JPH0291281A - Binder for printing pigment - Google Patents

Abstract

PURPOSE:To obtain the subject binder composition, consisting of an aqueous dispersion of a polyurethane resin consisting essentially of a specific compound and capable of exhibiting excellent color fastness to friction, washing and dry cleaning even without heat-treating printed fabrics. CONSTITUTION:A binder for printing pigments consisting of an aqueous dispersion of a polyurethane resin, obtained by reacting an aliphatic polyisocyanate (preferred example; hexamethylene diisocyanate) with a polycarbonate diol (preferred example; polycarbonate diol obtained by ester interchange of 1,6- hexanediol with an aryl carbonate), a carboxyl group-containing compound (e.g., alpha,alpha'-dimethylolpropionic acid) having two alcoholic active hydrogen atoms and a tertiary amine (preferred example; triethylamine) as essential components and containing 0.3-2wt.% (based on the polyurethane resin) carboxyl groups is applied to a natural, semisynthetic or synthetic fiber to afford a printed fabric excellent in color fastness to friction, etc., without heat-treating the printed fabric.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to a binder for pigment printing.

[Conventional technology] Conventionally, polyacrylic acid and
Some are made of ester resin emulsions.

[Problems to be Solved by the Invention] Conventional binders have insufficient abrasion fastness, washing resistance, and dry cleaning resistance when printed fabrics are not heat-treated.

[Means for Solving the Problems] The present inventors obtain a binder composition for pigment printing that exhibits good abrasion fastness, washing resistance, and dry cleaning resistance even without heat treatment of the printed fabric. As a result of intensive research, we have arrived at the present invention.

That is, the present invention consists of an aqueous dispersion of a polyurethane resin comprising an aliphatic polyisocyanate, a polycarbonate diol, a carboxyl group-containing compound containing at least two alcoholic active hydrogens, and a reactant containing a tertiary amine as an essential component. This is a binder for pigment printing which is characterized by the following.

Examples of aliphatic polyisocyanates include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3.f)
i-hexamethylene triincyanate, etc.), alicyclic polyisocyanate (inphorone diisocyanate, 4
．． ．． 4'-dicyclohexylmethane diisocyanate,
Bicyclohebutane triisocyanate, etc.).

Among these, preferred are hexamethylene diisocyanate, inphorone diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate.

The polycarbonate diol can be prepared using the usual methods, namely diol components (1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, 1,4-cyclohexanediol (1,4-butanediol), Diol, 1. It can be obtained by a method using tohexane diol, neopentyl glycol, 1, 8-octane diester exchange.

Among these, the preferred one is 1.6 as the diol component.
- Polycarbonate diol using hexane diol. The molecular weight of polycarbonate diol is usually 30
0-5 d 00. Preferably it is 500-3000.

Polyether polyols and polyester polyols can also be used in combination as polyol components other than polycarbonate diol. A chain extender may also be used in combination.

Examples of polyether polyols include low-molecular polyols [ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, l, tohexanediol, glycerin, trimethylolpropane, hexanetriol, sorbitol, sucrose, sodium sulfodi-(β Polyhydric alcohols such as -hydroxyethyl) isophthalate; Polyphenols (bisphenol A1, bisphenol S, etc.); Amines (
Examples include alkylene oxide (alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, butylene oxide) adducts of compounds with active hydrogen groups such as alkanolamines and polyamines, and ring-opening polymers of alkylene oxides. Examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

Polyester polyols include those obtained by reacting polycarboxylic acids (aliphatic polycarboxylic acids such as adipic acid, maleic acid, double linoleic acid; aromatic polycarboxylic acids such as phthalic acid and sodium sulfoisophthalic acid) with low-molecular polyols, or Polyester polyols containing terminal hydroxyl groups obtained by reacting polycarboxylic acids and polyether polyols, polycaprolactone polyols (for example, based on initiators [glycols (ethylene glycol, etc.), triols, etc.])
substitution) caprolactone (ε-caprolactone x 1 α-
methyl-ε-caprolactone, ε-methyl-ε-caprolactone, etc.) in the presence of a catalyst (organometallic compound, metal chelate compound, fatty acid metal acylated product, etc.).

