring method of weight ratio of insoluble components of polyurethane resin (U) and (U')>
The polyurethane resin aqueous dispersion (Q) or (Q') is poured into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, dried at 25 ° C. for 12 hours, and then heated at 105 ° C. for 3 hours in a circulation dryer. By drying, a polyurethane resin (U) or (U') for measurement was obtained. 1 g of the obtained polyurethane resin (referring to this weight as W) is placed in a pressure-resistant airtight container having an inner diameter of 6 cm and a depth of 12 cm together with a stirrer chip having a length of 3 cm. Was added, and the mixture was stirred at 80 ° C. for 180 minutes to obtain a mixed solution.
The obtained mixed solution is filtered through a SUS mesh (opening 75 μm) whose weight (W1) has been measured in advance, and then the filtration residue is washed with acetone at 25 ° C. (same weight as acetone charged in a pressure-resistant airtight container: 10 g). bottom. The filtration residue and the SUS mesh were dried at 105 ° C. for 30 minutes, and then the total weight (W2) was measured. The amount of insoluble matter was calculated by the following formula.
Weight ratio of insoluble component (%) = {(W2-W1) / W} x 100

<Measuring method of viscosity of polyurethane resin (U) and (U')>
The polyurethane resin aqueous dispersion (Q) or (Q') is poured into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, dried at 25 ° C. for 12 hours, and then heated at 105 ° C. for 3 hours in a circulation dryer. By drying, a polyurethane resin (U) or (U') for measurement was obtained.
The resin viscosity of the obtained polyurethane resin was measured using a rheometer (“MCR-302” manufactured by AntonioPaar).
(Measurement condition)
Measuring jig: Parallel plate "PP-08" (diameter 8 mm)
Distance between plates: 0.5 mm
Measurement temperature: 25 ° C
Measurement mode: Rotational shear rate: 0.1 / sec When the obtained polyurethane resin was filmed and the viscosity could not be measured under the above conditions, the resin viscosity was indicated as "∞".

<Acid value and hydroxyl value of polyurethane resin>
The polyurethane resin aqueous dispersion (Q) or (Q') is poured into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, dried at 25 ° C. for 12 hours, and then heated at 105 ° C. for 3 hours in a circulation dryer. By drying, a polyurethane resin (U) or (U') for measurement was obtained.
The acid value and hydroxyl value of the polyurethane resins (U) and (U') were measured according to JIS K0070 (1992).

<Evaluation method of storage stability>
A mixture was obtained by mixing 3.5 parts of "Cymel202" (manufactured by ALLNEX) and 72 parts of a polyurethane resin aqueous dispersion under stirring at 25 ° C. and 2000 rpm. The viscosity of the mixture was measured (V1). The mixture was stored at 40 ° C. for 10 days and then the viscosity was measured (V2). The thickening rate was calculated by the following formula, and the storage stability was evaluated according to the following criteria.
Thickening rate (%) = (V2-V1) / V1 × 100
◯: -50% ≤ thickening rate ≤ + 50%
Δ: -100% ≤ thickening rate <-50% or + 50% <thickening rate ≤ + 100%
X: thickening rate <-100% or + 100% <thickening rate

<Viscosity measurement conditions>
Measuring equipment: B-type viscometer Rotation speed: 60 rpm

<Evaluation method of paint gun cleaning property>
70 parts of rutile-type titanium dioxide, 10 parts of "Disperbyk 190" (manufactured by Big Chemie Japan) and 34.3 parts of ion-exchanged water were premixed and then dispersed with a paint shaker for 30 minutes to obtain a pigment-dispersed paste. 205.71 parts of urethane resin aqueous dispersion and 10 parts of "Cymel202" were added to the obtained pigment paste and mixed uniformly to obtain a paint for evaluating paint gun detergency.
Using a metallic bell (manufactured by ABB), the paint is discharged for 10 seconds under the conditions of an applied voltage of -90 kV, a rotation speed of 30,000 rpm, and a discharge rate of 200 cc / min. / Butyl cellosolve / N, N-dimethylethanolamine = 85/14/1 (weight ratio)) was discharged for 10 seconds, and the state of removal of the paint when washed was evaluated according to the following criteria.
⊚: There is no paint residue inside the bell, and there is no paint residue in the discharge hole.
◯: There is no paint residue on the inside of the bell, and the paint residue on the discharge hole is at a level where there is no problem with painting.
Δ: A little paint remains on the inside of the bell, and a little paint remains on the discharge hole.
X: A considerable amount of paint remains on the inside of the bell and in the discharge hole.

