JPH05117975A - Agent for preventing falling of pile of pile cloth, treating method and treated pile cloth - Google Patents

Abstract

PURPOSE:To provide the subject agent composed of an aqueous dispersion of a polyurethane resin having a specific glass transition temperature and effective for preventing the whitening of pile cloth and falling of pile at high temperature. CONSTITUTION:A pile cloth is treated with a treating agent composed of an aqueous dispersion of a polyurethane resin having a glass transition temperature of 0-100 deg.C and optionally incorporated with an organopolysiloxane (for improving the soft feeling, deep color, etc.) and heat-treated to prevent the whitening of pile cloth and falling of pile at high temperature. The cloth is further provided with excellent deep color and impact resilience by this treatment. The polyurethane resin is preferably composed of an aliphatic or alicyclic polyisocyanate and a diol such as hydrogenated bisphenol having a molecular weight of <=500. The treated pile cloth is suitable for upholstery material, automobile sheet, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a treatment agent for preventing hair fall of pile cloths, a method for treating pile yarns or cotton as a raw material using the treatment agent, a method for treating pile cloths, and the treated pile cloths. It is a thing. More specifically, the present invention relates to a treatment agent for preventing a hair fall and whitening phenomenon which causes deterioration in texture and quality of pile fabrics, the above treatment method, and the treated pile fabrics.

[0002]

2. Description of the Related Art Pile cloth is used in large amounts in upholstery and carpets, especially in recent years, as seat fabrics and carpets for vehicles such as automobiles and trains. However, the pile fabric is apt to cause hair collapse due to its structure, and since the side surface has high color brightness and gloss compared to the surface, when hair collapse occurs, the hair collapse portion looks whitish with respect to the normal portion, that is, so-called. A whitening phenomenon occurred, which was a problem in terms of surface texture and deterioration of quality. Specific examples of this phenomenon include a whitening phenomenon such as a finger mark generated when the surface of the pile fabric used for the car seat skin material is traced with a finger or a trace generated when a person sits down. In addition, hair fell over after long-term use and were fixed in a bleached state, or heavy objects such as seat belt metal fittings were left on the seat under high temperature conditions such as in a closed car in the summer. In that case, a phenomenon may occur in which the part is whitened due to irreversible hair collapse due to load and heat. As a method for solving the above-mentioned problems, Japanese Patent Laid-Open No. 61-6374 discloses a mixture of an emulsion of a polyvinyl resin having a 100% modulus of 40 kg / cm ² or more and an emulsion of a polyurethane resin having a 100% modulus of 30 kg / cm ² or less. Describes a method of preventing hair collapse by treating the pile portion with and imparting impact resilience.

[0003]

However, since a low modulus polyurethane resin is used in this method, a long-term hair fall prevention effect cannot be obtained, and in a high temperature environment, the impact resilience decreases and blocking occurs. However, there is a problem in that the above irreversible hair fall cannot be prevented, such as causing the fluff to stick.

[0004]

Means for Solving the Problems The inventors of the present invention can prevent hair collapse and whitening which occur in the pile portion of the pile fabric surface,
In addition, as a result of earnest research on a method for improving the above problems, the present invention has been achieved. That is, the present invention comprises an aqueous dispersion (I) of a polyurethane resin having a glass transition temperature of 0 to 100 ° C., which is a treating agent for preventing hair fall of pile fabrics; used for pile fabrics before forming the fabrics. A method of treating a yarn or a raw material thereof, which is used for a pile cloth, by applying the above-mentioned treating agent to a yarn or a raw material thereof, and heat-treating the same; applying the above-mentioned treating agent to at least a pile portion of the pile cloth. A method for treating a pile fabric, which is characterized by heat treatment; and a pile fabric in which at least a pile portion is treated with the above-mentioned treating agent. The glass transition temperature referred to in the present invention is immediately 2 after cooling with a scanning calorimeter (DSC) at 10 ° C./min (for example, up to −60 ° C.).
The extrapolated glass transition temperature (Tig) value according to JIS K7121-1987 measured while raising the temperature at 0 ° C./min (for example, up to 230 ° C.).

The pile portion on the surface of the pile fabric is required to be able to retain impact resilience even at high temperatures. In general, most of the polyurethane resins have a glass transition temperature of less than 0 ° C., but the polyurethane resin, which is a constituent component of the treatment agent of the present invention, corresponds to this requirement and has a glass transition temperature (hereinafter referred to as Tg).
Is described as 0) to 100 ° C, preferably 10 to 90
C., more preferably 20 to 80.degree. If the Tg is less than 0 ° C., the elasticity of the pile portion at a high temperature cannot be sufficiently obtained, hair fall occurs, and the whitened portion is fixed. Also, Tg
When the temperature exceeds 100 ° C., the film-forming temperature from the aqueous dispersion (I) is too high, and therefore the fiber surface does not form a film on the surface of the fiber under normal processing conditions, and a sufficient hair fall prevention effect is obtained. Absent. In addition, the dispersion form of the aqueous dispersion (I) is O /, which has good workability and is excellent in safety and pollution prevention.
W type is preferable.

