JP6965329B2 - Polyurethane resin aqueous dispersion and printing ink using it - Google Patents

Description

The present invention relates to a polyurethane resin aqueous dispersion and a printing ink using the same.

Polyurethane resins are widely used as binder resins for paints, printing inks, adhesives, etc. because they have excellent flexibility, chemical resistance, and mechanical strength. Further, in recent years, there is an increasing need for a water-dispersible polyurethane resin having less VOC in the drying process due to environmental considerations.

In general, polyurethane resin has excellent adhesion to polar substrates such as polyester and nylon due to polar groups such as urethane group and urea group, but adheres to low polar substrates such as polyethylene and polypropylene. The sex is inadequate.
In order to solve such a problem, for example, an aqueous polyurethane resin (Patent Document 1) in which an amine having a long-chain alkyl group and an oxyalkylene group is used as a neutralizing agent for an anionic group in the polyurethane resin, or acid anhydride is used. A urethane-modified polyolefin resin (Patent Document 2) in which a non-chlorine-based polyolefin resin having a physical group is reacted with a polyurethane resin having a primary and / or a secondary amino group has been proposed. It is not possible to satisfy both the adhesion to a polar substrate and the adhesion to a low polar substrate such as OPP.
Further, in applications such as printing inks, polyurethane resin is required to have scratch resistance of images in addition to adhesion, but conventional printing inks using polyurethane resins are required to satisfy scratch resistance of images. There wasn't.

Japanese Patent No. 4573155 Japanese Unexamined Patent Publication No. 2018-2896

The present invention has been made in view of the above problems, and the obtained dry film has excellent adhesion to both polar substrates such as PET and nylon and low polar substrates such as OPP. However, it is an object of the present invention to provide an aqueous dispersion of a polyurethane resin having excellent scratch resistance.

The present inventors have arrived at the present invention as a result of diligent studies to achieve the above object. That is, the present invention comprises a polyurethane resin (U) obtained by reacting an active hydrogen atom-containing component (A) containing a polymer polyol component (a1) having a number average molecular weight of 500 or more with an organic polyisocyanate component (B). A polyurethane resin aqueous dispersion containing an aqueous medium, wherein the polymer polyol component (a1) is a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2). Containing a polyolefin polyol (a11) and a polyester polyol (a12) having a structural unit represented by the chemical formula (3), the structural unit and the general formula represented by the general formula (1) in the polyurethane resin (U). The total weight ratio of the structural units represented by (2) is 11 to 55% by weight based on the weight of (U), and the structural units represented by the chemical formula (3) in the polyurethane resin (U). weight ratio of 4 to 40 wt% der Ru polyurethane resin aqueous dispersion based on the weight of the (U) (Q); a printing ink containing the polyurethane resin aqueous dispersion (L).

［式中、Ｒ^１は水素原子、メチル基、エチル基、ビニル基、イソプロピル基又はイソプロ
ペニル基を表し、Ｒ^２は水素原子又はメチル基を表す。］

[In the formula, R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a vinyl group, an isopropyl group or an isopropenyl group, and R ² represents a hydrogen atom or a methyl group. ]

［式中、Ｒ^３は水素原子又はメチル基を表す。］

[In the formula, R ³ represents a hydrogen atom or a methyl group. ]

The dry film obtained from the polyurethane resin aqueous dispersion (Q) of the present invention has excellent adhesion to both polar substrates such as PET and nylon and low polar substrates such as OPP, and is scratch resistant. Excellent in sex.

The polyurethane resin aqueous dispersion (Q) of the present invention is a polyurethane resin (U) obtained by reacting an active hydrogen atom-containing component (A) containing a polymer polyol component (a1) with an organic polyisocyanate component (B). Contains an aqueous medium.

The active hydrogen atom-containing component (A) containing the high molecular weight polyol component (a1) having a number average molecular weight of 500 or more includes a hydroxyl group-containing compound in addition to the high molecular weight polyol component (a1) having a number average molecular weight of 500 or more. Examples thereof include nitrogen atom-containing compounds, carboxyl group-containing compounds, thiol group-containing compounds, phosphate group-containing compounds, and compounds having two or more types of active hydrogen atom-containing functional groups in the molecule.

Examples of the active hydrogen atom-containing component containing a hydroxyl group include water and a compound having at least one or more hydroxyl groups in one molecule. For example, as a compound having one hydroxyl group in one molecule, an aliphatic hydrocarbon-based alcohol having a linear or branched structure such as methanol, ethanol, propanol, butanol, octanol, and stearyl alcohol, cyclohexanol, cyclohexanemethanol, and iso Examples thereof include hydrocarbon-based alcohols having an alicyclic structure such as Bornyl alcohol, aromatic hydrocarbon-based alcohols such as benzyl alcohol, and the like.
Polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl glycol, and 1,4-bis. Dihydric alcohols such as (hydroxymethyl) cyclohexane, 1,4-bis (hydroxyethyl) benzene, 2,2-bis (4,4'-hydroxycyclohexyl) propane, trihydric alcohols such as glycerin and trimethylolpropane, penta Examples thereof include 4- to 8-valent alcohols such as erythritol, diglycerin, α-methylglucoside, sorbitol, xylit, mannit, dipentaerythritol, glucose, fructose and sucrose.
Examples of the polyvalent phenol include pyrogallol, catechol, hydroquinone and the like, and examples of the bisphenol include bisphenol A, bisphenol F and bisphenol S.

Active hydrogen atom-containing components containing nitrogen atoms include ammonia, alkylamine compounds having 1 to 20 carbon atoms (butylamine, etc.), monoamine compounds (aniline, etc.), and polyamine compounds include aliphatic polyamines (ethylenediamine, trimethylenediamine, etc.). Hexamethylenediamine, diethylenetriamine, etc.), piperazine, heterocyclic polyamine compound (N-aminoethylpiperazin, etc.), alicyclic polyamine (dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamine (phenylenediamine, tolylenediamine, diethyl) Tolylene diamine, xylylene diamine, diphenylmethanediamine, diphenyletherdiamine, polyphenylmethanepolyamine, etc.), alkanolamine compounds as aminoalcohol compounds (monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, etc.), and dicarboxylics as others. Polyamide polyamines, polyether polyamines, hydrazine compounds (hydrazine, monoalkylhydrazine, etc.) and dihydrazide compounds (dihydrazide succinate, dihydrazide adipate, dihydrazide isophthalate, dihydrazide terephthalate, etc.) obtained by condensing an acid with an excess polyamine compound. , Guanidin compounds (butylguanidine, 1-cyanoguanidine, etc.), dicyandiamide and the like, and mixtures of two or more thereof.

Examples of the phosphoric acid compound containing 2 to 8 active hydrogen atoms having a phosphoric acid group include phosphoric acid, phosphite, and phosphonic acid.

The polymer polyol component (a1) in the present invention has a number average molecular weight (hereinafter abbreviated as Mn) having a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2). It contains 500 or more polyolefin polyols (a11) and polyester polyols (a12) having a number average molecular weight (hereinafter abbreviated as Mn) of 500 or more and having a structural unit represented by the chemical formula (3) as essential components.
Since (a1) contains (a11) and (a12), it has excellent adhesion to both polar substrates such as PET and nylon and low polar substrates such as OPP, and has scratch resistance. An excellent polyurethane resin can also be obtained.

In the general formula (1), R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a vinyl group, an isopropyl group or an isopropenyl group, and R ² represents a hydrogen atom or a methyl group. When the polyolefin polyol (a11) contains three or more consecutive methylene groups, it is interpreted that there is a structural unit (ethylene group) ^{in which R 1} and R ^{2 in the general formula (1) are hydrogen atoms.} ..

^{R 3} in the general formula (2) represents a hydrogen atom or a methyl group.

