JP2000119968A - Resin composition for processing cellulose-based substrate and processing of cellulose-based substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve adhesion to a cellulose-based substrate without impairing merits in the case of using a polyfunctional oxazoline compound and/or a polyfunctional carbodiimide compound. SOLUTION: In processing a cellulose-based substrate by using a resin composition containing a carboxy group-containing polymer (A) and at least one kind of a compound selected from a polyfunctional oxazoline compound and a polyfunctional carbodiimide compound as essential components, further at least one kind of a compound (C) selected from a compound containing a functional group which can be reacted with a hydroxy group and form a carboxy group by the reaction with the hydroxy group and a compound containing a functional group to be reacted with a hydroxy group and a carboxy group is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin for processing cellulose-based substrates useful as a binder for textile printing of cellulose-based substrates such as cotton woven fabric, a fiber processing agent, an impregnating agent, an adhesive, a coating agent and the like. The present invention relates to a composition and a method for processing a cellulose-based substrate.

[0002]

2. Description of the Related Art Pigment printing binders used for T-shirt prints and advertisement flag prints, fiber processing agents,
As the impregnating agent, adhesive, and coating agent, those containing a carboxyl group-containing polymer such as an acrylic resin, a polyester resin, a polyurethane resin, or a polyolefin resin and a crosslinking agent are generally used. At this time, the crosslinking agent is appropriately selected and used from the material of the woven fabric, the temperature of the treatment, and the like.

[0003]

For example, polyvalent oxazoline compounds are mainly used in polyester fibers because they have the characteristics of low-temperature curability, one-pack stability, excellent sharpness, and excellent adhesion to polyester fibers. It is used for printing on woven fabrics consisting of However, since the oxazoline group has low reactivity with the hydroxyl group, when the base material is a cellulosic base material such as cotton woven fabric, there is a problem that the interaction with the base material does not work and the adhesiveness is poor.

Although polyvalent carbodiimide compounds are superior to other crosslinking agents in terms of safety, they do not show very high adhesion to either polyester fibers or cellulose-based substrates. Therefore, an object of the present invention is to provide a resin for processing a cellulose-based substrate, particularly having improved adhesion to a cellulose-based substrate without impairing the advantages of using a polyvalent oxazoline compound and / or a polyvalent carbodiimide compound. An object of the present invention is to provide a composition and a method for processing a cellulose-based substrate.

[0005]

Means for Solving the Problems In order to solve the above problems, the present invention provides the following configurations. (1) A resin composition for processing a cellulose-based substrate, which contains, as an essential component, a carboxyl group-containing polymer (A) and at least one compound (B) selected from a polyvalent oxazoline compound and a polyvalent carbodiimide compound, At least one compound (C) selected from a compound having a functional group capable of reacting with a hydroxyl group and generating a carboxyl group upon reaction with the hydroxyl group, and a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group;
A resin composition for processing a cellulose-based substrate, comprising: (2) A method of processing a cellulose-based substrate with a resin composition containing a carboxyl group-containing polymer (A) and at least one compound (B) selected from a polyvalent oxazoline compound and a polyvalent carbodiimide compound as essential components. And wherein the resin composition further comprises a compound having a functional group capable of reacting with a hydroxyl group and generating a carboxyl group upon reaction with the hydroxyl group, and a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group. A method for processing a cellulosic substrate, characterized by containing at least one compound (C) selected from the group consisting of: (3) A method of processing a cellulose-based substrate with a resin composition containing a carboxyl group-containing polymer (A) and at least one compound (B) selected from a polyvalent oxazoline compound and a polyvalent carbodiimide compound as essential components. A compound having a functional group capable of reacting with a hydroxyl group and generating a carboxyl group upon reaction with the hydroxyl group, and at least one compound selected from a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group ( A method for processing a cellulosic substrate, comprising pre-treating the cellulosic substrate using C) and then treating the cellulosic substrate with the resin composition.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, in addition to a conventionally used polyvalent oxazoline compound and / or polyvalent carbodiimide compound, a compound capable of reacting with a hydroxyl group to form a carboxyl group by reacting with the hydroxyl group is used. Compound,
And a compound capable of reacting with a hydroxyl group and having a carboxyl group ”. It is thought that the main reason for the poor adhesion to the cellulose-based substrate when a polyvalent oxazoline compound or a polyvalent carbodiimide compound is used is that the reactivity between the oxazoline group or the carbodiimide group and the hydroxyl group of the substrate is low. Can be Therefore, the compound (C) capable of reacting with a hydroxyl group is reacted with a cellulose-based substrate, and a carboxyl group generated from this reaction and / or a carboxyl group originally possessed is replaced with an oxazoline group or a carbodiimide group of the compound (B). The reaction forms a bond between the carboxyl group-containing polymer (A) and the cellulosic base material. Thereby, the polyvalent oxazoline compound and / or
Alternatively, the adhesion to the cellulose-based substrate is improved without losing the advantages of the polyvalent carbodiimide compound.