The polyurethane resin is derived from an organic polyisocyanate and an active hydrogen component, and as the organic polyisocyanate, an organic polyisocyanate conventionally used for synthesizing a polyurethane resin can be used. In particular, in the present application where light resistance and heat resistance are required, the aliphatic or alicyclic polyisocyanate (a) is preferable. Specific examples of the aliphatic or alicyclic polyisocyanate (a) include hexamethylene diisocyanate (HDI) and aliphatic polyisocyanates such as water-crosslinked polyisocyanate of hexamethylene diisocyanate; isophorone diisocyanate (IPDI), 4,4′-methylenebis Alicyclic polyisocyanates such as (cyclohexyl isocyanate); and combinations of two or more of these.
Of these, alicyclic polyisocyanates are preferable for the present application where elasticity is required at a higher temperature, and 4,4′-methylenebis (cyclohexyl isocyanate) is particularly preferable.

As the active hydrogen component, active hydrogen compounds conventionally used in the synthesis of polyurethane resins can be used.
Examples of the method of increasing the Tg of the polyurethane resin include a method of using an active hydrogen compound containing a benzene ring, a cyclohexane ring, a spiro ring and the like in the molecule. Furthermore,
As a method for keeping the texture of the treated pile good, there is a method of combining the above active hydrogen compound with an active hydrogen compound having a relatively high molecular weight to give the polyurethane resin flexibility. Further, when the combination of the above active hydrogen compounds is insufficient in the effect of preventing the fixation of pile whitening at high temperature, it is necessary to increase the heat softening temperature of the polyurethane resin, so that the above active hydrogen compounds can be further reduced. A method of combining an active hydrogen compound having a molecular weight as a chain extender can be mentioned. A preferred active hydrogen component that satisfies these requirements relatively easily is a diol having a number average molecular weight of 500 or less and a cyclic group selected from hydrogenated bisphenols and / or alkylene oxide adducts of (hydrogenated) bisphenols. Class (b1), number average molecular weight 600
Up to 8000 active hydrogen compounds (b2) and optionally a chain extender (b3).

Specific examples of (b1) are described in hydrogenated bisphenols (b1-1), hydrogenated bisphenols alkylene oxide adducts (b1-2) and bisphenols alkylene oxide adducts (b1-3). The examples will be described separately below. (B1-1): Compound of hydrogenated benzene nucleus of bisphenol, that is, bis (4-hydroxycyclohexyl) methane, 2,2-bis (4-hydroxycyclohexyl) propane, 3,3-bis (4-hydroxycyclohexyl) ) Pentane etc. (B1-2): The above bishydroxy compounds to which an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and butylene oxide is added in a random or block form. Specifically, ethylene oxide 2 mol adduct of bis (4-hydroxycyclohexyl) methane, propylene oxide 2 mol adduct of bis (4-hydroxycyclohexyl) methane, ethylene oxide of 2,2-bis (4-hydroxycyclohexyl) propane 2-mole adduct, 2,2-bis (4-hydroxycyclohexyl) propane 2-mole propylene oxide, 2,2-bis (4-hydroxycyclohexyl) propane butylene oxide 2-mole adduct, 2,2-bis (4- Hydroxycyclohexyl) propane ethylene oxide 1 mol, propylene oxide 1 mol adduct, 3,3-bis (4-hydroxycyclohexyl) pentane ethylene oxide 4 mol adduct, and the like. (B1-3): 4,4′-isopropylidene bisphenol, 4,4′-hydroxy bisphenol, 4,
For bisphenols such as 4'-sulfonyl bisphenol and 4,4'-hydroxybenzophenone (b1-
The one to which alkylene oxide is added as in 2).
Specifically, 2,4'-methylene bisphenol ethylene oxide 2 mol adduct, 4,4'-methylene bisphenol propylene oxide 2 mol adduct, 4,
4'-isopropylidene bisphenol ethylene oxide 2 mol adduct, 4,4'-isopropylidene bisphenol propylene oxide 2 mol adduct, 4,
4'-isopropylidene bisphenol ethylene oxide 1 mol, propylene oxide 1 mol addition product,
2.2 mol of ethylene oxide of 4,4′-hydroxybisphenol, 3 mol of propylene oxide of 4,4′-sulfonylbisphenol,
Ethylene oxide 2 mol adduct of 4,4′-hydroxybenzophenone, butylene oxide 4 mol adduct of 4,4′-hydroxybenzophenone and the like. As the alkylene oxide used to obtain (b1-2) and (b1-3), ethylene oxide is preferable from the viewpoint of imparting elasticity. Since the elasticity at high temperature decreases as the number of addition moles of these alkylene oxides increases, the average number of addition moles per 1 mole of (hydrogenated) bisphenol is preferably 4 moles or less, more preferably 2.5 moles or less.
It is less than or equal to mol. Further, since OH groups at both ends of bisphenols are phenolic and have low reactivity with isocyanate groups, it is preferable to add at least 1 mol per 1 OH group. The amount of (b1) in the polyurethane resin is at least 5% by weight, preferably 10% by weight or more in terms of the content of (hydrogenated) bisphenol units in any one or more of (b1). , And more preferably 12% by weight or more. The higher the content, the higher the Tg of the polyurethane resin. The number average molecular weight of the above (b1) is usually obtained from the OH value of the component (b1).

