JP2007528922A - Composition and use of the composition for treating flexible substrates - Google Patents

Abstract

The present invention provides a method for producing a composition that is suitable for coating flexible substrates, has no deficiencies in the prior art, and emits little formaldehyde.
(A) At least one copolymer having a glass transition temperature Tg of less than 15 ° C. is produced by copolymerization in the presence of (b) at least one heterocyclic compound having at least two carbamate groups. Thus, a method for producing a composition was obtained.

Description

  The present invention relates to a method of using a heterocyclic compound having at least two carbamate groups to treat flexible substrates, in particular fibers.

  The invention particularly relates to a method of using a heterocyclic compound having at least two carbamate groups in the form of an aqueous copolymer composition to coat a flexible substrate.

In one embodiment, the present invention provides:
(A) at least one copolymer having a glass transition point Tg of less than 15 ° C.
(B) The present invention relates to a method for producing a composition, which is produced by copolymerization in the presence of at least one heterocyclic compound having at least two carbamate groups.

  Furthermore, the present invention provides a composition produced by the production method of the present invention, a method of using the composition of the present invention to treat a flexible substrate, and a flexible treated with one or more compositions of the present invention. The present invention relates to a substrate.

  Various substrates, especially flexible substrates such as fabrics, will only have the desired properties as a result of processing. In many cases, such treatments first involve coating (coating), after which the coating is, for example, thermally crosslinked. The compound used for crosslinking is usually called a crosslinking agent. The coating must meet stringent requirements, must be reasonably priced and must not have stickiness after curing. Flexible substrates after treatment, especially fibers, must have excellent resistance to washing. In addition, substances that are not generally safe in toxicology should not be used. Therefore, modern aqueous compositions are often used selectively. There are also strict requirements for one or more types of crosslinking agents. While cross-linking agents need to be highly reactive, they should not contain or release substances that are not generally toxicologically safe.

  Since crosslinkers in the prior art contain aldehydes, they are often unacceptable for toxicological reasons.

  For example, in textile pigment printers and pigment dyers using (meth) acrylate copolymer binders, up to 4% by weight of N-methylolacrylamide (Amol) incorporated during copolymerization. Alternatively, a copolymer containing N-methylol methacrylamide (MAMol) is often used. They may release formaldehyde before or during thermal crosslinking in certain circumstances.

  It is known to use a methylol compound such as a formaldehyde-urea-glyoxal condensation product represented by the following formula as a crosslinking agent.

  However, the possibility that the formaldehyde-urea-glyoxal condensation product does not react quantitatively during crosslinking cannot be ruled out, and a small amount of formaldehyde is later separated. Furthermore, the pot life is limited.

Triazine derivatives are known as crosslinking agents produced in the paint industry. For example, DE 196 23 370 discloses a process for the production of binder compositions, in particular (meth) acrylate copolymers, hydroxy-functional methacrylic acid polymers, hydroxy-functional polyesters and optionally other hydroxy functionalities. binder, and formula C ₃ N ₃ (NHCOOR) ₃ triazine carbamate (R = C ₁ -C ₂₀ alkyl, C ₆ -C ₂₀ aryl and / or C ₇ -C ₂₀ arylalkyl) dispersed in water together A method for producing a binder composition for multilayer coating using the dispersion obtained in this way for multilayer coating is described. If the multilayer coating material disclosed in the above document is used for electrophoretic coating of immersion pre-coated metal and then baked, a particularly hard coating is obtained, with a glass transition temperature exceeding 55 ° C. However, such coatings and coating techniques are not beneficial for coating flexible substrates such as fabrics.

  EP-A 604 922 discloses the use of a curable composition containing triazine triscarbamate and an acid catalyst such as an organic tin compound. The composition thus disclosed is used for coating hard substrates such as metals and wood, and has a high degree of scratch resistance. In addition, the concentration of formaldehyde is low. Similarly, EP 0 604 922 describes coating techniques that are not useful for coating fiber substrates.

WO 98/44060 relates to a coating containing three types of components. That is,
(I) 30 to 60% by mass of C ₁ -C ₈ alkyl (meth) acrylate monomer, 30 to 60% by mass of vinyl aromatic monomer, and 0.5 to 10% by mass of (meth) acrylic acid are used as raw materials. An acrylate copolymer having a glass transition temperature of preferably 15 to 35 ° C. and a number average molecular weight of 200,000 to 2,000,000 (page 5, lines 4 to 9),
A crosslinker comprising (ii) a flow stabilizer that does not produce a bond, and (iii) tris (alkoxycarbonylamino) triazine or a mixture of tris (alkoxycarbonylamino) triazines,
A coating comprising is described.

  According to the above-described technique, an advantage can be obtained with respect to the covering of the automobile body part, but it is not suitable for covering a flexible substrate such as a fabric.

  Binders based on methylol methacrylamide (sometimes AMol or MAMol) are known, for example, from DE 2920377. Since binders based on methylol methacrylamide separate formaldehyde after crosslinking, they are unacceptable in various applications.

  Formaldehyde-free binders used for nonwovens are known, for example, from DE 29 188 827 and DE 2 264 935. However, the storage of various types of epoxy binders used for non-woven fabrics decreases.

DE 196 23 370 EP-A 604922 EP 0604922 WO 98/44060 DE 2920377 DE 2918827 DE 2264935

  An object of the present invention is to provide a method for producing a composition suitable for coating a flexible substrate. Another object of the present invention is to provide a composition that is suitable for coating flexible substrates, has little (if little) formaldehyde released, and does not have the disadvantages of the prior art. . It is a further object of the present invention to provide a method for coating a flexible substrate and to provide a flexible substrate having a coating.

The inventors
(A) at least one copolymer having a glass transition point Tg of less than 15 ° C.
(B) The above-mentioned problem of the present invention is solved by a method for producing a composition, which is produced by copolymerization in the presence of at least one heterocyclic compound having at least two carbamate groups. I found it.

  The at least one copolymer (a) used in the present invention is a copolymer obtained by radical polymerization, and preferably emulsion polymerization.

  Hereinafter, the term emulsion polymerization is also used when two or more types of comonomers are used. Thus, emulsion polymerization includes emulsion copolymerization.

  In order to produce at least one copolymer (a) selectively using various emulsion polymerization operations, for example, a batch operation (non-continuous) or a continuous method, such as a feed addition method, can be used. . These can also be done in stages.

  A so-called seed procedure described in EP0810831 can also be used. The seed method is a very efficient method for producing an addition polymer or copolymer (a) having a particle size distribution that is particularly easily reproducible.

  The polymerization is generally performed using one or more initiators. Peroxides can be used as one or more initiators. Examples of suitable peroxides are alkali metal peroxodisulfates such as sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, organic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dialkyl peroxide. Octanoyl peroxide, didecanoyl peroxide, dilauryl peroxide, dibenzoyl peroxide, bis (o-tolyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert-butyl permaleate, tert-butyl perisobutyrate, perpival Tert-butyl acid, tert-butyl peroctanoate, tert-butyl perneodecanoate, tert-butyl perbenzoate, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydro Hydroperoxide, tert- butyl peroxy-2-ethylhexanoate, and diisopropyl peroxydicarbonate carbamate. Further suitable are azo compounds such as azobisisobutyronitrile, azobis (2-amidopropane) dihydrochloride, and 2,2'-azobis (2-methylbutyronitrile).