Hereinafter, the present invention will be described in detail. The carboxyl group-containing polymer (A) used in the present invention includes:
Polymer (A-1) having a plurality of carboxyl groups as side chains obtained by polymerizing a monomer component containing at least an unsaturated carboxylic acid: a condensation resin containing a carboxyl group as a terminal and / or a pendant (A-2); a resin (A-3) having a carboxyl group introduced by post-modification can be exemplified. Specific examples include an acrylic resin containing a carboxyl group, a styrene-containing resin, a polyester resin, an alkyd resin, a polyamide resin, a polyurethane resin, and a polyolefin resin. Since it is desirable that the resin composition of the present invention is water-soluble in consideration of the environment, the carboxyl group-containing polymer (A) is water-soluble,
It is preferably water-dilutable or water-dispersible, for example, a water-dispersible or water-soluble acrylic resin; a water-dispersible polyurethane resin; a water-dispersible polyester resin;
Water-dilutable or water-dispersible polyolefin resins and the like can be mentioned as preferable ones.

The supply form of the carboxyl group-containing polymer (A) may be any form such as an organic solvent solution, an aqueous solution, or an emulsion, but as described above, the resin composition of the present invention is aqueous based on environmental considerations. Is desirable,
The carboxyl group-containing polymer (A) is also preferably in the form of an aqueous solution or an emulsion. The compound (B) used in the present invention is at least one selected from a polyvalent oxazoline compound and a polyvalent carbodiimide compound. Among these, polyvalent oxazoline compounds are preferred from the viewpoints of friction fastness in pigment printing, washing resistance, storage stability of the resin composition, and the like.

As the polyvalent oxazoline compound, even a low molecular compound having two or more oxazoline groups,
An oxazoline group-containing polymer may be used, but an oxazoline group-containing polymer is preferable. Low molecular compounds having two or more oxazoline groups include 2,2'-bis-
(2-oxazoline), 2,2'-methylene-bis-
(2-oxazoline), 2,2'-ethylene-bis-
(2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'-tetramethylene-
Bis- (2-oxazoline), 2,2'-hexamethylene-bis- (2-oxazoline), 2,2'-octamethylene-bis- (2-oxazoline), 2,2'-ethylene-bis- ( 4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis- (2-oxazoline), 2,2'-m-phenylene-bis- (2-oxazoline), 2,2 ' -M-phenylene-bis-
(4,4'-dimethyl-2-oxazoline), bis-
(2-oxazolinylcyclohexane) sulfide, bis- (2-oxazolinyl norbornane) sulfide, and the like, and one or a mixture of two or more selected from these groups can be used.

The oxazoline group-containing polymer is represented by the following general formula (I)

[0011]

Embedded image

(Wherein R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, halogen, alkyl, aralkyl, aryl or substituted aryl group, and R ⁵ is a non-alkyl group having an addition polymerizable unsaturated bond. An oxazoline group-containing polymer obtained by polymerizing a monomer component containing a monomer copolymerizable with an addition-polymerizable oxazoline, if necessary, containing an addition-polymerizable oxazoline represented by the following formula: No.

Examples of the addition-polymerizable oxazoline include 2-vinyl-2-oxazoline and 2-vinyl-4-methyl-2.
-Oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-
Isopropenyl-4-methyl-2-oxazoline, 2-
Isopropenyl-5-methyl-2-oxazoline, 2-
Examples thereof include isopropenyl-5-ethyl-2-oxazoline, and one or a mixture of two or more selected from these groups can be used. Among them, 2-
Isopropenyl-2-oxazoline is readily available industrially and is preferred.

The amount of the addition-polymerizable oxazoline used is not particularly limited, but may be 5% by weight of the monomer component.
The above is preferable, and 30 to 60% by weight is more preferable. 5
If the amount is less than the weight percentage, the degree of curing becomes insufficient. 60% by weight
If it exceeds, water resistance is adversely affected. Monomers copolymerizable with the addition-polymerizable oxazoline include (meth)
Methyl acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, a monoester of (meth) acrylic acid and polyethylene glycol,
(Meth) acrylic esters such as 2-hydroxyethyl (meth) acrylate, 2-aminoethyl (meth) acrylate and salts thereof; unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamide, N- Unsaturated amides such as methylol (meth) acrylamide and N- (2-hydroxyethyl) (meth) acrylamide; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; ethylene and propylene Α-olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, etc .; halogen-containing α, β-unsaturated monomers such as styrene, α-methylstyrene, sodium styrenesulfonate, etc.
-Unsaturated aromatic monomers and the like, and one or more of these can be used.