As the high molecular weight active hydrogen compound (b2) having a number average molecular weight of 600 to 8000, there are polyether polyol (b2-1) and polyester polyol (b2-).
2), polybutadiene glycol (b2-3), polymer polyol (b2-4) and the like having the above-mentioned molecular weight. These can be used in combination of two or more.

Specific examples of (b2-1) include polyethylene glycol, polypropylene glycol, polyoxyethylene-oxypropylene (random and / or block) glycol, polytetramethylene ether glycol, polytetramethylene ether-ethylene (random and / or block). And / or block) glycol, polytetramethylene ether-oxypropylene (random and / or block) glycol, polyhexamethylene ether glycol and the like. These can be used in combination of two or more.

As (b2-2), a polyester polyol obtained by reacting a low molecular weight diol and / or a polyether diol having a number average molecular weight of 1,000 or less with dicarboxylic acids, ring-opening polymerization of lactones, etc. are produced. Examples thereof include polycarbonate diol obtained by reacting phosgene with diols such as polylactone diol and 1.6 hexanediol, bisphenols and the like. These can be used in combination of two or more.

As the low molecular weight diol, ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, 1,3-butanediol,
1,4-butanediol, neopentyl glycol,
Examples thereof include 1,6-hexanediol and 1,3-pentanediol. These can be used in combination of two or more.

As the polyether diol having a number average molecular weight of 1,000 or less, polyethylene glycol, polypropylene glycol, polyoxyethylene-oxypropylene (random and / or block) glycol,
Examples thereof include polytetramethylene ether glycol, polytetramethylene ether-oxyethylene (random and / or block) glycol, polytetramethylene ether-oxypropylene (random and / or block) glycol, polyhexamethylene ether glycol and the like. These can be used in combination of two or more.

As the dicarboxylic acid, aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid, fumaric acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, etc.), etc. Is mentioned. These can be used in combination of two or more.

As lactones, ε-caprolactone,
Examples include valerolactone. These can be used in combination of two or more.

Specific examples of the polyester polyol (b2-2) include polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polybutylene hexamethylene adipate, polydiethylene adipate, poly (polytetramethylene ether) adipate, polyethylene azelate, Examples thereof include polyethylene sebacate, polybutylene azelate, polybutylene sebacate, polycaprolacturone diol, polyhexamethylene carbonate, 4,4′-isopropylidene bisphenol type polycarbonate. These can be used in combination of two or more.

Examples of (b2-3) include a hydroxyl group-terminated polybutadiene homopolymer type, a hydroxyl group-terminated polybutadiene copolymer type (styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, etc.), and part or all of the unsaturated double bonds of the polybutadiene glycols are hydrogen. Those added may be mentioned. These can be used in combination of two or more. Specifically, Poly of Arco USA
Bd series and Nippon Soda Co., Ltd.'s NISSO-PB
G series of P and GI series of PB.

As (b2-4), (b2-1)-
The polymer polyol obtained by polymerizing an ethylenically unsaturated monomer (acrylonitrile, styrene, etc.) in any 1 or more types selected from (b2-3) is mentioned. These can be used in combination of two or more.

Among these high molecular weight active hydrogen compounds (b2) having a number average molecular weight of 600 to 8000, polycarbonate diol is preferable in terms of light resistance and hydrolysis resistance. The number average molecular weight of (b2) is usually O of the component (b2).
Calculated from H value. Further, the number average molecular weight of (b2) is from 1000, from the viewpoint of viscosity at the time of synthesis of the polyurethane resin, solubility in a solvent, elasticity imparting property to a pile portion, and the like.
The range of 3000 is particularly preferred.

In order to further improve the heat resistance, impact resilience and the like of the obtained treated pile, a chain extender (b3) may be optionally used in combination with a part of the active hydrogen component (b). (B
As 3), the average molecular weight is usually 400 (this molecular weight is O
The following active hydrogen compounds (determined by H value or amine value) are mentioned. Specific examples of (b3) include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, and 1,6-hexanediol; glycerin; Trihydric alcohols such as trimethylolpropane and pentaerythritol; amino alcohols such as monoethanolamine and diethanolamine; aliphatic amines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; isophoronediamine, 4,4′-methylenebis ( Alicyclic amines such as cyclohexylamine; hydrazine, dibasic acid dihydrazine (adipic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, isophthalic acid) Acid dihydrazide and the like), water and the like. You may use together 2 or more types of these.