Redox initiators are also preferably used, for example peroxides and oxidizable sulfuric acid compounds. Particularly suitable examples are acetone bisulfite and organic peroxides, for example _{tert-C 4 H 9 -OOH,} Na 2 S 2 O 5 ( sodium metabisulfite), and organic peroxides, for example tert-C ₄ H ₉ A system consisting of —OOH or HO—CH ₂ SO ₂ Na and an organic peroxide such as tert-C ₄ H ₉ —OOH. Similarly, ascorbic acid / H ₂ O ₂ is particularly preferred.

  The usable polymerization temperature is in the range of 20 to 105 ° C, preferably 50 to 85 ° C. The temperature is set depending on the nature of decomposition of each initiator used.

  There are no particular restrictions on the pressure conditions, but examples of suitable pressures are from atmospheric to 10 bar.

  At least one type of emulsifier can be used, and the type may be any of anionic, cationic and nonionic.

Examples of nonionic emulsifiers suitable are ethoxylated mono -, di- - and trialkylphenols (degree of ethoxylation: 3-50, alkyl radical: C ₃ -C _12), and ethoxylated fatty alcohols (degree of ethoxylation: 3 80, alkyl radical: a C ₈ -C _36). Examples of these are the Lutensol® brand from BASF and the Triton® brand from Union Carbide.

Examples of suitable anionic emulsifiers are alkyl sulfates (alkyl groups: C ₈ -C ₁₂ ) alkali metal salts and ammonium salts, ethoxyl alkanols (ethoxylation degree: 4-30, alkyl groups: C ₁₂ -C ₁₈ ) or ethoxylations. Sulfuric acid monoester obtained from alkylphenol (degree of ethoxylation: 3-50, alkyl group: C ₄ -C ₁₂ ), and alkali metal salt and ammonium salt of alkyl sulfuric acid (alkyl group: C ₁₂ -C ₁₈ ), and alkylaryl Sulfuric acid (alkyl group: C ₉ -C ₁₈ ) alkali metal salt and ammonium salt.

Suitable cationic emulsifiers are generally primary, secondary, tertiary or quaternary ammonium salts having C ₆ -C ₁₈ alkyl, C ₆ -C ₁₈ arylalkyl or heterocyclyl, alkanol ammonium salts, pyridinium salts, imidazoli The salts of onium, oxazolinium, morpholinium, thiazolinium, and amine oxide, quinolinium, isoquinolinium, tropylium, sulfonium, and phosphonium. Specific examples include dodecyl ammonium acetate salt, the corresponding hydrochloride salt, various 2- (N, N, N-trimethylammonium) ethyl paraffin ester chlorides or acetates, N-cetylpyridinium chloride, N-laurylpyridinium sulfate. N-cetyl-N, N, N-trimethylammonium bromide, N-dodecyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride, and Gemini interfaces The activator is N, N- (lauryldimethyl) ethylenediamine dibromide. For many other examples see H.C. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981, and McCutcheon's Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.

  Other additive materials commonly used in emulsion polymerization, such as glycols, polyethylene glycols, protective colloids, and buffer / pH adjusters may be added to the reaction mixture.

  The residence time is in the range of 30 minutes to 12 hours, preferably 2 to 5 hours.

In one embodiment, the composition of the present invention is 40% by mass or more, preferably 60% by mass or more, particularly preferably 80% by mass or more, based on the mass of each addition polymer or copolymer. Main monomers of the general formula I

の化合物、
一般式ＩＩ

A compound of
Formula II

の不飽和エステル、
一般式ＩＩＩ

Of unsaturated esters,
Formula III

のビニル芳香族化合物、
一般式ＩＶａ及びＩＶｂ

Vinyl aromatic compounds,
Formulas IVa and IVb

の不飽和化合物、及び
炭素原子数２〜８であり、少なくとも１個のＣ−Ｃ二重結合を有する非芳香族炭化水素からなる群から選択される複数の主モノマーから誘導された共重合単位から選択される複数の共重合単位、
を含み、前記各式中、
Ｒ¹、Ｒ⁴、Ｒ¹⁰が同一であっても異なってもよく、それぞれ分岐又は非分岐Ｃ₁−Ｃ₁₀アルキル、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ｎ−ペンチル、ｓｅｃ−ペンチル、ｎｅｏ−ペンチル、１，２−ジメチルプロピル、ｉｓｏ−アミル、ｎ−ヘキシル、ｉｓｏ−ヘキシル、ｓｅｃ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、２−エチルヘキシル、ｎ−ノニル、ｎ−デシル、特に好ましくはＣ₁−Ｃ₄アルキル、例えばメチル、エチル、ｎ−プロピル、ｎ−ブチル、ｉｓｏ−ブチル、ｓｅｃ−ブチル、及びｔｅｒｔ−ブチル、又は水素
から選択され、
特に好ましくは水素及びメチルであり、
Ｒ²、Ｒ⁵、Ｒ¹¹が同一であっても異なってもよく、それぞれ分岐又は非分岐Ｃ₁−Ｃ₁₀アルキル、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ｎ−ペンチル、ｓｅｃ−ペンチル、ｎｅｏ−ペンチル、１，２−ジメチルプロピル、ｉｓｏ−アミル、ｎ−ヘキシル、ｉｓｏ−ヘキシル、ｓｅｃ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、２−エチルヘキシル、ｎ−ノニル、ｎ−デシル、特に好ましくはＣ₁−Ｃ₄アルキル、例えばメチル、エチル、ｎ−プロピル、ｎ−ブチル、ｉｓｏ−ブチル、ｓｅｃ−ブチル、及びｔｅｒｔ−ブチル、又は
特に好ましくは水素、から選択され、
各Ｘが同一であっても異なってもよく、それぞれハロゲン、例えばフッ素、臭素、又は特に塩素、ＣＮ又はＯＲ¹²を意味し、
Ｒ³、Ｒ⁶、Ｒ¹²が同一であっても異なってもよく、それぞれＣ₁−Ｃ₂₀アルキル、例えばｎ−ウンデシル、ｎ−ドデシル、ｎ−トリデシル、ｎ−テトラデシル，ｎ−ペンタデシル、ｎ−ヘキサデシル、ｎ−ヘプタデシル、ｎ−オクタデシル、ｎ−ノナデシル、ｎ−エイコシル、好ましくは非分岐又は分岐Ｃ₁−Ｃ₁₀アルキル、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、
ｎ−ペンチル、イソペンチル、ｓｅｃ−ペンチル、ｎｅｏ−ペンチル、１，２−ジメチルプロピル、イソアミル、ｎ−ヘキシル、ｉｓｏ−ヘキシル、ｓｅｃ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、２−エチルヘキシル、ｎ−ノニル、ｎ−デシル、特に好ましくはＣ₁−Ｃ₄アルキル、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチルであり、
Ｒ⁷、Ｒ⁸、Ｒ⁹が同一であっても異なってもよく、それぞれ水素及びＣ₁−Ｃ₁₀アルキル、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、
ｎ−ペンチル、イソペンチル、ｓｅｃ−ペンチル、ｎｅｏ−ペンチル、１，２−ジメチルプロピル、イソアミル、ｎ−ヘキシル、ｉｓｏ−ヘキシル、ｓｅｃ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル、２−エチルヘキシル、ｎ−ノニル、ｎ−デシル、特に好ましくはＣ₁−Ｃ₄アルキル、例えばメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、イソ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチルから選択され、特に好ましくはメチル、ｎ−ブチル、イソ−ブチル、ｎ−デシル、及び特に水素であり、
ｋが０〜３の整数、好ましくは０又は１、最も好ましくは０を意味する共重合体（ａ）を含む。