As described above, it is desirable that the resin composition of the present invention is water-soluble in consideration of the environment and the like. Therefore, a water-soluble, water-dilutable or water-dispersible oxazoline group-containing polymer is used as the polyvalent oxazoline compound. It is preferably used, and particularly preferably an oxazoline group-containing water-soluble polymer.
By setting the proportion of the hydrophilic monomer in the monomer component to be subjected to polymerization to preferably 50% by weight or more, a water-soluble oxazoline group-containing polymer can be obtained. 60-90% by weight is particularly preferred. Examples of the hydrophilic monomer include addition-polymerizable oxazoline, 2-hydroxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, a monoester of (meth) acrylic acid and polyethylene glycol, and (meth) acrylic acid. 2-aminoethyl and its salts, sodium (meth) acrylate, ammonium (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, N-
Methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, sodium styrenesulfonate, and the like. Of these, monomers having a polyethylene glycol chain, such as methoxypolyethylene glycol (meth) acrylate, and a monoester of (meth) acrylic acid and polyethylene glycol, which are highly soluble in water, are preferred.

The oxazoline group-containing polymer can be produced by subjecting the above monomer component to solution polymerization in an aqueous medium by a conventionally known polymerization method. The aqueous medium is
There is no particular limitation as long as it is a solvent that can be easily mixed with water, and water alone; a mixture of water and an organic solvent; an organic solvent alone can be mentioned, and particularly water alone; a mixture of water and an organic solvent is preferable.
Examples of usable organic solvents include methanol, ethanol, propanol, isopropanol, butanol, tertiary butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol, acetone, and methyl ethyl ketone. One or more of these are used.

In the present invention, as the oxazoline group-containing polymer, a polymer having an oxazoline group introduced by post-modification of the polymer may be used. Specifically, a reaction between a nitrile group and an aminoethanol group, a dehydration of a hydroxylalkylamide group, and the like. Reactions and the like are available. The polyvalent carbodiimide compound is a compound having two or more carbodiimide groups, and can be produced, for example, by synthesizing an isocyanate-terminated polyvalent carbodiimide by a condensation reaction involving the removal of carbon dioxide from an organic diisocyanate.

As the organic diisocyanate as a raw material for synthesis, aliphatic, alicyclic or aromatic diisocyanates can be used alone or as a mixture of two or more. Specifically, 1,5-naphthylene diisocyanate, 4,4-diphenylmethane diisocyanate,
4,4-diphenyldimethylmethane diisocyanate,
1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexanemethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4-diisocyanate , Methylcyclohexane diisocyanate, tetramethylxylylene diisocyanate, and the like.

Along with the above-mentioned organic diisocyanate,
Using a compound that reacts with a terminal isocyanate group such as monoisocyanate, the molecule can be controlled to an appropriate degree of polymerization. Examples of the monoisocyanate for closing the terminal and controlling the degree of polymerization include phenyl isocyanate, tolyl isocyanate, cyclohexyl isocyanate, dimethylphenyl isocyanate, butyl isocyanate, and naphthyl isocyanate. In addition, as a terminal blocking agent, as an active hydrogen-containing compound capable of reacting with an isocyanate group, a hydroxyl group, an imino group, an amino group, a carboxyl group, a mercapto group, an aliphatic group having an epoxy group, an alicyclic or Aromatic compounds can also be used.

The above-mentioned condensation reaction of the organic diisocyanate with the removal of carbon dioxide proceeds in the presence of a carbodiimidization catalyst. Examples of the catalyst include 1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide and 3-phospholene isomers thereof. Phosphorene oxide or the like can be used.

As described above, it is desirable that the resin composition of the present invention is aqueous from the viewpoint of the environment and the like. Therefore, a water-soluble, water-dilutable or water-dispersible polyvalent carbodiimide compound is used as the polyvalent carbodiimide compound. Is preferred. In this case, self-emulsification or an aqueous solution form can be obtained by performing dispersion processing using an appropriate dispersant to form an aqueous dispersion, or adding a hydrophilic segment in the molecular structure of the polyvalent carbodiimide compound. As a dispersant for obtaining an aqueous dispersion, a nonionic surfactant is suitable, and specific examples include a nonylphenyl surfactant.

The self-emulsifying or water-soluble polyvalent carbodiimide compound is obtained by synthesizing an isocyanate-terminated polyvalent carbodiimide by a condensation reaction involving the removal of carbon dioxide from an organic diisocyanate and then further reacting with a functional group having reactivity with an isocyanate group. It can be produced by providing a hydrophilic segment having a group. Examples of the hydrophilic segment include quaternary ammonium salts of dialkylamino alcohols (eg, quaternary salts of 2-dimethylaminoethanol) and quaternary salts of dialkylaminoalkylamines (eg, 3-dimethylamino-n-propylamine). Alkyl sulfonates having at least one reactive hydroxyl group (eg, sodium hydroxypropanesulfonate), polyethylene oxide end-capped with an alkoxy group, or a mixture of polyethylene oxide and polypropylene oxide (eg, a methoxy group or an ethoxy group) Can be used.