The polyolefin polyol (a11) is not particularly limited as long as it is a polyolefin polyol having a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2), and specifically, polybutadiene. Acid-modified polyolefins and aminos obtained by modifying polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols, and polyolefins described in, for example, JP-A-2018-0764428 with unsaturated (poly) carboxylic acids (anhydrides). Examples thereof include hydroxyl group-modified polyolefins that can be obtained by reacting with alcohol. In (a11), one type may be used alone or two or more types may be used in combination.

Commercially available products of polyolefin polyol (a11) include, for example, NISSO-PB G series [polybutadiene polyol, manufactured by Nippon Soda Co., Ltd.], Poly bd series [polybutadiene polyol, manufactured by Idemitsu Kosan Co., Ltd.], NISSO-PB GI series. [Water-added polybutadiene polyol, manufactured by Nippon Soda Co., Ltd.], Polytail H [Water-added polybutadiene polyol, manufactured by Mitsubishi Chemical Co., Ltd.], Polyip series [Polyisoprene polyol, manufactured by Idemitsu Kosan Co., Ltd.], EPOL series [Water Additive polyisoprene polyol, manufactured by Idemitsu Kosan Co., Ltd.] and the like.

Among the polyolefin polyols (a11), those having a structural unit represented by the general formula (1) are preferable from the viewpoint of adhesion and scratch resistance of the polyurethane resin (U) to a low-polarity substrate such as OPP. Polyolefin polyols are more preferable, and polyolefin polyols having the following structural units (i) and / or (ii), and polyolefin polyols having the following structural units (iii) and (iv), and particularly preferable are the following structural units (i). ) And / or a polyolefin polyol having (ii), most preferably a hydrogenated polybutadiene polyol.
-Structural unit (i): R ¹ in the general formula (1) is an ethyl group and R ² is a hydrogen atom.-Structural unit (ii): R ¹ in the general formula (1) is a hydrogen atom and R ² is. Structural unit / structural unit (iii) in which two structural units that are hydrogen atoms are connected: Structural unit / structural unit (iv) ^{in which R 1} is a vinyl group and R ^{2 is a hydrogen atom in the general formula (1): general Constituent unit in which R 3} in equation (2) is a hydrogen atom

The total weight ratio of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the polyurethane resin (U) is a polar group such as PET or nylon of the polyurethane resin (U). From the viewpoint of achieving both adhesion to a material and a low polar group such as OPP and scratch resistance, it is preferably 15 to 55% by weight, more preferably 20 to 50% by weight, based on the weight of (U). Particularly preferably, it is 30 to 50% by weight.
The structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) are preferably structural units derived from the polyolefin polyol (a11).

The polyester polyol (a12) is not particularly limited as long as it is a polyester polyol containing a structural unit represented by the chemical formula (3), and is obtained, for example, by dehydration condensation of terephthalic acid and a polyhydric alcohol having 2 to 20 carbon atoms. Examples thereof include polyester polyols and terephthalic acids, polyvalent carboxylic acids having 4 to 20 carbon atoms other than terephthalic acid, or ester-forming derivatives thereof, and polyester polyols obtained by dehydration condensation of polyhydric alcohols having 2 to 20 carbon atoms. In (a12), one type may be used alone or two or more types may be used in combination.

As the polyhydric alcohol having 2 to 20 carbon atoms, a linear diol having 2 to 12 carbon atoms or an aliphatic diol having 3 to 12 carbon atoms having a branch [ethylene glycol, 1,3-propylene glycol, 1,4-butane] Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol and Linear alcohols such as tetraethylene glycol; 1,2-propylene glycol, 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2, 2-Diethyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,6-hexanediol, 3-methyl-1, 6-hexanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 2-methyl-1,8-octanediol, 3 -Branched alcohols such as methyl-1,8-octanediol and 4-methyloctanediol]; alicyclic diols with 6 to 20 carbon atoms [1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1, 4-Cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornandiol, tetrahydrofuran dimethanol, 1, 4-Bis (Hydroxyethoxy) Cyclohexane, 1,4-Bis (Hydroxymethyl) Cyclohexane and 2,2-Bis (4-Hydroxycyclohexyl) Propane, etc.]; -Xylylene glycol, bis (hydroxyethyl) benzene and bis (hydroxyethoxy) benzene, etc.]; Triols with 3 to 20 carbon atoms [aliphatic triols (glycerin, trimethylolpropane, etc.), etc.]; 4 with 5 to 20 carbon atoms ~ Octahydric alcohols [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.); sugars (sucrose, glucose, mannose, etc.)
Fructose, methylglucoside and its derivatives)]; and the like. Of these, an aliphatic diol having a branch and having 3 to 12 carbon atoms is preferable from the viewpoint of the flexibility and adhesion of the polyurethane resin (U).

Examples of polyvalent carboxylic acids having 4 to 20 carbon atoms other than terephthalic acid or ester-forming derivatives thereof include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebatic acid, fumaric acid, maleic acid, etc.) and alicyclic. Formula Dicarboxylic acid (dimeric acid, etc.), aromatic dicarboxylic acid excluding terephthalic acid (phthalic acid, isophthalic acid, etc.), trivalent or higher polycarboxylic acid (trimeritic acid, pyromellitic acid, etc.), anhydrides thereof (Succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), their acid halides (dichloroide adipate, etc.), these low molecular weight alkyl esters (dimethyl succinate, dimethyl phthalate, etc.), and these Can be mentioned. Of these, an aliphatic dicarboxylic acid and an ester-forming derivative thereof are preferable from the viewpoint of the flexibility and adhesion of the polyurethane resin (U).

The weight ratio of the structural unit represented by the chemical formula (3) in the polyurethane resin (U) is the adhesion and abrasion resistance of the polyurethane resin (U) to polar substrates such as PET and nylon and low polar groups such as OPP. From the viewpoint of achieving both properties, it is preferably 4 to 40% by weight, more preferably 7 to 30% by weight, and particularly preferably 10 to 25% by weight, based on the weight of (U).
The structural unit represented by the chemical formula (3) is preferably a structural unit derived from the polyester polyol (a12).

(A1) in the present invention may contain a polymer polyol (a13) other than (a11) and (a12). Examples of (a13) include polyester polyols with Mn500 or higher (a131), polyether polyols with Mn500 or higher (a132), and the like. In (a13), one type may be used alone or two or more types may be used in combination.

Examples of the polyester polyol (a131) include condensed polyester polyols other than (a12), polylactone polyols, polycarbonate diols, castor oil-based polyols, and the like.

The condensed polyester polyol other than (a12) is obtained by dehydration condensation of the polyhydric alcohol having 2 to 20 carbon atoms and a polyvalent carboxylic acid having 4 to 20 carbon atoms other than terephthalic acid or an ester-forming derivative thereof. Examples thereof include polyester polyols and the like.

Commercially available condensed polyester polyols include Sun Esther 2610 [Mn = 1000 polyethylene adipate diol, manufactured by Sanyo Kasei Kogyo Co., Ltd.], Sun Esther 4620 [Mn = 2000 polytetramethylene adipate diol], and Sun Esther 2620 [. Mn = 2000 polyethylene adipate diol, manufactured by Sanyo Kasei Kogyo Co., Ltd.], Clare polyol P-2010 [Mn = 2000 poly-3-methyl-1,5-pentane adipate diol], Clare polyol P-3010 [Mn = 3000 poly-3-methyl-1,5-pentaneadipatediol] and Clare polyol P-6010 [Mn = 6000 poly-3-methyl-1,5-pentaneadipatediol] and the like.

The polylactone polyol is a heavy adduct of lactone to the polyhydric alcohol having 2 to 20 carbon atoms, and the lactone includes lactones having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ-valerolactone and ε-caprolactone). ) Etc. can be mentioned.
Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, polycaprolactone triol and the like.

Examples of the polycarbonate diol include one or more of the polyhydric alcohols having 2 to 20 carbon atoms, a low molecular weight carbonate compound (for example, a dialkyl carbonate having 1 to 6 carbon atoms in an alkyl group, and an alkylene having 2 to 6 carbon atoms. Examples thereof include polycarbonate polyols produced by condensing alkylene carbonates having a group and diaryl carbonates having an aryl group having 6 to 9 carbon atoms while undergoing a dealcohol reaction.