Further, a monofunctional active hydrogen compound such as monoalcohol, monoamine, aminoalcohol or asymmetric dimethylhydrazine is added to a part of the active hydrogen component (b) for the purpose of molecular weight adjustment during prepolymer synthesis or chain extension reaction. It can be used by mixing with the other component (b), or can be added and used when the target molecular weight is reached.

The polyurethane resin is preferably obtained by subjecting (a) and the component (b) to a urethanization reaction. The method for producing the polyurethane resin from (a) and component (b) will be exemplified below. NCO group in the organic polyisocyanate (a) and N in the active hydrogen component (b)
The equivalent ratio of the CO group and the active hydrogen group capable of reacting is usually 0.
It is 7 to 1.3: 1.0, preferably 1.0: 1.0. As the method for producing the polyurethane resin, a one-shot method in which (a) and all of the component (b) are simultaneously reacted to obtain the polyurethane resin, and a method in which (a) and a part of the component (b) are reacted are A prepolymer method in which a polymer is produced, and then the rest of the component (b) is added and a chain extension reaction is performed to obtain the polyurethane resin can be mentioned. NCO group in the organic polyisocyanate (a) and N of the active hydrogen component (b) when producing a prepolymer by the prepolymer method
The equivalent ratio of the CO group and the active hydrogen group capable of reacting is usually 1.1.
˜2.5: 1, preferably 1.1 to 2.0: 1.0, more preferably 1.2 to 1.8: 1.0. If the value of the NCO group in this equivalent ratio is less than 1.1, the viscosity of the urethane prepolymer becomes too high and a special machine is required for dispersion in water, or the dispersion stability of the resulting aqueous dispersion becomes poor. Problems such as occur. On the other hand, if it exceeds 2.5, the film forming temperature of the aqueous dispersion becomes too high, and the ratio of (a) constituting the polyurethane resin increases, which is disadvantageous in terms of cost.

A catalyst may be used if necessary in the synthesis of the polyurethane resin by the one-shot method and the synthesis of the urethane prepolymer in the prepolymer method.
Specific examples of the catalyst include lead octylate, dibutyltin dilaurate, dioctyltin dilaurate, stanas octoate and other salts of organic and inorganic acids, and organic metal derivatives; organic tertiary amines such as triethylenediamine and triethylamine; Examples thereof include diazabicycloundecene catalyst.

The synthesis of the polyurethane resin by the one-shot method and the synthesis of the urethane prepolymer in the prepolymer method can be carried out without solvent or in a solvent. As this solvent, those generally used in the synthesis of urethane resins can be used. Preferred solvents include solvents that are inert to NCO groups or less active than the reaction components. Specifically, ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), aromatic hydrocarbon solvents (toluene, xylene, etc.), aliphatic hydrocarbon solvents (n-hexane, etc.),
Alcohol solvents (isopropyl alcohol, ethanol, etc.), ether solvents (dioxane, tetrahydrofuran, etc.), ester solvents (ethyl acetate, cellosolve acetate, etc.), amide solvents (dimethylformamide,
Dimethylacetamide and the like), sulfoxide type solvent (dimethyl sulfoxide and the like), lactam type solvent (n-methyl-2-pyrrolidone and the like) and the like. Of these, acetone and methyl ethyl ketone are particularly preferable from the viewpoints of solvent distillation, solubility, dispersibility in water, and the like. The solvent may remain in the O / W type aqueous dispersion of the polyurethane resin, but it is usually removed after forming the dispersion. When removing, it is heated at atmospheric pressure for distillation, or heated under reduced pressure for distillation.

The polyurethane resin may be of a self-emulsifying type by introducing into the molecule a cation group such as a quaternary ammonium group or a hydrophilic group such as an anion group such as a tertiary amine salt of carboxylic acid. The self-emulsification type is preferable because the dispersion stability of the aqueous dispersion is improved.