Chain extenders include, for example, low-molecular polyols (ethylene glycol, di-, tri- and tetra-ethylene glycol, propylene glycol, dipropylene glycol, ■, 3- and 1,4-butanediol, ■, tohexanediol, neopentyl). glycols, trimethylolpropane, pentaerythritol, etc.), alkanolamines (ethanolamine, propatoolamine,
jetanolamine, dibrobanolamine, etc.), aliphatic diamines (ethylene diamine, hexamethylene diamine, etc.), alicyclic diamines (isophorone diamine),
Examples include compounds having two or more hydrogen atoms reactive with isocyanate groups such as aromatic aliphatic diamines (such as xylylene diamine), hydrazine, piperazine, aromatic diamines (such as diaminodiphenylmethane), and water. Preferred among these are low molecular weight polyols.

Carboxyl group-containing compounds having at least two alcoholic active hydrogens include α,α'-dimethylolalkanoic acid (dimethylolpropionic acid, glyceric acid, etc.), tartaric acid, dioxymaleic acid, dioxyfumaric acid, 2. Examples include trioxybenzoic acid.

Among these, preferred is α,α'-dimethylolalkanoic acid, and particularly preferred is dimethylolpropionic acid.

Examples of the tertiary amine include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, and triethanolamine, but triethylamine is preferred.

Polyurethane resin aqueous dispersion does not contain carboxyl groups.
After creating an O-terminal urethane prepolymer, adding a solvent (N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, dioxane, dimethylformamide, etc.) as necessary, and neutralizing the carboxy and ru groups with a tertiary amine, the chain Obtained by stretching and dispersing in water. Chain elongation can also be carried out while dispersing in water or after dispersing in water.

Carboxyl group-containing NGO-terminated urethane prepolymers are prepared by conventional urethanization methods, i.e., aliphatic polyisocyanates, polycarbonate diols, carboxyl group-containing compounds having at least two alcoholic active hydrogens, and optionally polyols other than polycarbonate diols (polyethers). polyol, polyester polyol, etc.) and a chain extender in the presence or absence of a solvent (N-methyl-2-pyrrolidone, acetone, methyl ethyl ketone, dioxane, dimethylformamide, etc.).

The equivalent ratio of NGO groups and active hydrogen groups is usually 1.05 to 3.0.
Preferably it is 1.1 to 1.8.

The amount of tertiary amine used is generally 0.3 to 1.5 equivalents, preferably 0.5 to 1.1 equivalents, per equivalent of carboxyl group.

Chain extenders for NGO-terminated prepolymers containing carboxyl groups include low-molecular polyols (ethylene glycol, di-, tri- and tetra-ethylene glycol, propylene glycol, dipropylene glycol, l,3- and 1,4-butanediol, l,3- and 1,4-butanediol, .l1i-hexanediol, neopentyl glycol, trimethylolpropane, etc.), alkanolamines (ethanolamine,
Two hydrogen atoms reactive with incyanate groups such as propatoolamine, jetanolamine, etc.), aliphatic diamines (ethylene diamine, hexamethylene diamine, etc.), alicyclic diamines (isophorone diamine), hydrazine, piperazine, water, etc. Among the compounds having the above, preferred are water, aliphatic diamine, and alicyclic diamine.

An aqueous polyurethane resin dispersion can be obtained by the above method, and if necessary, emulsifiers, ultraviolet absorbers, antioxidants, etc. can be used, and these usually disperse the carboxyl-based NCO-terminated prepolymer in water. Added before.

Emulsifiers include nonionic surfactants (polyoxyalkylene adducts of higher alcohols, polyoxyalkylene adducts of alkylphenols, polyoxyalkylene adducts of higher fatty acids, etc.), anionic surfactants (sulfosuccinic acid dialkyl ester salts, alkylbenzene sulfonates, higher alcohol sulfate ester salts, higher alkyl ether sulfate ester salts, etc.) can be used.