Commercially available products of polycarbonate diol include Duranol T6002 [Mn = 2000 polycarbonate diol using 1,6-hexanediol, manufactured by Asahi Kasei Chemicals Co., Ltd.], and Mn using ETERNALCOL UH-300 [1,6-hexanediol]. = 3000 Polycarbonatediol, manufactured by Ube Kosan Co., Ltd.], ETERNALCOLL UM-90 (1/3) [Mn using 1,4-cyclohexanedimethanol / 1,6-hexanediol = 1/3 (molar ratio) = 900 polycarbonate diol, manufactured by Ube Kosan Co., Ltd.], Mn = 2000 polycarbonate diol using Duranol G4672 [1,4-butanediol / 1,6-hexanediol = 70/30 (molar ratio), Asahi Kasei Chemicals Made by Duranol T5652 [1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio) of Mn = 2000 polycarbonate diol, Asahi Kasei Chemicals Co., Ltd.], Clare polyol C-2090 [Mn = 2000 polycarbonate diol using 3-methyl-1,5-pentanediol / 1,6-hexanediol = 90/10 (molar ratio), manufactured by Kuraray Co., Ltd.], Kurare polyol C- Examples thereof include 2050 [polypolydiol of Mn = 2000 using 3-methyl-1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio), manufactured by Kuraray Co., Ltd.] and the like.

The castor oil-based polyol includes castor oil and a modified castor oil modified with a polyol or an alkylene oxide having 2 to 12 carbon atoms (hereinafter, abbreviated as 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 ethylene oxide (hereinafter abbreviated as EO) adducts (additional moles: 4 to 30 mol) of castor oil. ..

Examples of AO having 2 to 12 carbon atoms include EO, propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, and α-olefin oxide. , Styrene oxide, epichlorohydrin (epicchlorohydrin, etc.) and the like.

Examples of the polyether polyol (a132) include an aliphatic polyether polyol and an aromatic ring-containing polyether polyol.

Examples of the aliphatic polyether polyol include an AO addition having 2 to 12 carbon atoms to the aliphatic polyhydric alcohol having 2 to 20 carbon atoms, and specifically, a polyoxyalkylene polyol (polyethylene glycol and the like). Examples thereof include polyoxypropylene polyol (polypropylene glycol and the like), polyoxyethylene / propylene polyol and polytetramethylene ether glycol.

Commercially available aliphatic polyether polyols include PTMG1000 [Mn = 1000 poly (oxytetramethylene) glycol, manufactured by Mitsubishi Chemical Co., Ltd.], PTMG2000 [Mn = 2000 poly (oxytetramethylene) glycol, Mitsubishi Chemical (Mn = 2000 poly (oxytetramethylene) glycol). Made by PTMG3000 [Mn = 3000 poly (oxytetramethylene) glycol, manufactured by Mitsubishi Chemical Co., Ltd.], PTGL2000 [Mn = 2000 modified poly (oxytetramethylene) glycol, manufactured by Hodoya Chemical Industry Co., Ltd.] ], PTGL3000 [Mn = 3000 modified poly (oxytetramethylene) glycol, manufactured by Hodoya Chemical Industry Co., Ltd.], Sanniks PP-2000 [Mn = 2000 polyoxypropylene glycol, manufactured by Sanyo Kasei Kogyo Co., Ltd.] And Sanniks Diol GP-3000 [Mn = 3000 polyoxypropylene ether triol, manufactured by Sanyo Kasei Kogyo Co., Ltd.], TEGOMER D3403 [Mn = 1,200 polyoxyethylene polyol, manufactured by Ebonic Degusa], Ymer N120 [ Mn = 1,000 polyoxyethylene polyol, manufactured by Perstoop Co., Ltd.] and the like.

Examples of the aromatic polyether polyol include EO adduct of bisphenol A (EO 2 mol adduct of bisphenol A, EO 4 mol adduct of bisphenol A, EO 6 mol adduct of bisphenol A, EO 8 mol adduct of bisphenol A, bisphenol A). EO 10 mol adduct and bisphenol A EO 20 mol adduct, etc.) and bisphenol A PO adduct (bisphenol A PO 2 mol adduct, bisphenol A PO 3 mol adduct, bisphenol A PO 5 mol adduct, etc.), etc. Examples thereof include polyols having a bisphenol skeleton and EO or PO adducts of resorcin.

The Mn of the polymer polyol constituting the polymer polyol component (a1) is preferably 500 to 6000, more preferably 1000 to 4000, from the viewpoint of the flexibility and mechanical characteristics of the polyurethane resin (U).

The Mn of the polyol in the present invention can be measured by gel permeation chromatography under the following conditions, for example.
Equipment: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolum SuperH-L" (1), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected together"
Sample solution: 0.25 wt% tetrahydrofuran solution Injection volume: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polyethylene glycol

In addition to the high molecular weight polyol component (a1), the active hydrogen atom-containing component (A) in the present invention includes a low molecular weight polyol component (a2) having no ionic group or a low molecular weight polyol component (a2) having a number average molecular weight of less than 500, and ionicity. A chain extender (a4) and a reaction terminator (a5) other than the compound (a3) and (a2) containing a group and an active hydrogen atom can be contained.

Examples of the small molecule polyol component (a2) having no ionic group and having a chemical formula or number average molecular weight of less than 500 include the polyhydric alcohol having 2 to 20 carbon atoms. In (a2), one type may be used alone or two or more types may be used in combination.

Among (a2), the aliphatic diol having 3 to 12 carbon atoms having the branch is preferable, and neopentyl is more preferable, from the viewpoint of flexibility, adhesion, scratch resistance and mechanical properties of the polyurethane resin (U). It is glycol.

Examples of the compound (a3) containing an ionic group and an active hydrogen atom include a compound (a31) containing an anionic group and an active hydrogen atom and a compound (a32) containing a cationic group and an active hydrogen atom. In (a3), one type may be used alone or two or more types may be used in combination.

As (a31), for example, a compound containing a carboxyl group as an anionic group and having 2 to 10 carbon atoms [dialkylol alkanoic acid (for example, 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid) , 2,2-Dimethylol heptanic acid and 2,2-Dimethylol octanoic acid), tartrate and amino acids (eg glycine, alanine and valine)], containing a sulfonic acid group as an anionic group and having 2 to 2 carbon atoms. It contains 16 compounds [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, sulfoisophthalic acid di (ethylene glycol) ester, etc.], a sulfamic acid group as an anionic group, and has 2 to 10 carbon atoms. Compounds [N, N-bis (2-hydroxylethyl) sulfamic acid, etc.] and the like, and salts obtained by neutralizing these compounds with a neutralizing agent can be mentioned. In (a3), one type may be used alone or two or more types may be used in combination.

Examples of the neutralizing agent used for the salt of (a31) include ammonia, an amine compound having 1 to 20 carbon atoms, or an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, lithium hydroxide, etc.).
Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine and monoethanolamine, and secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine and diisopropanolamine and methylpropanolamine. Examples thereof include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine. As the neutralizing agent used for the salt of (a31), one type may be used alone or two or more types may be used in combination.

As the neutralizing agent used for the salt of (a31), a compound having a high vapor pressure at 25 ° C. is preferable from the viewpoint of the drying property of the produced polyurethane resin aqueous dispersion (Q) and the water resistance of the obtained film. .. From this point of view, as the neutralizing agent used for the salt of (a31), ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine are preferable.

Of (a31), 2,2-dimethylolpropionic acid and 2,2-dimethylol are preferable from the viewpoints of mechanical properties of the obtained film, water resistance, and dispersion stability of the polyurethane resin aqueous dispersion (Q). Butanoic acid and salts thereof, more preferably neutralized salts of 2,2-dimethylolpropionic acid and 2,2-dimethylolpropane acid with ammonia or an amine compound having 1 to 20 carbon atoms.