Examples of such compounds include carbodilite V-01, V-02, V-03, V-04, V
-05, V-06 (manufactured by Nisshinbo), UCARLNK X
Those commercially available as L-29SE and XL-29MP (manufactured by Union Carbide) can be used. The amount of the compound (B) used is preferably 0.1 to 100% by weight based on the carboxyl group-containing polymer (A).
20% by weight is more preferred. When the amount of the compound (B) is less than 0.1% by weight, the degree of curing is insufficient, and when the amount of the compound (B) is more than 100% by weight, the compound which does not contribute to the reaction is obtained. A large amount of (B) remains and may adversely affect water resistance.

The compound (C) used in the present invention is a compound having a functional group capable of reacting with a hydroxyl group and generating a carboxyl group upon reaction with the hydroxyl group, and a functional group capable of reacting with a hydroxyl group and a carboxyl group. At least one selected from compounds having Examples of the functional group capable of reacting with a hydroxyl group include an acid anhydride group, an aldehyde group, an epoxy group, an isocyanate group, a methylol group, and the like. It is an anhydride group. In addition, those which can react with a hydroxyl group only under severe conditions, such as a carboxyl group, are not included in the “functional group capable of reacting with a hydroxyl group”.

Accordingly, the "compound having a functional group capable of reacting with a hydroxyl group and generating a carboxyl group upon reaction with the hydroxyl group" includes an acid anhydride group-containing compound. However, the acid anhydride group in the acid anhydride group-containing compound may be wholly or partially ring-opened,
Alternatively, it may be a monoesterified product or a monoamidated product. The ring-opened product of the acid anhydride group is a product in which all or a part of the acid anhydride group is opened by hydrolysis and the carboxyl groups are adjacent to each other. Examples of the acid anhydride group-containing compound include an acid anhydride group-containing low molecular weight compound and an acid anhydride group-containing polymer.

Examples of the low molecular weight compound containing an acid anhydride group include maleic anhydride, citraconic anhydride, succinic anhydride, tetrapropenyl succinic anhydride, trimellitic anhydride, pyromellitic anhydride, glutaric anhydride, diglycol anhydride, and diglycol anhydride. Examples thereof include acids, butanetetracarboxylic anhydrides, and all or some of these ring-opened products, monoesterified products, monoamidated products, and the like.

As the acid anhydride group-containing polymer, one or more monomers selected from ethylenically unsaturated dicarboxylic anhydrides, all or some of these ring-opened products, monoesterified products and monoamidated products are essential. Examples include those containing as a repeating unit, a monomer component containing at least one of the above monomers as an essential component, or a monomer component containing only an ethylenically unsaturated dicarboxylic anhydride as an essential component, and polymerizing. Alternatively, after polymerization, all or part of the unsaturated dicarboxylic anhydride groups can be obtained by ring opening, monoesterification, or monoamidation. Examples of the monomer include itaconic anhydride, maleic anhydride, citraconic anhydride, and ring-opened, monoesterified, and monoamidated products thereof. Examples of such an acid anhydride group-containing polymer include a styrene-maleic anhydride copolymer and an isobutylene-maleic anhydride copolymer. Further, a polymer in which an acid anhydride group is introduced by post-modification can also be used.For example, a maleic anhydride-modified polyolefin, a maleic anhydride graft polymer, all or a part of an acid anhydride group contained in these polymers is used. Ring-opened product, monoesterified product,
Monoamidated compounds may be mentioned.

As the acid anhydride group-containing compound, a compound having two or more acid anhydride groups in a molecule is preferable, and from the viewpoint of not deteriorating physical properties such as water resistance, an acid anhydride group-containing polymer is particularly preferable. Is preferred. The ring-opened product, monoesterified product and monoamidated product of the acid anhydride group can be heated to 70
The ring was closed again at about 140 ° C. and returned to the acid anhydride group,
Next, it reacts with the hydroxyl group of the cellulosic substrate. These ring-opened products, mono-esterified products and mono-amidated compounds are particularly preferable because they have low reactivity and excellent stability because they do not have an acid anhydride group at room temperature. Examples of the monoesterifying agent for monoesterifying the acid anhydride group include methanol, ethanol, i-propanol, t-
Low molecular weight alcohols such as butanol, i-butanol, n-butanol, methyl cellosolve, dimethylaminoethanol, diethylaminoethanol, and acetol are exemplified. Examples of the monoamidating agent for monoamidating the acid anhydride group include low molecular weight amines such as monoethylamine, monobutylamine, diethylamine, and aniline. Among them, methanol, n-butanol, dimethylaminoethanol, diethylaminoethanol and acetol are preferred.