As a specific example of the method for introducing an anion group into the molecule, α, α'-dimethylolalkanoic acids are used as a part of the component (b), and the polyurethane resin or the polyurethane resin from (a) and (b) is used. A method in which a carboxyl group is introduced into the molecule during the synthesis of the urethane prepolymer and then neutralized with an amino compound may be used. Specific examples of α, α′-dimethylolalkanoic acids include α, α′-dimethylolpropionic acid, α, α′-dimethylolacetic acid and the like, and combinations thereof. Of these, α, α'-dimethylolpropionic acid is preferred. Examples of the above-mentioned amino compound used for neutralization include triethylamine, ammonia, 2-amino-2-methylpropanol, diethanolamine, dibutylamine, monoethanolamine and the like, and combinations thereof. As a specific example of the method of introducing a cationic group into the molecule, a quaternary nitrogen-containing polyol is used as a part of the component (b), and the polyurethane resin or urethane prepolymer is synthesized from (a) and the component (b). At this time, a cation group is introduced into the molecule, or a tertiary amino group-containing polyol is used as a part of the component (b), and when the polyurethane resin or urethane prepolymer is synthesized from (a) and the component (b), After introducing a secondary amino group into the molecule, a method of quaternizing with an alkylating agent or neutralizing with an acid can be mentioned. In the above, as the tertiary amino group-containing polyol, N, N-dialkylmonoalkanolamine (N, N-dimethylethanolamine, N, N-diethylethanolamine, etc.), N-alkyldialkanolamine (N-methyldiethanolamine, N -Butyldiethanolamine and the like), trialkanolamines (triethanolamine, tripropanolamine and the like), alkylene oxide adducts thereof having 2 to 4 carbon atoms, and the like, and combinations of two or more thereof. Among these, preferred is N-alkyl dialkanolamine. Examples of the quaternary nitrogen-containing polyol include those obtained by quaternizing the above-mentioned tertiary amino group-containing polyol with an alkylating agent. Examples of the alkylating agent and the alkylating agent used for quaternizing the tertiary amino group in the polyurethane resin or urethane prepolymer include dialkyl sulfuric acid (dimethyl sulfuric acid, diethyl sulfuric acid), aralkyl halide (benzyl chloride, benzyl bromide). Etc.), alkyl halides (methyl chloride, methyl iodide, ethyl chloride, etc.), and combinations of two or more of these. Examples of the acid used for neutralizing the tertiary amino group in the polyurethane resin or the urethane prepolymer include formic acid, lactic acid, acetic acid, and the like, and a combination of two or more kinds thereof.

The water-based dispersion (I) is prepared by dispersing the polyurethane resin obtained by the one-shot method or the prepolymer method in water with appropriate stirring, or in water at the stage of the urethane prepolymer in the prepolymer method. It is possible to obtain it by dispersing it in a chain and extending the chain. Examples of the dispersing method include a method in which water is added to the polyurethane resin or urethane prepolymer with appropriate stirring to disperse the same, or conversely, a method of dispersing them in water is used. When the urethane prepolymer is dispersed, the chain extension reaction is performed with water at the same time as the dispersion. The chain extension reaction may be performed using a chain extender other than water. In this case, it is preferable to select and use a chain extender having a higher reactivity with NCO groups than water in (b3).

The concentration of the polyurethane resin in the aqueous dispersion (I) can be 0.1 to 95% by weight, preferably 10 to 50% by weight, and particularly preferably 20 to 40% by weight in terms of production.

If necessary in the production of the aqueous dispersion (I), various additives may be added for the purpose of improving weather resistance and the like. Additives are usually added at the time of synthesizing the polyurethane resin or urethane prepolymer, but when the additive is water-soluble or reacts with a reaction component such as an isocyanate component, the polyurethane resin is added as an aqueous dispersion. Good to do. Specific examples of various additives include antioxidants (hindered phenol-based, phosphite-based, thioether-based, etc.), ultraviolet absorbers (benzophenone-based, benzotriazole-based, oxalic acid anilide-based, salicylate-based, salicylate-based, etc.), Examples include light stabilizers (hindered amine type), NOx gas stabilizers (hydrazine type, semicarbazilo type, etc.), metal deactivators (nickel complex salt type, etc.), flame retardants (organic halogen type, etc.), antistatic agents, etc. Be done.

Organopolysiloxane (II) can be optionally contained in the treatment agent of the present invention. It is preferable to contain the organopolysiloxane (II) because the texture of softness and the like and the bathochromic property can be further improved while maintaining the performance of preventing hair collapse and finger marks. (II)
Specific examples thereof include organopolysiloxane, amino-modified organopolysiloxane, epoxy-modified organopolysiloxane, carboxy-modified organopolysiloxane and the like, and those further modified with a polyoxyalkylene group. More specifically, processing technology Vol. Two
5, No. 6 (1990) 362-392 and processing technology Vol. 26, No. 6 (1991) 366-404
The silicone-based softening agent described in 1. The content of the organopolysiloxane (II) is 100% by weight or less based on the resin solid content of (I).

The treatment agent of the present invention further contains a water repellent treatment agent (II) for the purpose of improving stain resistance and water repellency, if necessary.
I) can also be included. Specific examples of (III) include perfluoroacrylate-based, paraffin-based, silicone-based, alkylethylene urea-based, higher fatty acid amide-based water repellent treatment agents in the form of a cationic, anionic or nonionic emulsion. Can be mentioned. Asahi Glass Co., Ltd.'s Asahi Guard LS-317
(Perfluoroacrylate type), Petrox P-2
00 (paraffin type), Parazid RS (alkyl ethylene urea type) Uniperan PW (higher fatty acid amide type)
Etc. Among these, the perfluoroacrylate type is preferable from the viewpoints of stain resistance and water repellency. The content of the water repellent treatment (III) is 2 with respect to the resin solid content of (I).
It is not more than 00% by weight.