Examples of the compound (a32) containing a cationic group and an active hydrogen atom include a compound having a tertiary amino group as a cationic group and a hydroxyl group as an active hydrogen atom, and a tertiary amino group having 1 to 20 carbon atoms. Diols [N-alkyldialkanolamines (eg N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine) and N, N-dialkylmonoalkanolamines (eg N, N-dimethylethanolamine) ), Etc.], etc.] can be mentioned as a salt obtained by neutralizing a compound such as] with a neutralizing agent.

Examples of the neutralizing agent used for the salt of (a32) include monocarboxylic acids having 1 to 10 carbon atoms (formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, benzyl chloride and the like. Be done.

The neutralizing agent used for the salts of (a31) and (a32) is used at any time before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step, during the water dispersion step, or after the water dispersion. Although it may be added, it is preferable to add it before the water dispersion step or during the water dispersion step from the viewpoint of the stability of the urethane resin and the stability of the aqueous dispersion. Further, the neutralizing agent volatilized at the time of solvent removal may be added after the solvent is removed, and the neutralizing agent type to be added can be freely selected from the above.

The content of the ionic group introduced in (a3) in (U) is preferably 0.1 to 1.5 mmol / g, more preferably 0.1 to 1, based on the weight of (U). It is 2 mmol / g, particularly preferably 0.1-0.9 mmol / g.

The content of the ionic group in the present invention means the weight% of the unneutralized cationic group or the anionic group, and does not include the weight of the counterion. For example, the content of the ionic group in (a31) is, in the case of the triethylamine salt of 2,2-dimethylolpropionic acid, the weight% of the carboxyl group (-COOH) is 3- (2,3-dihydroxypropoxy). -1- for triethylamine salt of sulfonic acid refers to the weight percent of the sulfo group _(-SO 3 H). Further, the content of the ionic group in (a32) refers to the weight% of only the nitrogen atom in the tertiary amino group.

Examples of the chain extender (a4) other than (a2) include water and aliphatic polyamines having 2-36 carbon atoms [alkylene diamines such as ethylenediamine and hexamethylenediamine; diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, and the like. Poly (n = 2 to 6) alkylene (2 to 6 carbon atoms) poly (n = 3 to 7) amines such as tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine], 6 to 20 carbon atoms Aliphatic polyamines (1,3- or 1,4-diaminocyclohexane, 4,4'-or 2,4'-dicyclohexylmethanediamine, isophoronediamine, etc.), aromatic polyamines with 6 to 20 carbon atoms (1,3) -Or 1,4-phenylenediamine, 2,4- or 2,6-tolylene diamine, 4,4'-or 2,4'-methylenebisaniline, etc.), heterocyclic polyamine with 3 to 20 carbon atoms ( 2,4-Diamino-1,3,5-triazine, piperazine and N-aminoethyl piperazine, etc.), hydrazine or a derivative thereof (dibasic acid dihydrazide, for example, dihydrazide adipate, etc.) and amino alcohol having 2 to 20 carbon atoms (for example, dihydrazide dibasic acid). (Ethanolamine, diamineamine, 2-amino-2-methylpropanol and triethanolamine) and the like can be mentioned. In (a4), one type may be used alone or two or more types may be used in combination.

Examples of the reaction terminator (a5) include monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohols, cetyl alcohols, stearyl alcohols, etc.) and monoamines having 1 to 20 carbon atoms (monoamines having 1 to 20 carbon atoms). Mono- or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctylamine, and mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine) can be mentioned. The reaction terminator (a5) may be used alone or in combination of two or more.

In addition to the high molecular weight polyol component (a1), the active hydrogen atom-containing component (A) in the present invention includes a low molecular weight polyol component (a2) having no ionic group or a low molecular weight polyol component (a2) having a number average molecular weight of less than 500. It is preferable that the compound (a3) containing an ionic group and an active hydrogen atom is contained, and the low molecular weight polyol component (a2) is a branched aliphatic diol having 3 to 12 carbon atoms.

The organic polyisocyanate component (B) in the present invention includes an aromatic polyisocyanate (b1) having 2 to 3 or more isocyanate groups and having 8 to 26 carbon atoms, and an aliphatic polyisocyanate having 4 to 22 carbon atoms (4 to 22 carbon atoms). Examples thereof include b2), an alicyclic polyisocyanate having 8 to 18 carbon atoms (b3), an aromatic aliphatic polyisocyanate having 10 to 18 carbon atoms (b4), and a modified product (b5) of these polyisocyanates. The organic polyisocyanate component (B) may be used alone or in combination of two or more.

Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter, tolylene diisocyanate is referred to as TDI). (Omitted), crude TDI, 4,4'-or 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4'-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4', 4 "-triphenyl Examples thereof include methanetriisocyanate and m- or p-isocyanatophenylsulfonylisocyanate.

Examples of the aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecantryisocyanate, and 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-Diisocyanatohexanoate can be mentioned.

Examples of the alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4'-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexene diisocyanate, and the like. Methylcyclohexylene diisocyanate, bis (2-isosianatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate can be mentioned.

Examples of the aromatic aliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α', α'-tetramethylxylylene diisocyanate.

The modified products (b5) of the polyisocyanates of (b1) to (b4) include the modified products of the polyisocyanate (urethane group, carbodiimide group, alohanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group). Or oxazolidone group-containing modified products, etc .; those having a free isocyanate group content of 8 to 33% by weight, preferably 10 to 30% by weight, particularly 12 to 29% by weight), for example, modified MDIs (urethane-modified MDI, carbodiimide-modified MDI and Examples thereof include modified products of polyisocyanate such as trihydrocarbyl phosphate-modified MDI), urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI and isocyanurate-modified IPDI.

Among the organic polyisocyanate components (B), from the viewpoint of flexibility and adhesion of the polyurethane resin (U), an alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms is preferable, and IPDI is even more preferable. Is.

The urethane group concentration of the polyurethane resin (U) in the present invention is preferably 1.0 to 2 based on the weight of (U) from the viewpoint of flexibility, mechanical properties, scratch resistance and adhesion of (U). It is .7 mmol / g, more preferably 1.3 to 2.5 mmol / g, and particularly preferably 1.5 to 2.3 mmol / g.

The urea group concentration of the polyurethane resin (U) in the present invention is preferably 0.1 to 0 based on the weight of (U) from the viewpoint of flexibility, mechanical properties, scratch resistance and adhesion of (U). It is .7 mmol / g, more preferably 0.2 to 0.6 mmol / g, and particularly preferably 0.3 to 0.5 mmol / g.

The Mn of the polyurethane resin (U) in the present invention is preferably 10,000 to 1,000,000 from the viewpoint of the mechanical properties, adhesion and scratch resistance of (U).

The Mn of the polyurethane resin (U) in the present invention can be measured by gel permeation chromatography under the following conditions, for example.
Equipment: "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: "Guardcolumn α" + "TSKgel α-M" [both manufactured by Tosoh Corporation]
Sample solution: 0.125% by weight dimethylformamide solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene

Additives such as antioxidants, color inhibitors, weather stabilizers, plasticizers and mold release agents can be added to the polyurethane resin (U) in the present invention, if necessary. 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 weight of (U).

The polyurethane resin (U) can be dispersed in an aqueous medium using a dispersant (H) instead of the compound (a3) having an ionic group and an active hydrogen group or in combination with (a3). From the viewpoint of water resistance of the obtained dry film, it is preferable to use a self-emulsifying aqueous dispersion using only (a3).

Dispersants (H) include nonionic surfactants (h1), anionic surfactants (h2), cationic surfactants (h3), amphoteric surfactants (h4) and other emulsified surfactants (h4). h5) can be mentioned. As for (H), one type may be used alone or two or more types may be used in combination.