Among these acid anhydride group-containing compounds, when the acid anhydride group has the acid anhydride group as it is, an organic solvent solution,
Alternatively, it can be used as an aqueous dispersion in which an organic solvent solution is dispersed in water. In the case of the ring-opened product, monoesterified product and monoamidated product of the acid anhydride group, they can be used as an aqueous dispersion or aqueous solution thereof. Also,
As the “compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group”, an aliphatic, alicyclic or aromatic aldehyde group-containing carboxylic acid having at least one aldehyde group and one carboxyl group in one molecule And the like. Examples of the aldehyde group-containing carboxylic acid include glyoxylic acid, formylacetic acid, β-formylpropionic acid, β-formylacrylic acid, and phthalaldehyde acid. In the present invention,
As the compound (C), a compound having a carboxyl group and a functional group capable of reacting with a hydroxyl group and generating a carboxyl group by reaction with the hydroxyl group may be used.

These aldehyde group-containing carboxylic acids can be used as an aqueous dispersion or an aqueous solution. The amount of the compound (C) used is preferably 5 to 2000% by weight of the amount of the polyvalent oxazoline compound (B),
0 to 500% by weight is more preferable, and 25 to 200% by weight
Is more preferred. When the amount of the compound (C) is less than 5% by weight, the effect of adding the compound (C) cannot be expected, and when the amount of the compound (C) is more than 2000% by weight, it does not contribute to the reaction. A large amount of the compound (C) remains and may adversely affect water resistance.

The resin composition of the present invention may optionally contain various additives other than those described above, for example, a solvent, a plasticizer, an inorganic or organic filler, a coloring pigment, a dye, a thickener, a dispersing agent, Agents, wetting agents, antifoaming agents, antiseptic / antifungal agents, rust inhibitors can be added. In addition, the washing resistance of the resin composition of the present invention can be improved by appropriately adding an aqueous elastomer such as SBR or a polyurethane elastomer. The amount of the aqueous elastomer used is preferably 2 to 10% by weight, more preferably 5 to 50% by weight of the amount of the carboxyl group-containing polymer (A) used.

As described above, the resin composition of the present invention is preferably aqueous from the viewpoint of consideration for the environment, and therefore, it is preferable to use water as the solvent. The method for processing the cellulose-based substrate of the present invention will be described. Examples of the processing method include the following two methods (1) and (2). (1) Method for processing using the resin composition of the present invention described above (2) First, a cellulose-based substrate is pre-treated using compound (C), and then carboxyl group-containing polymer (A) In the case of the method (1), wherein the resin composition of the present invention described above is applied or impregnated to a cellulose-based substrate, and dried, A method of heat treatment is employed. The temperature of the heat treatment can be selected in a wide range of about 100 to 200 ° C.

In the case of the method (2), as a first step, the compound (C) is applied or impregnated on a cellulosic substrate, dried, and then heat-treated. Subsequently, as a second step, a method of applying or impregnating a resin composition containing the carboxyl group-containing polymer (A) and the compound (B), drying the resin composition, and performing a heat treatment is adopted. The temperature of the heat treatment in the first step and the second step can be selected in a wide range of about 100 to 200 ° C.

The amount of the compound (B) used in the case (2) is the same as that in the case (1), and is preferably 0.1 to 100% by weight based on the carboxyl group-containing polymer (A). 5
-20% by weight is more preferred. The amount of the compound (C) to be used is appropriately selected depending on the type and thickness of the cellulose-based substrate to be used, and is not particularly limited. In the present invention, the cellulose-based substrate is a substrate made of a material containing cellulose. Examples of the shape of the substrate include a fiber, a film, and a plate. Specifically, cotton, cotton blend (refers to a blend of cotton and various synthetic fibers.
In addition to polyester blends, the same applies hereinafter), wood, paper, pulp, hemp, and cellulose derivatives (nitrocellulose, celluloid, cellulose lacquer, acetylcellulose,
Methylcellulose, ethylcellulose, benzylcellulose, viscose rayon, CMC, HEC, etc.), substrates containing these, and substrates coated with these.

The processing of the cellulosic substrate specifically includes a binder for pigment printing, a fiber processing agent, a coating or impregnating agent, an adhesive, a coating agent and the like.
When used as a binder for pigment printing, it is preferable to use an acrylic emulsion or an aqueous urethane resin as the carboxyl group-containing polymer (A), and the target cellulose-based substrate is mainly a cotton or cotton blended fiber. Specifically, a print of a T-shirt or an advertising flag is cited. As the composition of the resin composition, in addition to the carboxyl group-containing polymer (A), the compound (B) and the compound (C), a pigment and a diluent (for example, terpene, heptane, octane,
Emulsions of hydrophobic organic solvents such as petroleum benzine and kerosene in water, water-soluble acrylic resin, polyvinyl alcohol, CM
C) are usually used.

When used as a fiber processing agent, it is preferable to use an acrylic emulsion or rubber latex as the carboxyl group-containing polymer (A), and the target cellulosic base material is mainly a cotton, cotton blend, hemp or rayon fiber It is. Specifically, a binder for nonwoven fabric and the like can be used as the fiber processing adhesive. When used for coating or impregnation, it is preferable to use water-soluble acryl, acrylic emulsion, and styrene-containing resin as the carboxyl group-containing polymer (A), and the target cellulose-based substrate is mainly paper or cotton, especially paper. is there. Specific examples include paper strength enhancement and wrinkle processing.