And a copolymer unit derived from a plurality of main monomers selected from the group consisting of non-aromatic hydrocarbons having 2 to 8 carbon atoms and having at least one C—C double bond A plurality of copolymerized units selected from
Each of the above formulas,
R ¹ , R ⁴ , R ¹⁰ may be the same or different, each branched or unbranched C ₁ -C ₁₀ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl 2-ethylhexyl, n-nonyl, n-decyl, particularly preferably C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl, or Selected from hydrogen,
Particularly preferred are hydrogen and methyl,
R ² , R ⁵ , R ¹¹ may be the same or different and each is branched or unbranched C ₁ -C ₁₀ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl 2-ethylhexyl, n-nonyl, n-decyl, particularly preferably C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl, or Particularly preferably selected from hydrogen,
Each X may be the same or different and each represents a halogen, such as fluorine, bromine, or in particular chlorine, CN or OR ¹² ;
R ³ , R ⁶ , R ¹² may be the same or different and each is C ₁ -C ₂₀ alkyl such as n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n- Hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, preferably unbranched or branched C ₁ -C ₁₀ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,
n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl N-decyl, particularly preferably C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,
R ⁷ , R ⁸ , R ⁹ may be the same or different and each is hydrogen and C ₁ -C ₁₀ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec- Butyl, tert-butyl,
n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl N-decyl, particularly preferably C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, particularly preferably methyl, n-butyl, iso-butyl, n-decyl, and in particular hydrogen;
It includes a copolymer (a) wherein k is an integer of 0 to 3, preferably 0 or 1, and most preferably 0.

  Examples of the main monomers represented by the general formula I are methyl (meth) acrylate, n-butyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and mixtures thereof.

  Examples of unsaturated esters of formula II are vinyl acetate, allyl acetate, vinyl laurate, vinyl stearate, vinyl versatate such as vinyl pivalate, vinyl 2,2-dimethylbutyrate, 2,2 -Vinyl dimethyl octanoate and vinyl 2,2-ethylmethyl butyrate.

  Examples of aromatic compounds of formula III are α-methylstyrene, p-methylstyrene, α-n-butylstyrene, pn-butylstyrene, 4-n-decylstyrene, and especially styrene.

  Examples of unsaturated compounds of the formula IV are vinyl chloride, vinylidene chloride, methyl vinyl ether, methyl allyl ether, ethyl vinyl ether, (methyl) acrylonitrile, vinyl isobutyl ether.

  Examples of non-aromatic hydrocarbons having 2 to 8 carbon atoms and having at least one C—C double bond are ethylene, propylene, 1-octene, isoprene, 1,3-butadiene and chloroprene.

  The polymer and copolymer (a) may contain 40% by mass or more of units derived from at least one main monomer.

  In the present invention, the copolymer (a) is obtained by polymerization from a mixture containing at least 40% by mass of two different main monomers.

  In addition, it is possible to copolymerize one or more comonomers containing one or more alcoholic hydroxyl groups or one or more COOH groups. Formula V

で表され、式中
Ｙ²がＮ−Ｈ、又は好ましくは酸素、
ａが２〜１０、好ましくは２〜６、更に好ましくは４以下、最も好ましくは２又は３を意味し、式中の他の符号は上記定義と同様の意味を有する１種類以上のコモノマーを共重合させることが好ましい。

Wherein Y ² is N—H, or preferably oxygen,
a represents 2 to 10, preferably 2 to 6, more preferably 4 or less, most preferably 2 or 3, and the other symbols in the formula share one or more comonomers having the same meaning as defined above. It is preferable to polymerize.

  Particularly preferred examples of comonomers of the general formula V are hydroxyalkylene (meth) acrylates, and (meth) acrylated di- and polyols, in which at least one hydroxyl group in the molecule is not esterified, for example 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and ω-hydroxy-n-butyl (meth) acrylate.

  An example of a comonomer having at least one COOH group is (meth) acrylic acid.

  Another preferred comonomer is itaconic acid.

When it is preferable not to copolymerize a comonomer having one or more alcoholic hydroxyl groups, it is preferable to copolymerize one or more basic comonomer. Suitable examples are optionally compounds of the general formula VII (see formula below), optionally further N—C ₁ -C ₁₀ alkylated (methacrylic) amides, and (meth) acrylamide derivatives of the general formula VIII.

Wherein R ¹⁵ is methyl, or preferably hydrogen,
R ¹⁶ is the above C ₁ -C ₁₀ alkyl, preferably hydrogen.

    In one embodiment of the present invention, the copolymerized amount of at least one comonomer having at least one alcoholic hydroxyl group is 0.3% by mass to 5% by mass with respect to the copolymer, respectively. .

  Similar to the one or more main monomers and the one or more comonomers described above, the copolymer (a) may have units derived from other monomers. Examples of these are as follows.

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid,
Unsaturated sulfonic acid or phosphonic acid,
(Meth) acrylamide,
Phenoxyethylene glycol (meth) acrylate, glycidyl (meth) acrylate,
Compound represented by general formula VII

(In the above formula, Y ³ is oxygen or NH,
A ¹ is C ₂ -C ₆ alkylene, such as —CH ₂ —, —CH (CH ₃ ) —, — (CH ₂ ) ₂ —, —CH ₂ —CH (CH ₃ ) —, — (CH ₂ ) _{3. -, - CH 2 -CH (C} 2 H 5) -, - (CH 2) 4 -, - (CH 2) 5 -, - (CH 2) 6 -, preferably C ₂ -C ₄ alkylene, in particular - _{(CH 2) 2 -, -} CH 2 -CH (CH 3) -, - (CH 2) 3 -, - (CH 2) 4 -, and _{-CH 2 -CH (C 2 H 5} ) -,
Each R ¹⁴ may be different but is preferably the same and is C ₁ -C ₁₀ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl. , N-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n- Nonyl, n-decyl, particularly preferably C ₁ -C ₄ alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, most preferably methyl,
Hydrogen, and phenyl),
Ureido (meth) acrylate.

  In one embodiment, in the present invention, copolymerization is carried out with the amount of other comonomer used being 10% by mass or less based on the copolymer (a).

  For example, the glass transition temperature of at least one kind of addition polymer or copolymer (a) measured according to ASTM 3418/82 is less than 15 ° C. The glass transition temperature Tg of at least one kind of addition polymer or copolymer (a) is preferably in the range of −30 ° C. to less than 15 ° C., and more preferably in the range of −18 ° C. to + 5 ° C.

The aqueous composition according to the present invention comprises:
(B) produced in the presence of at least one heterocyclic compound having at least two carbamate groups.

  The at least one heterocyclic compound having at least two carbamate groups is a compound based on N, N′-disubstituted cyanuric acid, N, N ′, N ″ -trisubstituted cyanuric acid, or preferably triazine. Is preferably included.

  In one embodiment of the present invention, the at least one heterocyclic compound having at least two carbamate groups is a compound represented by general formula VI.

In which Y ¹ is R ¹³ , oxygen or NH, preferably NH.
Z ¹ is hydrogen or CO—O—R ¹³ , preferably CO—O—R ¹³ ,
R ¹³ may be the same or different, and C ₁ -C ₁₀ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n- Pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n - decyl, particularly preferably C ₁ -C ₄ alkyl, for example methyl, ethyl, n- propyl, isopropyl, n- butyl, isobutyl, sec- butyl and tert- butyl, and most preferably methyl or n- butyl,
C ₆ -C ₁₄ aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, Preferred are phenyl, 1-naphthyl and 2-naphthyl, and more preferred is phenyl or benzyl.

In a preferred embodiment of the invention, Y ¹ is N—H, Z ¹ is CO—O—R ¹³ , and R ¹³ groups are all the same.