Examples of (h1) include an AO-added nonionic surfactant and a polyhydric alcohol nonionic surfactant. The AO addition type includes EO adduct of aliphatic alcohol having 10 to 20 carbon atoms, EO adduct of phenol, EO adduct of nonylphenol, EO adduct of alkylamine having 8 to 22 carbon atoms, and polyoxypropylene glycol. Examples include EO adducts, and 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). , Glycerin monooleate, sorbitan monolaurate, sorbitan monooleate, etc.) and alkyl (carbon number 4 to 24) poly (polymerization degree 1 to 10) glycoside and the like.

As (h2), for example, an ether carboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof [sodium lauryl ether acetate and (poly) oxyethylene (additional molars 1 to 100) sodium lauryl ether acetate, etc.]; Sulfonate 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 (addition) Sodium lauryl sulfate triethanolamine and (poly) oxyethylene (additional moles 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.]; Sulfonate having a hydrocarbon group having 8 to 24 carbon atoms [Sodium dodecyl benzene sulfonate, etc.]; Sodium sulphonate having 1 or 2 hydrocarbon groups having 8 to 24 carbon atoms; Phosphate or ether phosphate ester having 8 to 24 carbon atoms and their ether phosphates. Salts [sodium lauryl phosphate and (poly) oxyethylene (additional moles 1 to 100) sodium lauryl ether phosphate, etc.]; fatty acid salts having a hydrocarbon group having 8 to 24 carbon atoms [sodium laurate and tri-laurate). Ethanolamine, etc.]; And acylated amino acid salts having a hydrocarbon group having 8 to 24 carbon atoms [sodium coconut oil fatty acid methyl taurine, coconut oil fatty acid sarcosin sodium, coconut oil fatty acid sarcosin triethanolamine, N-palm oil fatty acid acyl- L-Glutamic acid triethanolamine, N-palm oil fatty acid acyl-L-sodium glutamate, sodium lauroylmethyl-β-alanine, etc.] can be mentioned.

Examples of (h3) include quaternary ammonium salt type [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate, etc.] and amine salt type [diethylaminoethyl stearate]. Amido lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

Examples of (h4) include betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, laurylhydroxy. Sulfobetaine and lauroylamide ethylhydroxyethylcarboxymethylbetaine hydroxypropyl phosphate, etc.] and amino acid-type amphoteric surfactants [β-laurylaminopropionate, etc.] can be mentioned.

Examples of (h5) include 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 Pat. No. 5,906,704. Examples thereof include the above-mentioned emulsion dispersants having a urethane group or an ester group [for example, a polycaprolactone polyol and a polyether diol linked with a polyisocyanate].

The dispersant (H) may be added at any time after the urethanization reaction of the polyurethane resin (U), before the water dispersion step of (U), during the water dispersion step, or after the water dispersion, but (U) From the viewpoint of dispersibility and stability of the aqueous dispersion, it is preferable to add the mixture before the water dispersion step or during the water dispersion step.

When (H) is used, the content thereof is preferably based on the weight of the polyurethane resin (U) from the viewpoint of the water resistance of the dry film, the dispersibility of the polyurethane resin (U) and the stability of the aqueous dispersion. It is 0.01 to 15% by weight, more preferably 0.01 to 10% by weight, and particularly preferably 0.01 to 5% by weight.

Examples of the method for producing the polyurethane resin aqueous dispersion (Q) of the present invention include the following methods [1] and [2].

[1] A high molecular weight polyol component (a1), a low molecular weight polyol component (a2) having a chemical formula amount or a number average molecular weight of less than 500 that does not have an ionic group, and a compound (a3) having an ionic group and an active hydrogen group, if necessary. , The active hydrogen atom-containing component (A) containing the chain extender (a4) and the reaction terminator (a5) other than (a2) and the organic polyisocyanate component (B) in the presence of the organic solvent (S) or It is necessary after reacting in one step or multiple steps in the absence to produce a polyurethane resin (U), and if necessary, dispersing the ionic group moiety introduced by (a3) as a salt with a neutralizing agent in an aqueous medium. A method of distilling off the organic solvent (S).

[2] A high molecular weight polyol component (a1), a low molecular weight polyol component (a2) having a chemical formula amount or a number average molecular weight of less than 500 that does not have an ionic group, and a compound (a3) having an ionic group and an active hydrogen group, if necessary. The active hydrogen atom-containing component (A) containing the chain extender (a4) other than (a2) and the organic polyisocyanate component (B) are one-stage or multi-stage in the presence or absence of the organic solvent (S). To produce a urethane prepolymer (P) having an isocyanate group, and if necessary, the hydrophilic group portion introduced by (a3) in the prepolymer (P) is dispersed as a salt in an aqueous medium by neutralization. , (A2) and / or the reaction terminator (a5) are reacted until the isocyanate group in the prepolymer (P) is substantially eliminated, and then the organic solvent (S) is added as necessary. How to distill.

Of the methods [1] and [2], the method [2] is preferable from the viewpoint of the dispersion stability of the polyurethane resin (U) and the mechanical strength of the dry film.

Further, from the viewpoint of dispersion stability of the polyurethane resin (U), a method of producing the urethane prepolymer (P) in multiple stages to produce the polyurethane resin aqueous dispersion (Q) is more preferable, and particularly high except for (a12). An active hydrogen atom-containing component (A and an organic polyisocyanate component (B) containing a molecular polyol component (a1) and, if necessary, (a2), (a3) and (a4), in the presence of an organic solvent (S) or After reacting in the absence to produce a urethane prepolymer (P1) having an isocyanate group, the obtained urethane prepolymer (P1) and (a12) are reacted to produce a urethane prepolymer (P2) having an isocyanate group. Then, if necessary, the ionic group moiety introduced by (a3) in the prepolymer (P2) was dispersed as a salt in an aqueous medium by neutralization, and (a4) and / or (a5) was prepolymerized. A method is preferable in which the reaction is carried out until the isocyanate group in (P2) is substantially eliminated, and then the organic solvent (S) is distilled off, if necessary.

The reaction temperature at the time of producing the polyurethane resin (U) in the method [1] and the urethane prepolymer (P) in the method [2] is preferably 60 to 120 ° C., more preferably 60 to 120 ° C. from the viewpoint of suppressing side reactions. The temperature is 60 to 110 ° C, particularly preferably 60 to 100 ° C. The production time can be appropriately selected depending on the equipment to be used, but is generally preferably 1 minute to 100 hours, more preferably 3 minutes to 30 hours, and particularly preferably 5 minutes to 20 hours.

The organic solvent (S) is selected from solvents that are substantially non-reactive with isocyanate groups, such as ketone solvents (eg acetone and methyl ethyl ketone), ester solvents [eg ethyl acetate, dibasic acid ester (DBE)], and the like. Examples thereof include ether solvents (for example, tetrahydrofuran), amide solvents (for example, N, N-dimethylformamide and N-methylpyrrolidone), aromatic hydrocarbon solvents (for example, toluene) and the like. These organic solvents (S) may be used alone or in combination of two or more.
Further, the aqueous medium in the present invention means water or a mixture of water and an organic solvent (S).

The organic solvent (S) is preferably an organic solvent having a boiling point of less than 100 ° C., and examples thereof include acetone, methyl ethyl ketone, ethyl acetate and tetrahydrofuran.
When an organic solvent having a boiling point of 100 ° C. or higher is used, it becomes difficult to completely remove only the organic solvent from the aqueous medium, it remains in the aqueous dispersion, and the organic solvent is generated during drying, which is not preferable. Further, the organic solvent tends to remain in the film, and the mechanical properties of the film change with time, which is not preferable.

The content of the organic solvent (S) in the polyurethane resin aqueous dispersion (Q) is 1% by weight or less based on the weight of (Q) from the viewpoints of odor, stability over time, environmental load and safety. It is preferable, more preferably 0.8% by weight or less, and particularly preferably 0.5% by weight or less.