When used as an adhesive, it is preferable to use an acrylic emulsion or urethane as the carboxyl group-containing polymer (A), and the target cellulosic base material is mainly fiber (cotton, cotton blend, etc.), wood, paper , Cellophane, etc., which can be used for both adhesion to each other and adhesion to other substrates, especially for adhesion of wood, paper or cellulosic fibers (adhesion of wood, paper or cellulosic fibers;
Adhesion of wood, paper or cellulosic fibers to other substrates)
It is effective for

When used for coating, it is preferable to use water-soluble acryl, acrylic emulsion, polyester, urethane or the like as the carboxyl group-containing polymer (A), and the target cellulose-based substrates are mainly paper, wood, and cellulose-based polymers. Substrate coated with the above material.

[0039]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In the examples, “parts” and “%” are unless otherwise specified.
The terms “parts by weight” and “% by weight” are respectively represented. [Preparation Example of Water-Soluble Oxazoline Group-Containing Polymer (1)] A flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 92.1 parts of isopropyl alcohol and 368.5 parts of ion-exchanged water. The mixture was heated to 80 ° C. while gently flowing nitrogen gas. There was previously prepared a monomer mixture composed of 126 parts of methyl methacrylate, 210 parts of 2-isopropenyl-2-oxazoline, and 84 parts of methoxypolyethylene glycol acrylate (light acrylate 130A manufactured by Kyoeisha Chemical Co., Ltd.). , V
-50 (a polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd .: 2,2'-azobis (2-amidinopropane) dihydrochloride), 21 parts of an initiator solution composed of 189 parts of isopropyl alcohol, was respectively dropped from a dropping funnel for 2 hours. It dripped over. During the reaction, the nitrogen gas was kept flowing, and the temperature in the flask was kept at 80 ± 1 ° C. After maintaining the same temperature for 5 hours even after the completion of the dropwise addition, the mixture was cooled after cooling to obtain an aqueous solution of a 2-oxazoline group-containing polymer (1) having a nonvolatile content of 40.4%, a pH of 8.7 and a viscosity of 570 centipoise. [Preparation example of water-dispersible oxazoline group-containing polymer (2)]
In a flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a thermometer, 782.4 parts of deionized water and Hytenol N-08 (polyoxyethylene nonylphenyl ether sulfate ammonium salt manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Of 15
% Aqueous solution, and an appropriate amount of aqueous ammonia (28
%), And the mixture was heated to 70 ° C. while gently flowing nitrogen gas. 5% of potassium persulfate there
An aqueous solution (64 parts) was injected, and a previously prepared monomer mixture consisting of 288 parts of butyl acrylate, 288 parts of styrene and 64 parts of 2-isopropenyl-2-oxazoline was added dropwise over 3 hours. During the reaction, the nitrogen gas was kept flowing, and the temperature in the flask was kept at 70 ± 1 ° C.
After maintaining the same temperature for 2 hours after the completion of the dropping, the internal temperature was raised to 80 ° C.
And the stirring was continued for 1 hour to complete the reaction. Thereafter, the mixture was cooled to obtain an aqueous dispersion of the 2-oxazoline group-containing polymer (2) having a nonvolatile content of 39.8% and a pH of 8.0. [Preparation Example of Carboxyl Group-Containing Polymer (1)] Stirrer,
A flask equipped with a reflux condenser, a nitrogen inlet tube and a thermometer was charged with 782.4 parts of deionized water and Hytenol N-0.
8 (128 parts of a polyoxyethylene nonyl phenyl ether sulfate ammonium salt manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was charged, and 7 parts of nitrogen solution were supplied while gently flowing nitrogen gas.
Heated to 0 ° C. There 5% aqueous solution of potassium persulfate 6
4 parts were injected, followed by 320 parts of previously prepared butyl acrylate, 288 parts of styrene and 32 parts of acrylic acid.
Parts of the monomer mixture were added dropwise over 3 hours.
During the reaction, the nitrogen gas was kept flowing, and the temperature in the flask was reduced to 70
It was kept at ± 1 ° C. After maintaining the same temperature for 2 hours after the completion of the dropwise addition, the internal temperature was raised to 80 ° C., and stirring was continued for 1 hour to complete the reaction. Thereafter, the mixture was cooled and an appropriate amount of aqueous ammonia (2
8%) to adjust the pH to 8.5 to obtain an aqueous dispersion of the carboxyl group-containing polymer (1) having a nonvolatile content of 39.8%. [Preparation Example of Carboxyl Group-Containing Polymer (2)] In the preparation example of carboxyl group-containing polymer (1), 544 parts of butyl acrylate and acrylonitrile 6
An aqueous dispersion of the carboxyl group-containing polymer (2) having a nonvolatile content of 40.2% was obtained in exactly the same manner except that 4 parts and 32 parts of acrylic acid were used. [Examples 1 to 6 and Comparative Examples 1 to 3] First, 3 parts of a thickening emulsifier (Bissurf 1400, manufactured by Kao Corporation) were dissolved in 34 parts of water, and 63 parts of a mineral turpentine were added while stirring with a homomixer. Was added to obtain a reducer.