<Evaluation method of coating film appearance>
A commercially available cationic electrodeposition coating test piece is coated with the above-mentioned coating gun detergency evaluation paint by air spray coating so that the film thickness is 20 μm, preheated at 80 ° C. for 5 minutes, and then 30 at 140 ° C. The test piece was heat-cured for 1 minute to obtain a test piece on which a coating film was formed. The quality (◯ or ×) of the appearance of the coating film on the test piece was visually evaluated.

<Evaluation method of water resistance>
3.3 parts of "Cymel 327" and 20 parts of the polyurethane resin aqueous dispersion were mixed under stirring at 25 ° C. and 2000 rpm to obtain a mixture.
The mixture is applied to a commercially available cationic electrodeposition coating test piece by air spray coating to a thickness of 20 μm, preheated at 80 ° C. for 5 minutes, and then heat-cured at 140 ° C. for 30 minutes to obtain a coating film. Obtained. The obtained coating film was immersed in warm water at 40 ° C. for 240 hours, pulled up, and the surface moisture was removed with a dry cloth, and then dried at 25 ° C. for 2 hours.
Subsequently, six orthogonal cuts were made in each of the vertical and horizontal directions at 1 mm intervals on the coating film surface, and then a peeling test was performed with cellophane tape (registered trademark) to check the number of remaining 1 mm square coating films. Adhesion was evaluated according to the following criteria.
⊚: Residual number 24 or more ○: Residual number 20 or more and less than 24 Δ: Residual number 15 or more and less than 20 ×: Residual number less than 15

<Evaluation method for heat-resistant water adhesion>
The coating film for evaluation of water resistance and adhesion was immersed in warm water at 80 ° C. for 168 hours, pulled up, and the surface moisture was removed with a dry cloth, and then dried at 25 ° C. for 2 hours.
Subsequently, six orthogonal cuts were made in each of the vertical and horizontal directions at 1 mm intervals on the coating film surface, and then a peeling test was performed with cellophane tape (registered trademark) to check the number of remaining 1 mm square coating films. Adhesion was evaluated according to the following criteria.
⊚: Residual number 24 or more ○: Residual number 20 or more and less than 24 Δ: Residual number 15 or more and less than 20 ×: Residual number less than 15

The polyurethane resin aqueous dispersion of the present invention is excellent in storage stability and detergency after using a coating gun, and can obtain a film having excellent appearance after coating, water resistance and water resistance, and thus has a coating composition. It can be suitably used for products, adhesive compositions, fiber processing agent compositions and the like.

Claims

The polyurethane resin (U) having an acidic group containing the active hydrogen component (A) and the organic polyisocyanate component (B) as essential constituent monomers and / or the acidic group of the polyurethane resin (U) is neutralized. A polyurethane resin aqueous dispersion containing a polyurethane resin (U1) and an aqueous medium.
The polyurethane resin (U) has a hydroxyl group and has
The polyurethane resin (U) has an acid value of 5 to 18 mgKOH / g.
A polyurethane resin aqueous dispersion (Q) having a viscosity of the polyurethane resin (U) of 100 to 1,000,000 Pa · s at 25 ° C. measured at a shear rate of 0.1 / s using a rheometer.
The weight ratio of the insoluble component generated when the polyurethane resin (U) and acetone having a weight 10 times that of the polyurethane resin (U) are stirred at 80 ° C. for 180 minutes in a hermetically sealed manner is the weight of the added polyurethane resin (U). The polyurethane resin aqueous dispersion according to claim 1, which is 5% by weight or less as a reference.
The polyurethane resin aqueous dispersion according to claim 1 or 2, wherein the urethane group content of the polyurethane resin (U) is 1.0 to 3.5 mmol / g based on the weight of (U).
The polyurethane resin aqueous dispersion according to any one of claims 1 to 3, wherein the polyurethane resin (U) has a urea group content of 0.8 mmol / g or less based on the weight of (U).
The polyurethane resin aqueous dispersion according to any one of claims 1 to 4, wherein the polyurethane resin (U) has a hydroxyl value of 15 to 100 mgKOH / g.
The polyurethane resin aqueous dispersion according to any one of claims 1 to 5, wherein the active hydrogen component (A) contains a polyether polyol having a number average molecular weight of 500 or more.
Claims 1 to 6 in which the organic polyisocyanate component (B) contains a chain aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms and / or an alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms. The polyurethane resin aqueous dispersion according to any one of the above items.
Further, at least one cross-linking agent selected from the group consisting of a blocked isocyanate compound (c1), a melamine compound (c2), an oxazoline compound (c3), a carbodiimide compound (c4), an aziridine compound (c5) and an epoxy compound (c6). The polyurethane resin aqueous dispersion according to any one of claims 1 to 7, which contains (C).