In a preferred embodiment of the invention, Y ¹ is N—H, Z ¹ is CO—O—R ¹³ , R ¹³ groups are all the same and are methyl or n-butyl.

  The order of addition of the comonomer is not usually limited, but at least one heterocyclic compound having two or more carbamate groups is added before or during the initiation of copolymerization or in particular emulsion polymerization. And preferably, the emulsion polymerization reaction will take place at a predetermined time during the presence of at least one heterocyclic compound having at least two carbamate groups.

In one embodiment of the method of the present invention, at least one heterocyclic compound having at least two carbamate groups is converted to n-butanol, ethylene glycol, diethylene glycol, triethylene glycol, or room temperature liquid polyethylene glycol (C ₁ -C ₆ alkanol, C ₂ -C ₆ alkanediol or C ₃ -C ₆ alkanetriol may be monoesterified).

  In another embodiment of the present invention, during copolymerization or emulsion polymerization, at least one heterocyclic compound having at least two carbamate groups is used as a solid powder and an organic solvent such as n-butanol or Add ethylene glycol. Here, at least one heterocyclic compound having at least two carbamate groups is suspended in at least one kind of comonomer or main monomer, or a mixture containing the comonomer and main monomer, and this is suspended in one or more kinds of organic compounds. It is highly preferred to add gradually to the reaction mixture with the solvent.

  In one embodiment of the present invention, the aqueous composition of the present invention is represented by at least one heterocyclic compound having at least two carbamate groups, preferably represented by the general formula VI, wherein the symbols in the formula are as defined above. It is produced by emulsion polymerization in the presence of two or more compounds.

  In one embodiment of the invention, in the presence of at least one heterocyclic compound having at least two carbamate groups and a solubilizer, for example at least one liquid at room temperature without ethylenically unsaturated double bonds The copolymer (a) is produced in the presence of a hydroxycarboxylic acid ester such as 2-hydroxyethyl acetate.

  Furthermore, according to the present invention there is provided a composition obtainable by the inventive method. The composition of the present invention may be non-aqueous, but is preferably aqueous.

In one embodiment, the preferably aqueous composition of the present invention comprises
The total amount of the polymer (a) or each copolymer (a) of 88% to 99% by weight, preferably 75% to 95% by weight, based on the solid component content of the composition of the present invention, and One or more kinds having at least two carbamate groups in a total amount of 0.2 to 12% by weight, preferably 0.5 to 5% by weight, based on the total amount of the union (a) or each copolymer (a). Heterocyclic compounds,
including.

  The aqueous composition of the present invention may have a solid content of 20 to 70% by mass, preferably 35 to 50% by mass, and the remaining amount is preferably water.

  In one embodiment of the invention, the pH of the composition is 3-8.

  Furthermore, in one embodiment, the viscosity of the at least one copolymer (a) contained in the composition of the present invention is 20 to 1000 mPa.s. s (for example, when Brookfield viscometer, spindles 2 to 6 are used by Brookfield method).

  In one embodiment of the present invention, the number average particle size of the solid particles contained in the composition of the present invention is 20 to 500 nm, preferably 200 nm, and is measured by quasi-elastic light scattering (QELS). Suitable measuring methods are described, for example, in ISO13321, and very dilute aqueous dispersions with a solids content of 0.005% by weight or less are used.

  Furthermore, according to the present invention, a method of using the composition of the present invention to coat (apply) a flexible substrate, a method of coating a flexible substrate using the composition of the present invention (hereinafter also referred to as the coating method of the present invention). And a flexible substrate having a coating obtained by the coating method of the present invention.

  The flexible substrate according to the invention is in particular leather, various textiles or fiber substrates.

  The coating method of the present invention is preferably carried out by coating a flexible substrate with at least one composition of the present invention and then heat treating.

  The fiber substrate according to the present invention comprises textile fibers, textile intermediates and finished products, and finished products made therefrom, and textiles for the garment industry, for example carpets and other household Includes woven and industrial fiber structures. Further specific examples include irregularly shaped structures such as short fibers (hair bundles), linear structures such as twisted yarns, filaments, yarns, ropes, strings, laces, moldings, ropes, yarns, and three-dimensional shaped structures. For example, felt, woven fabric, non-woven fabric, and wadding. Fabrics are natural materials such as cotton, wool, flax, or synthetic materials such as polyamide, polyester, modified polyester, polyester blend fabric, polyamide blend fabric, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride, polyester Microfiber and glass fiber fabrics may be used.

  The thermal crosslinking in the present invention is performed by first bringing a flexible substrate and the composition of the present invention into contact, for example, by spraying, padding, impregnation or the like.

  The flexible substrate that has just been contacted with the composition of the present invention may then be subjected to pre-drying. The preliminary drying is performed, for example, so that the residual moisture is in the range of 0.5 to 20% by mass based on an untreated flexible substrate. A woven fabric containing synthetic fibers is preferably pre-dried to a residual moisture of 0.5 to 2% by weight, and a woven fabric made of pure cotton is preferably pre-dried to a residual moisture of 6 to 8% by weight. The viscous rayon woven fabric is preferably pre-dried to a residual moisture content of 10 to 16% by mass. In the case of a rayon woven fabric, the processing steps described below are performed in a partially swollen state.

  Subsequent to the above treatment, treatment is carried out in the range of 100 to 180 ° C., preferably 120 to 160 ° C. for 1 to 10 minutes, preferably 3 to 7 minutes. The processing temperature is adapted to the material making up the flexible substrate to which the composition of the invention is applied. For example, a flexible substrate made of polypropylene is preferably heat-treated at a temperature of less than 130 ° C., and wool, cotton, polyamide, polyester, modified polyester, polyester mixed fiber, polyamide mixed fiber, polyacrylonitrile, triacetate, acetate, and polycarbo The nat is preferably treated at a temperature of 130 ° C to 160 ° C. The temperature referred to here is roughly the temperature of the medium surrounding the flexible substrate to be processed.

  The processing method of the present invention is performed using conventional equipment. For example, the fiber substrate is processed in any curing and drying equipment conventional in the textile industry.

  Since use of an acidic catalyst may cause damage to the substrate, it is preferable to avoid the use of an acidic catalyst such as ammonium sulfate or diammonium hydrogen phosphate.

  In a special embodiment, the textile substrate of the present invention is coated using the printing method according to the present invention.

  In another embodiment of the present invention, a method for producing a flexible substrate and in particular a fiber (printed fabric) printed using one or more compositions of the present invention (hereinafter also referred to as the printing method of the present invention). Is obtained.

  The textile printing method of the present invention is performed, for example, by introducing at least one kind of the composition of the present invention into a printing paste (hereinafter also referred to as the printing paste of the present invention) and then printing the substrate by a known method. .

  The printing paste of the present invention containing at least one composition of the present invention is produced by mixing with an auxiliary used in a normal printing method and at least one pigment. Usually, the depth of shade is adjusted by adjusting the proportion of the pigment in the composition of the present invention.

  The printing paste of the present invention may contain one or more pigments. The pigments used in the present invention are substantially insoluble, finely dispersed organic or inorganic colorants as defined in German Industrial Standard DIN 55944. In the method of the present invention, an organic pigment is preferably used.

  Typical examples of organic pigments are as follows.