Nicazole A-01 (a 45.2% aqueous dispersion of a water-dispersible acrylic resin manufactured by Nippon Carbide Industry Co., Ltd.) as a reducer, a carboxyl group-containing polymer, a compound (B) (oxazoline prepared above) Aqueous solution of group-containing polymer (1), aqueous dispersion of oxazoline group-containing polymer (2), or polyvalent carbodiimide compound (UCARLNK XL-29SE (manufactured by Union Carbide): 50% methylpropazole acetate solution), compound (C) (an acid anhydride group-containing compound or glyoxylic acid), and an aqueous pigment (Ryudaye-WB)
lue KW (manufactured by Dainippon Ink and Chemicals, Inc., aqueous dispersion having a solid content of 40.3%) was blended in the amount shown in Table 1 to prepare a pigment-printing resin composition, and a printing cloth was prepared under the following conditions. Obtained. <Printing conditions> Printing method: Flat screen printing (using 100 mesh screen gauze) Fabric: Cotton No. 40 Broad process: Printing-drying (100C x 3 minutes)-heat treatment (130
(° C. × 3 minutes) Table 1 shows the results of the evaluation of the obtained printed fabric according to the following evaluation method. <Evaluation method of printed cloth>-Friction fastness test: JIS L-0849 (wet type) ：: No change, や: Slight discoloration, Δ: Quite discoloration,
×: severe color fading, ××: very severe color fading ・ Washing resistance: JIS L-0217 (103 method) ◎: no change, ○: slight color fading, Δ: considerable color fading,
×: severe color fading, xx: very severe color fading

[0041]

[Table 1]

Examples 7 to 12, Comparative Examples 4 to 6 Aqueous dispersions of the carboxyl group-containing polymer (1) prepared above,
Compound (B) (an aqueous solution of the oxazoline group-containing polymer (1) prepared above, an aqueous dispersion of the oxazoline group-containing polymer (2), or a polyvalent carbodiimide compound (UCAR
LNKXL-29SE (manufactured by Union Carbide): 5
0% methylpropazole acetate solution) and compound (C) (acid anhydride group-containing compound or glyoxylic acid)
Was blended in the amounts shown in Table 2 to prepare a resin composition for paper impregnation processing, and paper impregnation processing was performed under the following conditions. <Impregnation conditions> After impregnating the substrate (filter paper: # 1, manufactured by Advantech) so as to have an impregnation amount of 30% by weight, 1
Heat treatment was performed at 30 ° C. for 3 minutes to obtain a test piece.

The obtained impregnated paper was evaluated according to the following evaluation method.
Table 2 shows the results of the evaluation. <Evaluation Method of Impregnated Paper> The tensile strength of a test piece after immersion in distilled water for 1 hour was measured in accordance with JIS P-8113.

[0044]

[Table 2]

[Examples 13 to 18, Comparative Examples 7 to 9] Aqueous dispersion of carboxyl group-containing polymer (2) prepared above, compound (B) (oxazoline group-containing polymer (1) prepared above) , An aqueous dispersion of the oxazoline group-containing polymer (2), or a polyvalent carbodiimide compound (UCARLNKXL-29SE (manufactured by Union Carbide): a 50% methylpropazole acetate solution) and the compound (C) (acid anhydride group) (Comprising compound or glyoxylic acid) in the amounts shown in Table 3 to prepare a resin composition for wood bonding, and bond 5 m / m thick birch birch materials to each other under the following conditions. Weight: 150 g / m ² Pressing: 10 kg / cm ² × 1 hour Heat treatment: After pressing, 130 ° C. × 3 minutes The results of evaluating the bonded wood according to the following evaluation method are shown in Table 3. <Evaluation Method of Adhered Wood> Using an Instron universal tester, normal adhesiveness (normal condition of materials and interfaces at the time of a tensile test at 20 ° C. and 65% RH) and water-resistant adhesiveness (20
The material and the interface at the time of the tensile test in a state of being left wet in water of 1 ° C. for 1 day were evaluated.

：: Material destruction, Δ: Cohesive peeling, ×: Interfacial peeling

[0047]

[Table 3]

[Examples 22 to 26, Comparative Example 10] [First step: treatment of base material] First, 3 parts of a thickening emulsifier (Bissurf 1400, manufactured by Kao Corporation) was dissolved in 34 parts of water, and homogenized. Mineral turpentine 6 while stirring with a mixer
3 parts were added to obtain a reducer.