In the urethanization reaction in the above methods [1] and [2], a known urethanization catalyst or the like can be used, if necessary, in order to accelerate the reaction. The amount of the urethanization catalyst added is preferably 0.001 to 3% by weight, more preferably 0.005 to 2% by weight, and particularly preferably 0. 01 to 1% by weight
Is.

Examples of the urethanization catalyst include metal catalysts [tin-based catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stanas octoate, dibutyltin maleate, etc.), lead-based catalysts. (Lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.), cobalt-based catalysts (cobalt naphthenate, etc.), bismuth-based catalysts {bismastris (2-ethylhexanoate, etc.}} and mercury-based catalysts Catalysts (phenylmercury propionate, etc.)], amine catalysts [triethylenediamine, tetramethylethylenediamine, tetramethylhexylene diamine, diazabicycloalkene {1,8-diazabicyclo [5.4.0] -7-undecene} Etc .; Dialkylaminoalkylamine {dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine, etc.] or heterocyclic aminoalkylamine [2- (1-aziridinyl) ) Ethylamine and 4- (1-piperidinyl) -2-hexylamine, etc.] carbonates or organic acid salts (geate, etc.); N-methylmorpholin, N-ethylmorpholin, triethylamine, diethylethanolamine, dimethylethanolamine, etc. Etc.] and a mixture of two or more of these.

The apparatus for dispersing the polyurethane resin (U) or its organic solvent solution in the method [1], the urethane prepolymer (P) in the method [2] or its organic solvent solution in water is not particularly limited, but is rotating. It is preferable to use a type dispersion mixing device, an ultrasonic type dispersion machine or a kneading machine, and among them, a rotary type dispersion mixing device having a particularly excellent dispersion ability is more preferable.

Examples of the rotary dispersion mixer include a mixer having general stirring blades such as Max Blend and helical blades, TK Homo Mixer [manufactured by Primix Corporation], Claire Mix [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 represented as an example.

The polyurethane resin aqueous dispersion (Q) in the present invention can contain dimethyl silicone (E). When (Q) contains dimethyl silicone (E), the scratch resistance of the polyurethane resin (U) can be improved.

Examples of the dimethyl silicone (E) include an emulsion type dimethyl silicone (e2) in which oil type dimethyl silicone (e1) and (e1) are dispersed in an aqueous medium with a dispersant. In (E), one type may be used alone or two or more types may be used in combination.

Commercially available oil-type dimethyl silicone oil (e1) includes SH200 series [manufactured by Toray Dow Corning Co., Ltd.], KF-96 series [manufactured by Shin-Etsu Chemical Co., Ltd.] and TSF451 series [Momentive Performance Materials Inc.] Made by Japan GK] and so on.

Commercially available products of emulsion type dimethyl silicone (e2) include SM8706EX, FSXE-2098, IE-7045, SM7036EX, IE7046T and SM8701EX [manufactured by Toray Dow Corning Co., Ltd.], POLON MF-7, POLON MF-17, POLON. Examples thereof include MF-32 and POLON MF-33 [manufactured by Shin-Etsu Chemical Co., Ltd.] and TSM630, TSM631, TSM6344 and TSM6343 [manufactured by Momentive Performance Materials Japan GK].

Among the dimethyl silicones (E), (e2) is preferable from the viewpoint of the dispersion stability of the polyurethane resin aqueous dispersion (Q).
One type of dimethyl silicone (E) may be used alone, or two or more types may be used in combination.

The amount of dimethyl silicone (E) used is preferably 0.2 to 15% by weight, more preferably 0, based on the weight of (U) from the viewpoint of adhesion and scratch resistance of the polyurethane resin (U). It is 5 to 10% by weight, particularly preferably 1.0 to 5% by weight.

As a method for producing the polyurethane resin aqueous dispersion (Q) containing the dimethyl silicone (E), when the (E) is an oil-type dimethyl silicone oil (e1), the polyurethane resin (U) or the urethane prepolymer (P) is used. (U) and (e1) may be mixed before being dispersed in the aqueous medium, and the above-mentioned dispersion step in the aqueous medium may be performed. If (E) is the emulsion type dimethyl silicone oil (e2), (U) ) May be added after the dispersion step of (e2).

The volume average particle diameter (Dv) of the polyurethane resin (U) in the polyurethane resin aqueous dispersion (Q) is preferably 0.01 to 1.0 μm, more preferably 0.01 to 0.5 μm. When (Dv) is 0.01 μm or more, the viscosity of the polyurethane resin aqueous dispersion (Q) is appropriate and the handleability is good, and when it is 0.5 μm or less, the dispersion stability is good.

The volume average particle size (Dv) of (U) can be controlled by the amount of ionic groups, neutralizers, and dispersants in (U), the type of disperser used in the dispersion step, and the dispersion conditions.
The volume average particle size (Dv) can be measured with a light scattering particle size distribution measuring device [“LA950 V2” manufactured by HORIBA, Ltd.].

The solid content concentration (content of components other than volatile components) of the polyurethane resin aqueous dispersion (Q) is preferably 20 to 65% by weight, more preferably 25 to 55, from the viewpoint of ease of handling of (Q). 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.

The viscosity of the polyurethane resin aqueous dispersion (Q) at 25 ° C. is preferably 5000 mPa · s or less, more preferably 1000 mPa · s or less, from the viewpoint of handleability. The viscosity can be measured using a BL type viscometer.

The pH of the polyurethane resin aqueous dispersion (Q) at 25 ° C. is preferably 2 to 12, more preferably 4 to 10 from the viewpoint of dispersion stability. The pH can be measured using a pH Meter M-12 [manufactured by HORIBA, Ltd.].

The printing ink (L) of the present invention contains the polyurethane resin aqueous dispersion (Q) of the present invention. By using (Q), a printing ink having excellent image adhesion and scratch resistance can be obtained.

In addition to (Q), the printing ink (L) contains a coloring material as an essential component and a moisturizer, a penetrant, water and other additives as optional components.

Examples of the coloring material include dyes and pigments.
The dye is not particularly limited, but a reactive dye, a bat dye, a naphthol dye, a sulfur dye, a direct dye, an acidic dye, a metal complex salt type dye, a disperse dye, a cationic dye and the like can be selected depending on the medium to be used. ..

Pigments include inorganic pigments (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, natural organic pigment 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, xanthan lakes, anthraquinone lakes, Pigments from bat dyes and phthalocyanine pigments).

Of these coloring materials, pigments are preferable. One type of coloring material may be used alone, or two or more types may be used in combination.
The content of the coloring material is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of (L).

The moisturizing agent is not particularly limited, but for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexane. Diol, 2-methyl-2,4-pentanediol, tripropylene glycol, polyethylene glycol with Mn of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, glycerin, mesoerythritol, pentaerythritol, 2-pyrrolidone , N-Methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. The moisturizer may be used alone or in combination of two or more.

The penetrant is not particularly limited, but for example, glycol ether (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl). Ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monobutyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Propropylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, etc.) and aliphatic diols having 4 to 8 carbon atoms (1, 1,2-alkyldiols such as 2-pentanediol and 1,2-hexanediol and 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, Organic solvents such as 7-heptanediol and linear alcohols such as 1,8-octanediol); acetylene glycol-based surfactants; acetylene alcohol-based surfactants; polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, Ether-based surfactants such as polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxyalkylene alkyl ether; polyoxyethylene oleic acid , Polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate and other ester-based interfaces. Activator; Silicon-based surfactant such as dimethylpolysiloxane; Examples thereof include surfactants such as fluorine-based surfactants such as arsenic alkyl esters and perfluoroalkyl carboxylic acid salts. The penetrant may be used alone or in combination of two or more.

Examples of other additives include preservatives and pH adjusters.
Examples of the preservative include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, 1,2-dibenzinethiazolin-3-one and the like.

pH adjusters include potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, triisopropanolamine, potassium carbonate, sodium carbonate and hydrogen carbonate. Examples include sodium and the like.