Monoazo pigments: CI Pigment Brown 25, CI Pigment Orange 5, 13, 36 and 67, CI Pigment Red 1, 2, 3, 5, 8, 9, 12, 17, 22, 23, 31, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 52: 1, 52: 2, 53, 53: 1, 53: 3, 57: 1, 63, 112, 146, 170, 184, 210, 245 and 251, CI Pigment Yellow 1, 3, 73, 74, 65, 97, 151 and 183,
Diazo pigments: CI Pigment Orange 16, 34 and 44, CI Pigment Red 144, 166, 214 and 242, CI Pigment Yellow 12, 13, 14, 16, 17, 81, 83, 106, 113, 126, 127, 155, 174, 176 and 188,
Antanthrone Pigment: CI Pigment Red 168 (CI Bat Orange 3)
Anthraquinone pigments: CI pigment yellow 147 and 177, CI pigment violet 31,
Anthrapyrimidine pigment: CI pigment yellow 108 (CI vat yellow 20),
Quinacridone pigments: CI pigment red 122, 202 and 206, CI pigment violet 19,
Quinophthalone pigment: CI Pigment Yellow 138
Dioxazine pigments: CI pigment violet 23 and 37,
Flavantrone Pigment: CI Pigment Yellow 24 (CI Bat Yellow 1),
Indantron pigments: CI pigment blue 60 (CI bat blue 4) and 64 (CI bat blue 6),
Isoindoline pigments: CI pigment orange 69, CI pigment red 260, CI pigment yellow 139 and 185,
Isoindoline pigments: CI pigment orange 61, CI pigment red 257 and 260, CI pigment yellow 109, 110, 173 and 185,
Isoviolanthrone pigment: CI pigment violet 31 (CI vat violet 1),
Metal complex pigments: CI pigment yellow 117, 150 and 153, CI pigment green 8,
Perinone pigment: CI pigment orange 43 (CI vat violet 7), CI pigment red 194 (CI vat red 15),
Perylene pigment: CI pigment black 31 and 32, CI pigment red 123, 149, 178, 179 (CI vat red 23), 190 (CI vat red 29) and 224, CI pigment violet 29,
Phthalocyanine pigments: CI pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 and 16, CI pigment green 7 and 36,
Pyrantron pigment: CI Pigment Orange 51, CI Pigment Red 216 (CI Bat Orange 4),
Thioindigo pigments: CI pigment red 88 and 181 (CI vat red 1), CI pigment violet 38 (CI vat violet 3),
Triarylcarbonium pigments: CI pigment blue 1, 61 and 62, CI pigment green 1, CI pigment red 81, 81: 1 and 169, CI pigment violet 1, 2, 3 and 27, CI pigment black 1 (aniline black) ,
CI Pigment Yellow 101 (Aldazine Yellow),
CI Pigment Brown 22.

  Examples of particularly preferred pigments include CI Pigment Yellow 138, CI Pigment Red 122, CI Pigment Violet 19, CI Pigment Blue 15: 3 and 15: 4, CI Pigment Black 7, CI Pigment Oranges 5, 38 and 43, and CI Pigment Green 7.

  The average particle diameter of the pigment used in the printing paste of the present invention is usually 20 nm to 1.5 μm, preferably 300 to 500 nm.

  In one embodiment, the one or more pigments used in the printing paste of the present invention are spherical or substantially spherical (ie, the ratio of major axis: minor axis is 1.0: 2.0, preferably 1. 5 or less).

  A pigment is preferably added to the printing paste to form a pigment preparation. The pigment preparation usually contains 20 to 60% by weight of pigment, water and one or more surfactant compounds, for example one or more emulsifiers.

  The ratio between the pigment and the composition of the present invention can be selected within a wide range. For example, pigment: composition of the present invention is selected in a mass ratio of 20: 1 to 1:50. In a preferred embodiment, the ratio of pigment to the composition of the invention is determined such that the mass ratio of pigment: solid portion of the composition of the invention is from 1: 1 to 1:10.

  In addition, the pigment and the composition of the present invention are preliminarily mixed at a mass ratio of 20: 1 to 10: 1, and the composition of the present invention or a conventional acrylate binder is mixed immediately before printing. Also good.

  Other auxiliaries conventionally used for printing pastes in textile printing are Ullmann, Handbuch der technischen Chemie und Verfahrenstechnik, eg Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, heading: Textile Auxiliaries, Volume A26, pages 286 onwards, pages 296 onwards Verlag Chemie, Weinheim, Deerfield / Florida, Basle, 1996. Examples of conventional printing aids are thickeners, fixing agents, texture improvers, antifoaming agents, flow improvers, and emulsifiers.

  Natural and synthetic thickeners can be used. Preferable examples include a synthetic thickener, for example, an emulsion in oil or an aqueous solution or a water-in-oil dispersion in which a synthetic (co) polymer is generally dissolved in white oil or the like, and a (co) polymer content of about 40 mass. % Is preferable.

  Preferred examples of the thickener include 85 to 95% by weight of acrylic acid, 4 to 14% by weight of acrylamide, and about 1% by weight of a (meth) acrylamide derivative represented by the following formula VIII and having a molecular weight Mw of 100,000 to 200,000 g / mol. It is.

  The symbols in the above formula are the same as the above definition.

  The printing paste of the present invention may contain 30 to 70% by weight of white oil as an additional thickener. The aqueous thickener contains the (co) polymer in an amount of usually 25% by mass or less, and sometimes 50% by mass or less (so-called thickener dispersion). When using an aqueous composition of a thickener, aqueous ammonia is usually added. By using a solid composition of a granular thickener, it is possible to avoid volatilization / emission and obtain a pigment print.

  The paste of the present invention may further contain a texture improver, examples of which include silicones, especially polydimethylsiloxane, and fatty acid esters. Specific examples of commercially available texture improvers suitably added to the printing paste of the present invention include Acramin (registered trademark) Weichmacher SI (Bayer AG), Luprimol SIG (registered trademark) and Luprimol CW (registered trademark) (manufactured by BASF). ).

  The printing paste of the present invention may contain one or more emulsifiers as other components, particularly when the paste contains an extender containing white oil and is obtained as an oil-in-water emulsion. Examples of suitable emulsifiers are aryl- or alkyl-substituted polyglycol ethers. Examples of suitable emulsifier products are Emulgator W® (Bayer), Luprintol PE New® and Luprintol MP® (BASF) and Solegal W (Hoechst).

  Examples of other usable components are Bronsted acids such as ammonium hydrogen phosphate, but it is preferred not to add Bronsted acids.

  The printing paste of the present invention can be produced, for example, by mixing water with one or more antifoaming agents, for example, silicone-based antifoaming agents. At least one composition of the invention is added with mixing, for example by stirring. One or more pigments are then added, for example in the form of a pigment preparation. It is also possible to provide a next step and add a texture improving agent such as one or more silicone emulsifiers.

  Then, one or more thickeners can be added and further mixed by stirring or the like to be uniform.

Typical printing pastes of the present invention are each 1 kg of printing paste,
5 to 250 g, preferably 10 to 200 g of the composition of the invention,
0.1-10 g, preferably 1-5 g of emulsifier,
1 to 200 g, preferably 10 to 100 g thickener,
0.1 to 100 g, preferably 1 to 60 g of pigment,
Optionally other auxiliaries, and remaining components, preferably water,
including.

    In one embodiment of the present invention, the printing paste of the present invention has a viscosity at 20 ° C. of 50 to 150 dPa · s, preferably 60 to 100 dPa · s.

  Pigment printing using at least one printing paste of the present invention is performed by various known methods. Usually, a screen that allows the printing paste to pass through by pressing with a squeegee is used. This method is a kind of screen printing. According to the pigment printing process using the printing paste according to the present invention, the substrate on which the printing has been performed, in particular, provides an excellent combination of gloss and depth of shade of the printed material, as well as the superiority of the printed substrate. Can also be obtained. The flexible substrate obtained by the method of the present invention has excellent washing fastness and good dry cleaning resistance. Therefore, according to the present invention, a flexible substrate printed by the method of the present invention using the printing paste of the present invention is produced. The flexible substrate of the present invention has excellent fastness. Furthermore, the substrate of the present invention has a very low formaldehyde content.