The treatment agent of the present invention can be used by adding a crosslinking agent, if necessary. Specific examples of the cross-linking agent include compounds such as melamine, epoxy, and block isocyanate, and combinations of two or more of these. Examples of the method of using these include a method of introducing a hydroxyl group, a carboxyl group, an amino group or the like into the molecule of the polyurethane resin for the purpose of improving water resistance, and crosslinking with the crosslinking agent at the time of processing. Be done.

If necessary, isopropyl alcohol (a penetrating agent) is added to the treating agent of the present invention, and water is added in an amount of 0.01 to 30% by weight, preferably 0.05 to 10.0%, more preferably 0.3 to 5%. It is used as a diluting solution adjusted to a resin solid content concentration of 0.0%.

The treatment agent of the present invention treats the yarn or the raw material cotton used in the pile before forming the pile fabric, or
Alternatively, it can be used in a method of treating at least a pile portion (puffed portion) of the pile fabric.

The material for forming the pile portion of the pile cloth may be either natural fibers or synthetic fibers, and examples thereof include fibers such as wool, cotton, polyester, polyamide and rayon, and a mixture thereof. Pile cloth (moquette, W Russell, knit, etc.) can be formed by weaving, knitting, tufting or the like using the threads of these fibers.

The method of applying the treatment agent of the present invention includes:
It can be carried out in any of the state of cotton before spinning, the state of yarn after spinning, and the state of pile fabric. To apply in the state of cotton, a method of immersing the above-mentioned treatment agent in the cotton dyeing step, a method of spraying before spinning, and the like can be mentioned. In order to apply it in the state of a thread, a dipping method, a roller method, or a spray method is used. Particularly, in the case of a yarn-dyed product, the method of dipping at the time of the yarn-dying step requires only one drying step and is economical. The dipping method, the roller method, and the spray method are used to apply the cloth in the state of the cloth. Either way,
The treating agent of the present invention is usually added in an amount of 0.01 to 0.01 in terms of resin solid content per the weight of at least the pile portion of cotton or yarn or pile cloth.
20% by weight, preferably 0.03 to 10% by weight, and more preferably 0.05 to 5.0% by weight. When the applied amount is 0.01% by weight or less, the effect of preventing whitening becomes insufficient, and when the applied amount is 20% by weight or more, the texture becomes rough and hard.

The amount of the treatment agent of the present invention applied to cotton or yarn or pile cloth may be adjusted by adjusting the concentration of the compounding solution, after application, a centrifugal dehydrator, mangle roll,
Examples thereof include a method of adjusting the applied amount to the fibers with a vacuum dehydrator, a method of adjusting the spray amount with a spray, a method of adjusting the applied amount with various coaters, and the like.

After adjusting the application amount of the treatment agent of the present invention, heat treatment is performed. Here, the heat treatment means drying, and if necessary, curing and / or annealing. The drying temperature is usually 50 to 200 ° C., preferably 80 to 150.
C., curing and / or annealing temperature is usually 50 to 200.degree. C., preferably 120 to 180.degree.

In the case of a method for treating a pile fabric, after the treatment agent of the present invention is applied to the pile fabric by the above-mentioned method, if necessary, before or during the drying or after the drying, a roll brush, an air brush or the like is used to fluff the pile. It is good to arrange. Before or during drying, the fluff in the pile is not completely fixed, so it is easy to arrange. Further, it is preferable to arrange the fluff of the pile in an upright state as much as possible or to adjust it so that it has no directionality. When fixed on one side, light reflects in a specific direction and appears white.

[0040]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. Hereinafter, parts are parts by weight. The abbreviations used in the examples have the following meanings.