Benzotriazoles and hindered amines can be used as ultraviolet absorbers, and hindered phenols can be used as antioxidants.

In the polyurethane resin aqueous dispersion constituting the binder of the present invention, the amount of carboxyl groups in the polyurethane resin is usually 0.3 to 2.0% by weight, preferably 0.5 to 1.0% by weight.
It is 5% by weight. If the carboxyl group content is 0.3% by weight, a stable aqueous dispersion cannot be obtained, and if it exceeds 2% by weight, the washing resistance becomes poor. The aqueous polyurethane resin dispersion preferably contains N-methyl-2-pyrrolidone in an amount of IO weight or more, particularly 20 to 60% by weight, based on the solid content of the polyurethane resin.

If N-methyl-2-pyrrolidone is less than 10% by weight based on the solid content of the polyurethane resin in the aqueous polyurethane resin dispersion, the wash resistance will be poor.

N-methyl-2-pyrrolidone may be added as a solvent during the urethanization reaction, or may be added after urethanization and before dispersion in water. It may optionally be added to the water in which it is dispersed. Further, it may be added after obtaining the aqueous polyurethane resin dispersion, but is preferably added before obtaining the aqueous dispersion.

The binder composition of the present invention is printed on fabrics. Fiber materials that make up the fabrics to be printed include natural fibers such as cotton, hemp, wool, and silk, semi-synthetic fibers such as rayon and acetate, synthetic fibers such as polyester, polyamide, polyacrylonitrile, and polyolefin, and their fibers. Examples include blended textiles and mixed knitted textiles.

For printing on fabrics, the same method as for ordinary pigment printing is used. In other words, color paste (pigment finely and uniformly dispersed in water), binder additive (sizing agent made by simply diluting sodium alginate, modified starch, carboxymethyl cellulose, etc. with water), and turpentine (O/V) with a nonionic surfactant. Half-emulsion paste containing sodium alginate, modified starch, carboxymethyl, etc.)
The printing paste (viscosity of 3,000 to 20,000 cps) is adjusted with auxiliary agents (printability imparting agents, gum-up inhibitors, etc.) and fabrics are printed using an auto screen printing machine, rotary screen printing machine, roller printing machine, etc. It will be stamped on.

The printed fabrics are dried for one day at room temperature.

[Example] The present invention will be further explained below with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited thereto.

Parts in Examples, Comparative Examples, and Test Examples are parts by weight.

Examples 1-3, Comparative Examples 1-2 Example I Polycarbonate diol (D
uracab124 (manufactured by PBG Industries), 80 parts of isophorone diisocyanate, and 15 parts of dimethylolpropionic acid were combined with N-methyl-
100-1 in 100 parts of 2-pyrrolidone under nitrogen atmosphere
The mixture was reacted at 20° C. for 10 hours and diluted with 200 parts of acetone. 710 parts of triethylamine and 2 parts of a hindered amine ultraviolet absorber (Tinuvin 144, manufactured by Ciba Gaiki) were added, and 490 parts of water was added at ~50°C to dilute the emulsion.

Acetone was distilled off, and the viscosity was 250 cps, pH (1%
Aqueous solution) 1000 parts of an aqueous dispersion of a polyurethane resin as a binder of the present invention of 9.5 was obtained.

Example 2 Polycarbonate diol (Du
racab124 (manufactured by PPC Industries), 65 parts of hexamethylene diisocyanate and 15 parts of dimethylolpropionic acid were combined with N-methyl-
100-1 in 100 parts of 2-pyrrolidone under nitrogen atmosphere
The mixture was reacted at 20'C for 10 hours and diluted with 200 parts of acetone. 10 parts of triethylamine and hindered amine ultraviolet absorber (Tinuvin 144, manufactured by Ciba Gaiki Co., Ltd.)
2 parts were added and diluted by adding 490 parts of water at ~50''C~.The acetone was distilled off and the viscosity was 300cps1pH (
1% aqueous solution) 1000 parts of an aqueous dispersion of a polyurethane resin, which is a binder of the present invention, having a concentration of 9.5 was obtained.