  In another embodiment of the present invention, a pigment dyeing method using at least one kind of the composition of the present invention (hereinafter also referred to as the pigment dyeing method of the present invention) is used. The dyeing process according to the invention is carried out by treating at least one flexible substrate, preferably a textile substrate, with at least one dye solution according to the invention comprising at least one composition according to the invention. Hereinafter, the dye solution containing at least one composition of the present invention is also referred to as the dye solution of the present invention.

  The dyeing liquid of the present invention may further contain a wetting agent, preferably a wetting agent which is a low foaming wetting agent. This is because the quality of the dyeing is impaired if undulations occur due to foaming caused by turbulent flow in the dyeing operation. Examples of wetting agents that can be used are for example ethoxylated and / or propoxylated products of fatty alcohols, or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fats or oxo process alcohols, and oleic acid or An ethoxylated product of an alkylphenol, an alkylphenol ether sulfate, an alkyl polyglycoside, an alkyl phosphate, an alkyl phosphonate, an alkyl phosphate or an alkyl phenyl phosphate.

  Dry woven fabrics or fabrics knitted while forming loops by continuous pigment dyeing contain a large amount of air. Therefore, the dyeing in this case requires the use of a deaerator. An example of a main component of the degassing agent is a polyether siloxane copolymer. Used in the staining solution of the present invention in an amount of 0.01 to 2 g / liter.

  The dye solution of the present invention may further contain an antimigration agent. Examples of suitable migration inhibitors are copolymers of ethylene oxide and propylene oxide, for example with a molecular weight Mn of 500 to 5000 g / mol, preferably 800 to 2000 g / mol.

  The dyeing solution of the present invention may further contain one or more texture improving agents. In general, polysiloxane or wax is used as a texture improver. Polysiloxane is excellent in durability, and the wax is gradually washed away during use.

  The staining solution of the present invention usually exhibits a weakly acidic pH, preferably a pH in the range of 4 to 6.5. The viscosity of the staining liquid of the present invention is preferably less than 100 mPa · s. The surface tension of the dyeing liquid of the present invention is adjusted so that the fibers can be wetted. A surface tension of less than 50 mN / m is widely used.

In one embodiment, the staining solution of the present invention comprises 10 to 100 g, preferably 20 to 50 g of the composition of the present invention per liter,
0-5 g, preferably 0.1-2 g of wetting agent,
1 to 20 g, preferably 5 to 15 g of Na ₂ SO ₄ ,
1 to 20 g, preferably 5 to 15 g of migration inhibitor,
0.5 to 25 g, preferably 1 to 12 g of pigment.

    Furthermore, this invention provides the manufacturing method of the said dyeing | staining liquid. In the production process according to the invention, a pigment, preferably one or more surfactants, a pigment preparation comprising pigment and water, and other solvents, antifoams, texture improvers, emulsifiers and / or biocides. The above additives such as the above are mixed, and water is replenished to a predetermined amount. In order to produce the dyeing liquid of the present invention, the components of the dye liquid of the present invention are generally stirred in a mixing container. There are no restrictions on the size and shape of the container. It is preferable to carry out filtration for purification after stirring.

  Furthermore, the present invention provides a method for dyeing a textile substrate using the above dyeing liquid (hereinafter also referred to as a pigment (pigment) dyeing method of the present invention). The pigment staining method of the present invention is carried out in an ordinary apparatus. A pad mangle mainly composed of two pressing rolls (nip rolls) through which the fabric passes is preferably used. The dye liquor is present on the roll and wets the fabric. The fibers are compressed by the nip pressure, and a certain amount of impregnation is ensured.

  After the actual impregnation step, a heat drying step and a fixing step are usually performed. The fiber is preferably dried at 100 ° C. to 110 ° C. for 30 seconds to 3 minutes and fixed at 150 ° C. to 190 ° C. for 30 seconds to 5 minutes. The pigment dyeing step is preferably performed by padding. The printed and dyed substrate has a particularly excellent brightness (gloss) and excellent texture. Moreover, in this invention, the base | substrate dye | stained by the method of this invention using the dyeing liquid of this invention is provided.

  The present invention further provides a dyed flexible substrate obtained by the pigment dyeing method of the present invention. The flexible substrate obtained according to the present invention has excellent scratch resistance and good fastness when dry and wet, in particular, the shade of shade caused by blush wash at boil is minimized. Good fastness is obtained due to the above.

  The present invention further provides the use of the composition of the present invention or the composition produced by the method of the present invention as a binder for nonwovens. Furthermore, the present invention provides a method for producing a nonwoven fabric by using the composition of the present invention or the composition produced by the method of the present invention. 5 to 100 (based on the solids content of the composition of the invention) of the composition of the invention or the composition produced by the method of the invention, based on the fiber mass of the unconsolidated nonwoven %, Preferably 20 to 50% by mass. Non-woven fabric is made of polyamide, polyester, polyacrylonitrile, polyolefin, such as polypropylene or polyethylene, cellulose, cotton, wool, silk, glass fiber, etc. It is preferable to obtain it by contacting by a method. For example, unbonded nonwoven can be dipped, impregnated or sprayed with the composition of the present invention. Thereafter, an excess amount of the composition of the present invention may be squeezed prior to conventional drying treatment. The crosslinking temperature is 100 ° C to 200 ° C, preferably 130 ° C to 170 ° C.

  The fleece can be, for example, duplexed, yarn reinforced, stitched, wound, and / or shrunk.

  Contact between the fleece and the composition of the present invention may be effected, for example, by face padding, impregnation, such as foam impregnation, spraying or drying.

  After the contact step, the composition of the present invention may be removed by pressing or the like, and then dried at a temperature of, for example, 70 ° C. to 110 ° C. for 30 seconds to 20 minutes, preferably 1 minute to 10 minutes.

  Thereafter, heat treatment (crosslinking) is performed at 100 to 200 ° C., preferably 130 to 1170 ° C., for 30 seconds to 5 minutes, preferably 3 minutes or less.

  The present invention further provides consolidated nonwovens made using one or more compositions of the present invention. The bonded nonwoven fabric of the present invention comprises 5 masses of one or more kinds of copolymers produced by copolymerization in the presence of one or more heterocyclic compounds having two or more carbamate groups having a glass transition temperature Tg of less than 15 ° C. % To 60% by mass. The bonded nonwoven fabric of the present invention is excellent in extremely excellent workability and extremely low formaldehyde content.

  Hereinafter, the present invention will be described in more detail with reference to examples.

General considerations: Completely demineralized water means water from which salt has been removed using conventional ion exchangers.

  The glass transition temperature Tg was measured by a method according to German Industrial Standard DIN53765 using a Matter suggestion scanning calorimeter.

  Sample mass: A 10-20 mg copolymer dispersion was measured in a 40 ml standard aluminum crucible.

  In the standard method for the dispersion, the glass transition temperature Tg is automatically measured as an intermediate value of the second heating curve by macro evaluation. A blank curve was obtained in advance by measurement using an empty (without sample) crucible, and this value was subtracted.

  The heating process conforms to the current German industry standard, DIN 53765.