(Organic polyisocyanate) MDI-H: 4,4'-methylenebis (cyclohexyl isocyanate) IPDI: Isophorone diisocyanate TDI: Tolylene diisocyanate [Chemical Upjohn Co., Ltd., product name: T-80] (active hydrogen component) BPEO: 4,4'-isopropylidene bisphenol, ethylene oxide 2 mol adduct molecular weight = 319.7 Hydroxyl value = 351 PC-2000: Polycarbonate diol [Nippon Polyurethane Industry Co., Ltd., product name: Nipolan 980R] Molecular weight Amount = 1996 Hydroxyl value = 56.2 PG-2000: Polytetramethylene glycol [manufactured by Sanyo Chemical Industry Co., Ltd., product name: PTMG-2000] Molecular mass = 2000 Hydroxyl value = 56.1 Ester 20: Butylene adipate [Sanyo Chemical engineering Co., Ltd., product name: San Ester 4620] molecular amount = 2000, hydroxyl value = 56.1 Ester 10: butylene adipate [manufactured by Sanyo Kasei Co., Ltd., product name: Sun Ester 4610] molecular amount = 1005 hydroxyl value = 111.6 DMPA: dimethylol propionic acid n-MDA: n-methyl-diethanolamine CDH: carbohydrazide EG: ethylene glycol (quaternary agent) DMS: dimethyl sulfate (neutralizing agent) TEA: triethylamine (reaction terminator) ) MEA: monoethanolamine (solvent) MEK: methyl ethyl ketone DMK: acetone IPA: isopropanol (other compounding agents) KR58: silicon softening agent manufactured by Meisei Chemical Co., Ltd. (product name: high softer KR58), (resin content 20%) LS-317: Asahi Glass Fluorine-based water repellent agent manufactured by Koji Kogyo Co., Ltd. (Product name: Asahi Guard LS-317), (resin content 20
%) M-3: Melamine-based crosslinking agent manufactured by Sumitomo Chemical Co., Ltd. (Product name: Sumitex resin M-3), (resin content 80
%)

Example 1 PC-2000: 42 was placed in a reaction can which was replaced with dry nitrogen gas.
0.2 parts, BPEO: 194.2 parts, DMPA: 35.
Charge 8 parts, MDI-H: 350.0 parts, MEK: 430 parts and carry out urethane prepolymerization reaction at a reaction system temperature of 50 ° C. to 130 ° C. for about 15 hours to obtain NCO% 1.47.
% Urethane prepolymer solution was obtained. This was cooled to 40 ° C., TEA: 24.3 parts was charged, the mixture was stirred for 30 minutes, and then ion-exchanged water: 4560 parts and MEA: under high speed stirring.
A 20% aqueous solution in which 4.59 parts and CDH: 19.2 parts were mixed was continuously charged. Next, attach a distiller, raise the temperature to 80 ° C, and gradually reduce the pressure to remove MEK by distillation to obtain a resin concentration of 1
9.8%, viscosity 9.5%, skeleton 1 derived from [(b1)
An O / W type aqueous dispersion of a polyurethane resin having a content of 3.4% by weight and a glass transition temperature of 43.3 ° C. was obtained. The O / W type aqueous dispersion of the polyurethane resin was used to prepare a mixed solution having the following formulation. O / W type aqueous dispersion of polyurethane resin: 2.5 parts Water: 97.5 parts 30 dyed in a dark gray color with the above disperse dye
Cut pile moquette that uses / 2 spun ester yarn as a pile with a pile length of 2.8 mm (ground yarn 20/2, ester /
Rayon [65% / 35%], weight 620 g / m ²⁾ 5 minutes at 100 ° C. By adjusting pin tenter to stop basis weight 248 g / m ² by a dip after mangle roll, 0.99 ° C.
Was heat-treated for 5 minutes. The obtained mocket had a good texture and deep color, and no finger marks were attached even when it was traced with a finger. Furthermore, when a weight of 500 g (grounding area: 12.6 cm ² ) was placed and the pile state was observed at 80 ° C. for 2 hours, hair fall and whitening did not occur at all. The untreated moquette tested at the same time did not recover due to the bleaching heat set.

Example 2 Using the O / W type aqueous dispersion of the polyurethane resin obtained in Example 1, a liquid mixture having the following formulation was prepared. O / W type aqueous dispersion of polyurethane resin: 10.0 parts KR58: 2.0 parts LS-317: 5.0 parts M-3: 0.5 parts IPA: 3.0 parts Water: 79.5 parts Above 2) Dye dark gray with disperse dye
Cut pile moquette with 0/2 spun ester yarn as pile with 2.8 mm pile length (ground yarn 20/2, ester / rayon [65% / 35%], weight 620 g / m ² ).
After dipping, squeeze with a mangle roll and weigh 248 g / m ²
After that, heat treatment was performed at 150 ° C. for 10 minutes with a pin tenter. The obtained mocket had a good texture and deep color, and no finger marks were attached even when it was traced with a finger. Furthermore, a weight of 500 g (ground area: 12.6
cm ² ), and after 2 hours at 80 ° C., the state of the pile was observed. As a result, hair fall and whitening did not occur at all. The untreated moquette tested at the same time did not recover due to the bleaching heat set.