Examples of the printing method using the printing ink (L) of the present invention include printing methods used for conventional plastic printing, such as gravure printing, inkjet printing, offset printing, and thermal transfer printing. Among these, inkjet printing is particularly suitable as the printing method for the printing ink (L) of the present invention.

In addition to printing ink, the polyurethane resin aqueous dispersion (Q) of the present invention includes water-based paints, water-based adhesives, water-based fiber processing agents (nonwoven fabric binders, reinforcing fiber bundling agents, antibacterial agent binders, and artificial leather. It can be used for synthetic leather raw materials, etc.), water-based coatings, water-based paper treatment agents, etc.

When used for these applications, in addition to the above pigments, moisturizers, penetrants, preservatives and pH adjusters, other resins as well as cross-linking agents, viscosity modifiers, leveling agents, deterioration inhibitors, and stables are required. One or two or more kinds of agents, antifreeze agents and the like can be added.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following, the part represents the weight part.

<Production example of polyolefin polyol (a11-1)>
<Manufacturing example 1>
A reaction vessel is charged with 1000 parts of polyolefin [trade name "Vistamaxx3980", manufactured by ExxonMobil) containing 94% by weight of propylene and 6% by weight of ethylene as constituent monomers, and heated with a mantle heater while aerating nitrogen into the liquid phase. It was melted and heat-decomposed at 370 ° C. for 90 minutes with stirring to obtain a polyolefin. Twenty parts of maleic anhydride are charged therein, and after nitrogen substitution, the temperature is raised to 180 ° C. under nitrogen aeration to uniformly dissolve the radical initiator [dicumyl peroxide, trade name "Parkmill D", Nichiyu (Nichiyu). Manufactured by Co., Ltd.] A solution prepared by dissolving 5 parts in 50 parts of xylene was added dropwise over 5 minutes, and then stirring was continued for 1 hour under reflux of xylene. Then, unreacted maleic anhydride was distilled off under reduced pressure (1.5 kPa) to obtain an acid-modified polyolefin. In a similar reaction vessel, 500 parts of acid-modified polyolefin and 32 parts of 2-aminoethanol were charged and reacted at 180 ° C. for 1 hour in a nitrogen gas atmosphere. Then, unreacted 2-aminoethanol was distilled off under a reduced pressure of 180 ° C. and 2.7 kPa to obtain a hydroxyl group-modified polyolefin (a11-1). The hydroxyl value of (a11-1) was 25, and Mn was 4,500.

<Production example of polyester polyol (a12)>
<Manufacturing example 2>
770 parts of terephthalic acid, 880 parts of 1,2-prepyrene glycol, and 0.5 part of tetrabutoxytitanate as a polymerization catalyst were charged in a reaction vessel equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer at 210 ° C. After distilling off 1,2-prepyrene glycol with water generated under a nitrogen stream, the reaction was carried out for 5 hours, and then the reaction was carried out under a reduced pressure of 5 to 20 mmHg for 1 hour. The obtained resin was cooled to room temperature and then pulverized to obtain 1000 parts of a polyester polyol (a12-1) containing 76% by weight of the structural unit represented by the chemical formula (3) based on the weight of the polyol. The Mn of (a12-1) was 1500.

<Manufacturing example 3>
In a reaction vessel equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, 498 parts of terephthalic acid, 263 parts of adipic acid, 1400 parts of 3-methyl-1,5-pentanediol, and tetrabutoxytitanate 0 as a polymerization catalyst. .5 parts were charged and reacted for 5 hours while distilling off water generated under a nitrogen stream at 210 ° C. and 3-methyl-1,5-pentanediol, and then reacted under a reduced pressure of 5 to 20 mmHg for 1 hour. rice field. The obtained resin was cooled to room temperature and then pulverized to obtain 1000 parts of a polyester polyol (a12-2) containing 49% by weight of the structural unit represented by the chemical formula (3) based on the weight of the polyol. The Mn of (a12-2) was 1500.

<Example 1>
NISSO-PB as (a11) in a simple pressurization reactor equipped with a stirrer and a heating device
GI-2000 [manufactured by Nippon Soda Co., Ltd.] 161.6 parts, 13.2 parts of neopentyl glycol as (a2), 14.6 parts of 2,2-dimethylol propionic acid as (a3), organic polyisocyanate 99.9 parts of IPDI as component (B), 0.07 parts of Neostan U-600 [manufactured by Nitto Kasei Co., Ltd.] as a urethanization catalyst, and 150.0 parts of methyl ethyl ketone as an organic solvent for reaction were charged at 80 ° C. The urethanization reaction was carried out with stirring for 6 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer (P1) having an isocyanate group. Further, 60.6 parts of (a12-1) obtained in Production Example 1 was charged into the obtained urethane prepolymer (P1), and the mixture was stirred at 80 ° C. for 4 hours to carry out a urethanization reaction, and a urethane prepolymer having an isocyanate group was carried out. A methyl ethyl ketone solution of the polymer (P2) was produced.
Next, 8.3 parts of triethylamine as a neutralizing agent and 74.2 parts of methyl ethyl ketone as an organic solvent for dilution were added to the obtained methyl ethyl ketone solution of the urethane prepolymer (P2) to homogenize the mixture, and then the mixture was stirred at 200 rpm. A chain extender (a4) other than (a2) and 485.4 parts of water as an aqueous medium were added, and the polyurethane prepolymer was dispersed in water. The obtained dispersion was heated to 50 ° C. and stirred for 4 hours to carry out an extension reaction with water, and further heated to 60 ° C. under reduced pressure to distill off methyl ethyl ketone. Then, after cooling the obtained dispersion to room temperature, 23.6 parts of SM8706EX [solid content concentration 37% by weight, manufactured by Toray Dow Corning Co., Ltd.] as dimethyl silicone (E) was added to homogenize and water was added. In addition, a polyurethane resin aqueous dispersion (Q-1) was obtained by adjusting the solid content concentration to 30% by weight.

<Examples 2 to 11>
Polyurethane resin aqueous dispersions (Q-2) to (Q-11) were obtained in the same manner as in Example 1 except that the raw materials used and the amounts used were changed to those shown in Table 1.

<Example 12>
NISSO-PB as (a11) in a simple pressurization reactor equipped with a stirrer and a heating device
GI-2000 [manufactured by Nippon Soda Co., Ltd.] 161.6 parts, 60.6 parts of (a12-1) obtained in Production Example 1, 13.2 parts of neopentyl glycol as (a2), as (a3) 2,2-Dimethylol propionic acid 14.6 parts, IPDI 99.9 parts as an organic polyisocyanate component (B), Neostan U-600 [manufactured by Nitto Kasei Co., Ltd.] 0.07 parts as a urethanization catalyst, and 150.0 parts of methyl ethyl ketone as an organic solvent for reaction was charged and stirred at 80 ° C. for 6 hours to carry out a urethanization reaction to obtain a methyl ethyl ketone solution of a urethane prepolymer (P) having an isocyanate group.
Next, in the methyl ethyl ketone solution of the obtained urethane prepolymer (P), 8.3 parts of triethylamine as a neutralizing agent, 74.2 parts of methyl ethyl ketone as an organic solvent for dilution, and Naroacty CL120 as a dispersant [Sanyo Kasei Kogyo (Sanyo Kasei Kogyo (Sanyo Kasei Kogyo) Made by Co., Ltd.] After homogenizing by adding 35.0 parts, add a chain extender (a4) other than (a2) and 485.4 parts of water as an aqueous medium while stirring at 200 rpm, and add water to the polyurethane prepolymer. Distributed in. The obtained dispersion was heated to 50 ° C. and stirred for 4 hours to carry out an extension reaction with water, and further heated to 60 ° C. under reduced pressure to distill off methyl ethyl ketone. Then, after cooling the obtained dispersion to room temperature, 23.6 parts of SM8706EX [solid content concentration 37% by weight, manufactured by Toray Dow Corning Co., Ltd.] as dimethyl silicone (E) was added to homogenize and water was added. In addition, a polyurethane resin aqueous dispersion (Q-12) was obtained by adjusting the solid content concentration to 30% by weight.