  The starting point in the measurement was 25 ° C. The sample is heated at 20 ° C. per minute to 150 ° C. (ie a temperature exceeding Tg). The temperature of 150 ° C. is maintained isothermally for 3 minutes, then the sample is cooled to 20 ° C. per minute to −110 ° C. After maintaining the temperature at −110 ° C. for a further 7 minutes, the sample was heated to 20 ° C. per minute to 150 ° C. (this fraction is the object of evaluation), and the temperature of 150 ° C. was further maintained for 5 minutes.

  Free (separated) formaldehyde was measured by Law 112 and AATCC 112 methods (EN ISO 14 184, parts 1 and 2) and DEN EN ISO 14184-1 and DEN EN ISO 14184-2, respectively. Only the results of Law 112 are listed as an example.

1. Production of Composition of the Invention 1.1 Production of Composition F.1 of the Invention The following mixture was prepared.

Mixture 1.1:
735 g n-butyl acrylate, 360 g styrene, 72 g 2-hydroxyethyl acrylate, 8.4 g freshly distilled acrylic acid, 24 g of the formula VI. 1 compound,

730 g of complete demineralized water,
15.1 g sodium lauryl sulfate is dissolved in 38.5 g water,
Furthermore, these are dispersed together in 770 g of complete demineralized water.

Mixture 1.2:
Material with 1 g Na ₂ S ₂ O ₈ (sodium peroxodisulfate) dissolved in 150 ml complete demineralized water.

Mixture 1.3:
Material containing 1.2 g HO—CH ₂ —SO ₂ Na in 100 ml complete demineralized water.

  A 5 liter tank equipped with a stir bar and fed with nitrogen and equipped with three feeding means was charged with 750 ml of complete demineralized water and 27.2 g of polystyrene seeds with an average particle size of 25 nm.

  The initial charge was stirred for 15 minutes while purging with nitrogen, then it was heated to 75 ° C. The temperature was maintained at 75 ° C. during the emulsion polymerization in the next step.

  In addition, the addition of mixtures 1.1, 1.2 and 1.3 by parallel flow feeding was started. The addition of mixture 1.1 took about 180 minutes and the addition of mixtures 1.2 and 1.3 took about 195 minutes.

When the addition of mixture 1.3 was completed, the batch was polymerized for an additional 30 minutes. Then a solution containing 5.2 g tert-butyl hydroperoxide (70% by weight in water) in 45 ml distilled water and a solution containing 2.4 g HO—CH ₂ —SO ₂ Na in 50 ml distilled water, Deodorization was performed by simultaneous addition for minutes.

  Then, it cooled to 30 degreeC in 10 minutes, and also 25 mass% ammonia water was added after this, and it adjusted to pH 6.7. Thereafter, the mixture was further stirred for 10 minutes.

  Subsequently, it cooled to room temperature and filtered using a 125 micrometers net | network.

  The composition F. obtained in this way Table 1 shows the properties of 1.

1.2 Production of Composition F.2 of the Invention The following mixture was prepared:

Mixture 2.1:
240 g n-butyl acrylate, 282.0 g ethyl acrylate, 7.8 g freshly distilled acrylic acid, 58.2 g styrene, 25.2 g diethylene glycol, 12 g of the formula VI. 1 compound,

  The mixture was stirred until a clear solution was formed, then the following materials were added.

Dissolve 7.2 g sodium lauryl sulfate in 18.5 g water,
4.2 g n-C ₁₈ H ₃₇ O (CH ₂ CH ₂ O) ₁₈ H is dissolved in complete demineralized water,
A material in which these are dispersed together in 300 ml of complete demineralized water.

Mixture 2.2:
A material in which 2.4 g Na ₂ S ₂ O ₈ (sodium peroxodisulfate) is dissolved in 100 ml complete demineralized water.

Mixture 2.3:
Material containing 0.2 g HO—CH ₂ —SO ₂ Na in 50 ml complete demineralized water.

  A 5 liter tank equipped with a stir bar and fed with nitrogen and equipped with three feeding means was charged with 300 ml of complete demineralized water and 13.6 g of polystyrene seeds with an average particle size of 25 nm.

  The initial charge was stirred for 15 minutes while purging with nitrogen, then it was heated to 75 ° C. The temperature was maintained at 75 ° C. during the next copolymerization.

  In addition, the addition of mixtures 2.1, 2.2 and 2.3 by parallel flow feeding was started. The addition of mixture 2.1 took about 3 hours and the addition of mixtures 2.2 and 2.3 took about 3 hours and 15 minutes.

When the addition of mixture 2.2 was complete, the batch was polymerized for an additional 30 minutes. It is then mixed with 3.5 g of 25% aqueous ammonia and then 2.6 g of tert-butyl hydroperoxide (70% by weight in water) in 25 ml of distilled water and 1.7 g of HO—CH ₂ —SO ₂ Deodorization was performed by simultaneously adding a solution containing Na in 25 ml of distilled water for 90 minutes.

  Then, it cooled to room temperature and stirred with the following materials, and obtained the mixture.

A solution of 6 g n-C ₁₈ H ₃₇ O (CH ₂ CH ₃ O) ₁₈ H in 24 g complete demineralized water,
3 g of 1,2-benzisothizol-3 (2H) -one fungicide (2.5% by weight) and 2-methyl-2H-isothiazol-3-one (2.5% by weight) in propylene glycol Solution (3 g), and 70 g of complete demineralized water.

  Next, 25% by mass of aqueous ammonia was added to adjust the pH of the mixture to 6.5.

  Next, filtration using a 125 μm net was performed.

  The composition F. obtained in this way Table 1 shows the properties of 2.

II. Production of pigment printing paste of the present invention (general formulation)
2.1. Manufacture of pigment preparations 2.1.1 Manufacture of blue pigment preparations
The following materials were ground together in a Drais DCP SF 12 Superflow stirred ball mill.

1800g Pigment Blue 15: 3
450g of _{n-C 18 C 37 O (} CH 2 CH 2 O) 25 H
3700 g distilled water.

  Grinding was continued until the average particle size of the pigment particles reached 320 nm. A blue pigment preparation P1 was obtained.

2.1.2 Production of red pigment preparation
The following materials were ground together in a Drais DCP SF 12 Superflow stirred ball mill.

1800g Pigment Red 122
450g of _{n-C 18 C 37 O (} CH 2 CH 2 O) 25 H
3700 g distilled water.

  Grinding was continued until the average particle size of the pigment particles reached 350 nm. A red pigment preparation P2 was obtained.

2.2 Treatment of the pigment preparation of the invention and the composition of the invention, production of the printing paste of the invention, and printing of the pigment of the invention General formulation 700 g of fully desalted water in a glass beaker, 0.25 g Of 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 0.25 g of ethylene glycol antifoam is added, then 120 g of each composition of the invention is stirred. Then, 25 g of a conventional thickener (water-in-oil emulsion of a cross-linked copolymer of acrylic acid and acrylamide, solid content 40% by weight) was added with stirring.

  Then, it stirred for 8 to 10 minutes with the high-speed stirrer, and the thickener was fully swollen. Then 40 g of one of the above pigment preparations was added. The pH was adjusted to a final value of 8.5 with ammonia.

  Finally, the batch was homogenized by stirring for an additional 12-15 minutes and completely desalted water was replenished to a total volume of 1 liter.

  Haake Mess-Technik GmbH & Co., (Karlsruhe), the final viscosity measured with a VT02 viscometer is 7 Pa. s. All of the products were produced as a pigment-free paste printing DP having a smooth appearance and smooth fluidity and having no aggregation.

Printing substrate: Cotton fabric fiber Printing: 8mm squeegee, magnet attractive force 6th stage,
E55 screen gauze
Drying: Drying cabinet 80 ° C.