The above-mentioned reducer and the compound (C) as a substrate treating agent were blended in the amounts shown in Table 4 to prepare a substrate treating composition, and a treated substrate was obtained under the following conditions. <Substrate treatment conditions> Coating method: Flat screen printing (using 100 mesh screen gauze) Cloth: Cotton 40th broad Process: Printing-drying (100 ° C. × 3 minutes) -heat treatment (130
C. x 3 minutes) [Second step: printing] Next, Nicazole A-01 (a water-dispersible acrylic resin manufactured by Nippon Carbide Industry Co., Ltd., 45.
2% aqueous dispersion), compound (B) (an aqueous solution of the oxazoline group-containing polymer (1) prepared above, an aqueous dispersion of the oxazoline group-containing polymer (2), or a polyvalent carbodiimide compound (UCARLNK XL-29SE) (Manufactured by Union Carbide Co.): 50% methylpropazole acetate solution)), and an aqueous pigment (Ryudie-W Blu)
e KW (manufactured by Dainippon Ink and Chemicals, Inc., solid content 4)
0.3% aqueous dispersion)) were blended in the amounts shown in Table 5 to prepare three types of resin compositions, and the substrate treated in step 1 was printed under the following conditions to obtain a printed cloth. <Printing conditions> Printing method: Flat screen printing (using 100 mesh screen gauze) Fabric: Substrate treated in step 1 Process: printing-drying (100C x 3 minutes)-heat treatment (130
(° C. × 3 minutes) Table 5 shows the results of evaluating the obtained printed fabric in the same manner as in Example 1.
Shown in

[0050]

[Table 4]

[0051]

[Table 5]

[0052]

According to the present invention, the adhesion to a cellulose-based substrate can be improved without impairing the advantages of using a polyvalent oxazoline compound and / or a polyvalent carbodiimide compound. That is, by using the compound (C), it is possible to provide a cellulose-based substrate processing resin composition and a processing method which can be preferably used for various processing of the cellulose-based substrate. Specifically, according to the present invention, effects such as improvement of the friction fastness and washing resistance of the pigment at the time of pigment printing, enhancement of paper strength, and improvement of adhesion can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 79/00 C08L 79/00 Z 101/08 101/08 D06P 1/46 D06P 1/46 3/60 3 / 60 Z F term (reference) 4H057 AA01 AA02 BA15 CA35 CB05 CB08 CB11 CC01 CC02 DA01 DA24 DA34 GA04 GA25 JA10 JB01 4L033 AA02 AC11 AC15 BA56 CA13 CA18

Claims (5)

[Claims] 1. A resin composition for processing a cellulose-based substrate, comprising as essential components a carboxyl group-containing polymer (A) and at least one compound (B) selected from a polyvalent oxazoline compound and a polyvalent carbodiimide compound. Further, at least one compound selected from a compound having a functional group capable of reacting with a hydroxyl group and generating a carboxyl group upon reaction with the hydroxyl group and a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group (C A) a resin composition for processing a cellulose-based substrate. 2. The resin composition for processing a cellulose-based substrate according to claim 1, wherein the compound (C) is a compound containing an acid anhydride group and / or a carboxylic acid containing an aldehyde group. 3. A cellulose-based substrate is processed with a resin composition containing, as essential components, a carboxyl group-containing polymer (A) and at least one compound (B) selected from a polyvalent oxazoline compound and a polyvalent carbodiimide compound. The method, wherein the resin composition further comprises a compound having a functional group capable of reacting with a hydroxyl group and generating a carboxyl group by reacting with the hydroxyl group, and a functional group capable of reacting with a hydroxyl group and a carboxyl group. A method for processing a cellulosic base material, comprising at least one compound (C) selected from compounds having the same. 4. A resin composition containing a carboxyl group-containing polymer (A), at least one compound selected from a polyvalent oxazoline compound and a polyvalent carbodiimide compound (B), and a pigment as essential components, into a cellulose-based fiber. A method for printing a pigment on a cellulosic fiber, which is applied or impregnated, dried, and then heat-treated, wherein the resin composition further reacts with a hydroxyl group and generates a carboxyl group by a reaction with the hydroxyl group. A pigment printing method comprising: a compound having a group; and at least one compound (C) selected from a compound having a carboxyl group and a functional group capable of reacting with a hydroxyl group. 5. A cellulose-based substrate is processed with a resin composition containing, as essential components, a carboxyl group-containing polymer (A) and at least one compound (B) selected from a polyvalent oxazoline compound and a polyvalent carbodiimide compound. A method having a functional group capable of reacting with a hydroxyl group and generating a carboxyl group by reacting with the hydroxyl group, and at least one compound selected from a compound having a functional group capable of reacting with a hydroxyl group and a carboxyl group A method for processing a cellulose-based substrate, comprising pre-treating a cellulose-based substrate with the compound (C), and thereafter treating the cellulosic substrate with the resin composition.