<Comparative Examples 1-2>
Polyurethane resin aqueous dispersions (Q'-1) and (Q'-2) were obtained in the same manner as in Example 1 except that the raw materials used and the amounts used were changed to those shown in Table 1.

The composition of each raw material in Table 1 is as follows.
NISSO-PB GI-2000: Hydrogenated polybutadiene diol with Mn = 2000 [
Nippon Soda Co., Ltd.]; It has a structural unit in which ^{R 1 in the general formula (1) is an ethyl group.}
NISSO-PB G-2000: Polybutadiene diol with Mn = 1900 [manufactured by Nippon Soda Co., Ltd.]; It has a structural unit in which ^{R 1 in the general formula (1) is a vinyl group.}
Kuraray Polyol P-2020: Poly3-methyl-pentamethylene terephthalate with Mn = 2000 [manufactured by Kuraray Co., Ltd.]; has a structural unit represented by the general formula (3).
-Kuraray Polyol P-2010: Poly3-methyl-pentamethylene adipate with Mn = 2000 [manufactured by Kuraray Co., Ltd.]
-Sanniks PP-2000: Polyoxypropylene diol with Mn = 2000 [manufactured by Sanyo Chemical Industries, Ltd.]
-Ymer N120: Polyoxyethylene polyol with Mn = 1,000 [manufactured by Perstoop]
-PTMG2000: Polytetramethylene ether glycol with Mn = 2,000 [manufactured by Mitsubishi Chemical Corporation]
-SM8706EX: Aqueous emulsion of dimethyl silicone (solid content concentration 37% by weight) [manufactured by Toray Dow Corning Co., Ltd.]
-POLON MF-32: Aqueous emulsion of dimethyl corn (solid content concentration 31% by weight) [manufactured by Shin-Etsu Chemical Co., Ltd.]
-Neostan U-600: Bismuth Tris (2-ethylhexanoate) [manufactured by Nitto Kasei Co., Ltd.]
・ Naroacty CL120: Polyoxyalkylene alkyl ether [manufactured by Sanyo Chemical Industries, Ltd.]

The results of evaluating the adhesion of the polyurethane resin aqueous dispersions (Q-1) to (Q-12) and (Q'-1) to (Q'-2) by the following methods are the constituent units of the polyurethane resin (U). It is shown together with the weight ratio of.

<Evaluation method of adhesion of polyurethane resin (U)>
Surface-treated polypropylene film (OPP) [Toyobo Co., Ltd. "Pyrene P-2161" (thickness 30 μm)], Surface-treated polyester film (PET) [Toyobo Co., Ltd. "Espet E-5102" (thickness 12 μm)] And surface-treated nylon film ["Harden N-1130" (thickness 15 μm) manufactured by Toyobo Co., Ltd.] with polyurethane resin aqueous dispersions (Q-1) to (Q-12) and (Q'-1) to (Q'-1) -2) was applied with a bar coater so that the thickness after drying was 2 μm, and dried at 90 ° C. for 10 minutes to prepare test pieces in which a polyurethane resin was coated on each plastic film. In accordance with JIS K5600-5-6, make a notch with a cutter knife to a width of 1 mm so that 100 (10 x 10) masses can be formed on the dry film surface of the polyurethane resin aqueous dispersion of the prepared test piece. A peeling test was performed with a transparent pressure-sensitive adhesive tape, and the number of cells remaining on the base film was counted. The larger the number of remaining cells, the better the adhesion of the polyurethane resin.

<Examples 13 to 22 and Comparative Examples 3 to 4>
2.7 parts of the polyurethane resin aqueous dispersions (Q-1) to (Q-12) or (Q'-1) to (Q'-2) obtained in Examples 1 to 12 or Comparative Examples 1 and 2. Pigment [Carbon black aqueous dispersion {"Aqua-Black162" manufactured by Tokai Carbon Co., Ltd., solid content concentration 20% by weight}] 2.5 parts, glycerin 1.0 part as moisturizer, triethylene glycol 0.1 part , 0.1 part of 1,2-hexanediol as a penetrant and 3.6 parts of water are charged in a container and mixed for 10 minutes to print inks (L-1) to (L-12) and printing for comparison. Inks (L'-1) to (L'-2) were prepared.

Table 2 shows the results of evaluating the adhesion and scratch resistance of the printing inks (L-1) to (L-12) and (L'-1) to (L'-2) by the following methods.

<Evaluation method of image adhesion using printing ink (L)>
Adhesion of the polyurethane resin (U) except that printing inks (L-1) to (L-12) and (L'-1) to (L'-2) are used instead of the polyurethane resin aqueous dispersion. The adhesion of the printing ink was evaluated by the same method as the evaluation method.

<Evaluation method of scratch resistance of printing ink (L)>
A drying test and a wetting test were performed on the dried film surface of the polyurethane resin aqueous dispersion of the test piece prepared by evaluating the adhesion of the printing ink (L) in accordance with the method specified in JIS L0849 (Type II). After the test, the degree of peeling of the image was visually judged, and the scratch resistance of the printing ink was evaluated according to the following criteria.
⊚: Image survival rate is 70 to 100%
◯: Image survival rate is 50 to 69%
X: Image survival rate is less than 50%

The polyurethane resin aqueous dispersion (Q) of the present invention is an aqueous ink composition (particularly inkjet ink), an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (binder composition for pigment printing, a non-woven fabric). Binder composition for reinforcing fibers, binder composition for reinforcing fibers, raw material composition for artificial leather / synthetic leather, etc.), water-based coating composition (waterproof coating composition, water-repellent coating composition and antifouling) It can be suitably used for coating compositions, etc.) and water-based paper treatment agent compositions, etc.

Claims (6)

Contains a polyurethane resin (U) obtained by reacting an active hydrogen atom-containing component (A) containing a polymer polyol component (a1) having a number average molecular weight of 500 or more with an organic polyisocyanate component (B), and an aqueous medium. Polyurethane resin aqueous dispersion, wherein the polymer polyol component (a1) has a structural unit represented by the general formula (1) and / or a structural unit represented by the general formula (2). ) And the polyester polyol (a12) having the structural unit represented by the chemical formula (3), and the structural unit represented by the general formula (1) and the general formula (2) in the polyurethane resin (U). The total weight ratio of the constituent units to be formed is 11 to 55% by weight based on the weight of (U), and the weight ratio of the constituent units represented by the chemical formula (3) in the polyurethane resin (U) is 4-40 wt% der Ru polyurethane resin aqueous dispersion based on the weight of the (U) (Q).

[In the formula, R ¹ represents a hydrogen atom, a methyl group, an ethyl group, a vinyl group, an isopropyl group or an isopropenyl group, and R ² represents a hydrogen atom or a methyl group. ]

[In the formula, R ³ represents a hydrogen atom or a methyl group. ]

The polyolefin polyol (a11) is represented by the general formula (1) is a polyolefin polyol having structural units represented by claim 1 Symbol placement polyurethane resin aqueous dispersion. The active hydrogen atom-containing component (A) is a low-molecular-weight polyol component (a2) having no ionic group and having a chemical formula or number average molecular weight of less than 500, and / or a compound containing an ionic group and an active hydrogen atom ( The aqueous dispersion of a polyurethane resin according to claim 1 or 2 , which contains a3) and contains an aliphatic diol having 3 to 12 carbon atoms in which the low molecular weight polyol component (a2) has a branch. Dimethyl silicone (E) is added from 0.5 to 0.5 based on the weight of the polyurethane resin (U).
The polyurethane resin aqueous dispersion according to any one of claims 1 to 3 , which contains 15% by weight. The polyurethane resin aqueous dispersion according to any one of claims 1 to 4 , which is used for printing ink. A printing ink (L) containing the polyurethane resin aqueous dispersion according to any one of claims 1 to 5.