  Next, heat treatment (crosslinking) was performed on the tension frame with hot air to 150 ° C. for 5 minutes.

  Textiles-Tests for color fastness Part C07: Color fastness to wet scrubbing of pigment-printed textiles (ISO 105 -C07; 1999); German version EN ISO 105-C07: 2001).

Boiling brush cleaning according to DIN EN ISO 105-C07: Evaluation grade criteria: Very good, good, satisfactory, sufficient, insufficient, nonconforming.

  The relative color intensities were measured after brush washing without heat treatment and after brush washing after heat treatment. Compared to the case where no heat treatment was performed, the relative color intensity when the heat treatment was performed was 2 grades higher.

  The printed fabric of the present invention did not show a sticky tendency.

2.3 Processing of the composition of the present invention into the dye solution of the present invention and implementation of the pigment dyeing method of the present invention 2.3.1 Production of the dye solutions FF1 to FF4 of the present invention General formulation:
The following materials were mixed in a stirring vessel.
800g of completely desalted water
Pigment preparation P1 or P2 5 g / l (calculated on the basis of pure pigment)
Composition of the invention 30 g / l
(Calculated based on binder solid content)
EO ₈ PO ₇ EO ₈ 5g / l (migration inhibitor)
Na ₂ SO ₄ 10 g / l
(NH ₄ ) H ₂ PO ₄ 2 g / l
The above material was supplemented with a complete amount of demineralized water to a total volume of 1 liter.

Migration inhibitor: The migration inhibitor used in the general formulation has a cloud point of 40 ° C. in water, an average molecular weight Mw of 1100 g / ml, a freezing point <5 ° C., a viscosity 175 mPa.s at 25 ° C. EO ₈ PO ₇ A block copolymer represented by EO ₈ (EP is ethylene oxide, PO is propylene oxide).

2.3.2 Implementation of the pigment dyeing method of the present invention and performance test of fabric dyed according to the present invention
Using a Mathis HVF 12085 pad mangle, a fiber substrate (polyester / cotton 60/40) was dyed with the dyeing solution of the present invention prepared according to 2.3.1 above. The nip pressure of the roll pair was 2.6 bar, the moisture absorption rate (content) was 55%, and the application speed was 2 m / min. The fabric was then dried in a LTF89534 circulating air cabinet manufactured by Mathis for 60 minutes at 110 ° C. (air circulation 50%). In the next step, curing was performed for 30 minutes at 190 ° C. while circulating air (100%).

  The fastness after the pigment dyeing method of the present invention and the resulting difference in light and darkness were insufficient before curing, but were good after curing at 190 ° C./30 minutes. That is, it was shown that the crosslinking was performed well.

  In order to measure the quality of the pigment dyed binder used for dyeing and printing, the test was conducted by a predetermined test method.

  The test apparatus used was performed using a friction brush and a motor-driven clock meter having two measuring instruments. One meter is used to measure the total number of strokes, and the other meter is used to measure the number of strokes per test.

[Production of test sample]
A strip having a length of 25 cm and a width of 4 cm was cut out from each sample made of polyester-cotton produced by the pigment dyeing method of the present invention.

[Examination]
A soap-soda solution (5 g / liter soap (Verna Needle soap as specified in ISO 105-C03 and 3 g / liter Na ₂ CO ₃ ) was boiled in a stainless steel pot. -It was introduced into an aqueous soda solution and boiled for 30 minutes at a dye solution ratio of 50: 1.

  Thereafter, the sample was clamped and held on a brush cleaning device, introduced into 100 ml of hot cleaning liquid, and rubbed back and forth along a 10 cm area. The number of strokes (reciprocating motion) of scrubbing was 50 back-and-forth reciprocating strokes.

  The sample was removed from the brush washer and rinsed twice with chilled distilled water and then with cold running tap water for 10 minutes. Samples were subjected to concentric dehydration and ironed to dryness.

Boiling brush cleaning according to DIN EN ISO 105-C07: Evaluation grade criteria: Very good, good, satisfactory, sufficient, insufficient, nonconforming.

  Discoloration was evaluated by the ISO 105 / A02 gray scale.

Claims (22)

(A) at least one copolymer having a glass transition point Tg of less than 15 ° C.
(B) A method for producing a composition, which is produced by copolymerization in the presence of at least one kind of heterocyclic compound having at least two carbamate groups.   The production method according to claim 1, wherein the composition is an aqueous composition.   The production method according to claim 1 or 2, wherein at least one heterocyclic compound is a triazine derivative. The copolymer (a) is represented by the general formula I

A compound of
Formula II

Of unsaturated esters,
Formula III

Vinyl aromatic compounds,
Formulas IVa and IVb

And a copolymer unit derived from a plurality of main monomers selected from the group consisting of non-aromatic hydrocarbons having 2 to 8 carbon atoms and having at least one C—C double bond In a ratio of 40% by mass or more of the total mass of the copolymer,
R ¹ , R ⁴ , R ¹⁰ may be the same or different and each is selected from hydrogen and C ₁ -C ₁₀ alkyl;
R ² , R ⁵ , R ¹¹ may be the same or different and are each selected from hydrogen and C ₁ -C ₁₀ alkyl;
Each X may be the same or different and each represents halogen, CN or OR ¹² ;
R ³ , R ⁶ , R ¹² may be the same or different and each is selected from C ₁ -C ₂₀ alkyl;
R ⁷ , R ⁸ , R ⁹ may be the same or different and each is selected from hydrogen and C ₁ -C ₁₀ alkyl;
The production method according to any one of claims 1 to 3, wherein k is a copolymer meaning an integer of 0 to 3.   5. The method according to claim 1, wherein the at least one copolymer comprises at least one copolymerized comonomer having at least one alcoholic hydroxyl group or at least one COOH group. The production method according to item. At least one heterocyclic compound having at least two carbamate groups is represented by the general formula VI

Wherein Y ¹ is selected from R ¹³ , oxygen and N—H,
Z ¹ is selected from hydrogen or CO—O—R ¹³ ;
It may be different from one another each R ¹³ is the same, the production method according to any one of claims 1 to 5, characterized in that it is selected from C ₁ -C ₁₀ alkyl, respectively. Y ¹ is N-H,
Z ¹ is CO-O-R ^13, method according to claim 1, characterized in that all of R ¹³ are the same.   The production method according to any one of claims 1 to 7, wherein the compound (a) is produced in the presence of at least two kinds of heterocyclic compounds each having at least two carbamate groups.   The method according to any one of claims 1 to 8, wherein the glass transition temperature Tg of at least one copolymer is in the range of -30 ° C to less than 15 ° C.   The composition manufactured by the manufacturing method of any one of Claims 1-9.   The composition according to claim 10, which is aqueous.   Use of the composition according to claim 10 or 11 for treating flexible substrates.   A method for treating a flexible substrate, comprising using the composition according to claim 10 or 11.   12. A method of treating a flexible substrate, comprising first contacting the flexible substrate with at least one composition according to claim 10 or 11 and then heating.   The processing method according to claim 13 or 14, wherein the flexible substrate is a woven fabric.   The processing method according to any one of claims 13 to 15, wherein a pigment dyeing method is used.   The processing method according to any one of claims 13 to 15, which is a textile printing method.   The processing method according to claim 13, wherein the processing method is a web joining method.   The flexible base | substrate obtained using the processing method in any one of Claims 13-18.   A printing paste comprising at least one composition according to claim 10 or 11 and at least one pigment.   A method for producing a printing paste, comprising mixing at least one composition according to claim 10 or 11 and a pigment.   A bonded web produced by using at least one composition according to claim 10 or 11.