Example 3 Polycarbonate diol with an average molecular weight of 12000 (
300 parts of Duracab 124 (manufactured by PB-G Industries), 85 parts of 4,4'-dicyclohexylmethane diisocyanate and 15 parts of dimethylolpropionic acid were mixed in 100 parts of tomethyl-2-pyrrolidone at 100 to 120'C for 10 hours under a nitrogen atmosphere. The mixture was reacted and diluted with 200 parts of acetone. triethylamide 710
and hindered amine ultraviolet absorber (Tinuvin 1)
44 (manufactured by Ciba Gaiki Co., Ltd.) was added thereto, and 490 parts of water was added at ~50°C to dilute the emulsion. After distilling off the acetone, an aqueous dispersion of polyurethane resin, which is the binder of the present invention, with a viscosity of 260 cps and a pH (1% aqueous solution) of 9.5 was prepared.
I got the department.

Comparative Example 1 Polypropylene glycol 3 with average molecular weight ff 12000
05 parts of inphorone diisocyanate and 15 parts of dimethylolpropionic acid were mixed in 100 parts of N-methyl-2-pyrrolidone at 100 to 120°C under a nitrogen atmosphere.
The mixture was reacted for 0 hours and diluted with 200 parts of acetone. Add 710 parts of triethylamine and 2 parts of a hindered amine ultraviolet absorber (Tinuvin 144, manufactured by Ciba Gaiki),
At 0°C or higher, 490 parts of water was added to dilute the emulsion.

Acetone was distilled off, and the viscosity was 150 cps, pH (1%
Aqueous solution) 1000 parts of a polyurethane resin aqueous dispersion of 9.5 was obtained.

Comparative Example 2 Reactive self-crosslinking acrylic ester copolymer emulsion (WS Blender 5Ei3; binder manufactured by Toyo Ink) Test Example 1 Performance evaluation when printed on cotton knit A pigment printing paste was prepared with the following formulation and used for test autoscreen printing. Cotton knit (width 30 cm x 40
cm) with line pattern (3cm x 30cm) 6 pieces for 80
It was printed using a mesh screen. Drying the printed material (
After (room temperature x 1 day), abrasion fastness: JIS L-0849 Jakushin type, 200g
X 100 times, dry and wet washing resistance: JIS L-0844, A4 method Dry cleaning resistance: JIS L-0880, Perclean method was used for evaluation. The evaluation results are shown in Table-1.

(Formulation of pigment printing paste) Pigment paste 50 parts (Blue FL (10% aqueous dispersion of iB)) Binder SOO part Carboxymethylcellulose 100-300 parts 20%
The viscosity was adjusted to about 15,000 cps with aqueous ammonia solution. Table 1 Evaluation Results: A product with good dry cleaning properties was obtained and is useful as a binder for pigment printing.

[Effects of invention

Claims (1)

[Scope of Claims] 1. Aqueous polyurethane resin consisting of aliphatic polyisocyanate, polycarbonate diol, a carboxyl group-containing compound having at least two alcoholic active hydrogens, and a reactant containing a tertiary amine as an essential component A binder for pigment printing, characterized by comprising a dispersion liquid. 2. The binder according to claim 1, wherein the carboxyl group-containing compound having at least two alcoholic active hydrogens is α,α'-dimethylolalkanoic acid. 3. 0.3 to 2 carboxyl groups in polyurethane resin
．． The binder according to claim 1 or 2, containing 0% by weight. 4. Claim 1, wherein the polyurethane resin is a resin obtained by chain-extending a carboxyl group-containing NCO-terminated urethane prepolymer.
The binder according to any one of items 1 to 3. 5. N-methyl-2- in polyurethane resin aqueous dispersion
The binder according to any one of claims 1 to 4, which contains pyrrolidone in an amount of 10% by weight or more based on the solid content of the polyurethane resin.