Example 3 PC-2000: 21 was placed in a reaction can which was replaced with dry nitrogen gas.
3.2 parts, BPEO: 95.8 parts, n-MDA: 16.
2 parts, MDI-H: 174.8 parts, MEK: 214 parts were charged, and a urethane prepolymerization reaction was performed at a reaction system temperature of 50 ° C. to 130 ° C. for about 15 hours to obtain NCO% 1.47.
% Urethane prepolymer solution was obtained. This was cooled to 40 ° C., charged with DMS (15.8 parts), subjected to a quaternization reaction for 3 hours, diluted with MEK (167 parts), and ion-exchanged water (1505 parts) and MEA (1.75 parts) under high-speed stirring. , And C
A 20% aqueous solution prepared by mixing DH: 7.3 parts was continuously charged. Next, a distiller was attached, the temperature was raised to 80 ° C., and the pressure was gradually reduced to remove MEK by distillation, and the resin concentration was 28.2% and the viscosity was 7.
5 CPS / 20 ° C., skeleton 13.4 derived from [(b1)
% By weight, glass transition temperature: 38 ° C.] to obtain an O / W type aqueous dispersion of polyurethane resin. Furthermore, ion-exchanged water was added to adjust the resin concentration to 20%. The O / W type aqueous dispersion of the polyurethane resin was used to prepare a mixed solution having the following formulation. O / W type aqueous dispersion of polyurethane resin: 2.5 parts Water: 97.5 parts 30 dyed in a dark gray color with the above disperse dye
Cut pile moquette that uses / 2 spun ester yarn as a pile with a pile length of 2.8 mm (ground yarn 20/2, ester /
Rayon [65% / 35%], and hair shaping the napped by weight 620 g / m ²⁾ adjusting the roll brush to squeeze basis weight 248 g / m ² by a dip after mangle rolls. Next, heat treatment was performed with a pin tenter at 120 ° C. for 5 minutes and 160 ° C. for 5 minutes. The obtained mocket had a good texture and deep color, and no finger marks were attached even when it was traced with a finger. In addition, a 500g weight (ground area: 1
When the state of the pile was observed after 2 hours at 80 ° C. by placing 2.6 cm ² ) on it, hair fall and whitening did not occur at all. The untreated moquette tested at the same time did not recover due to the bleaching heat set.

Example 4 An O / W type aqueous dispersion of the polyurethane resin obtained in Example 3 was used to prepare a mixed solution having the following formulation. 0 / W type aqueous dispersion of polyurethane resin: 10.0 parts KR58: 2.0 parts LS-317: 5.0 parts M-3: 0.5 parts IPA: 3.0 parts Water: 79.5 parts Above 30 dyed in dark gray with disperse dye in formulation
Cut pile moquette that uses / 2 spun ester yarn as a pile with a pile length of 2.8 mm (ground yarn 20/2, ester /
Rayon [65% / 35%], and hair shaping the napped by weight 620 g / m ²⁾ adjusting the roll brush to squeeze basis weight 248 g / m ² by a dip after mangle rolls. Next, heat treatment was performed with a pin tenter at 120 ° C. for 5 minutes and 160 ° C. for 5 minutes. The obtained mocket had a good texture and deep color, and no finger marks were attached even when it was traced with a finger. In addition, a 500g weight (ground area: 1
When the state of the pile was observed after 2 hours at 80 ° C. by placing 2.6 cm ² ) on it, hair fall and whitening did not occur at all. The untreated moquette tested at the same time did not recover due to the bleaching heat set.

Example 5 The formulation liquor of Example 4 was added to a beige dyed with a disperse dye, and a 75 mm denier ester filament yarn was knitted with 28 gauge and 63 courses to form an ester raised knit (weight: 500 g / 500 g / weight). m ² ) was dipped and adjusted with a mangle roll to have a basis weight of 200 g / m ² , and the hair was napped with a roll brush. Then 1 with a pin tenter
Heat treatment was performed at 20 ° C. for 5 minutes and at 160 ° C. for 5 minutes. The obtained knit had a good texture and had a deep color, and no finger marks were attached even when it was traced with a finger. Furthermore, when a weight of 500 g (grounding area: 12.6 cm ² ) was placed and the pile state was observed at 80 ° C. for 2 hours, hair fall and whitening did not occur at all. The untreated knits tested at the same time did not recover because the whitening was heat set.

Comparative Example 1 A reactor which had been purged with dry nitrogen gas was added with Esther 20:99.
2.0 parts, Esther 10: 71.4 parts, DMPA: 5
8.2 parts, TDI: 261.0 parts, DMK: 593 parts were charged and a urethane prepolymerization reaction was carried out at a reaction system internal temperature of 50 ° C. to 80 ° C. for about 15 hours to obtain NCO% of 2.13%.
A urethane prepolymer solution of was obtained. After cooling this to 40 ° C., DMK: 790 parts, TEA: 44.0 parts were charged 3
After stirring for 0 minutes, 6298 parts of ion-exchanged water was charged under high-speed stirring. Next, attach a distiller, raise the temperature to 50 ° C and gradually reduce the pressure to remove DMK by distillation to obtain a resin concentration of 20.5%.
Viscosity 12.7 cps / 20 ° C [glass transition temperature: -53
C.] to obtain an O / W type aqueous dispersion of polyurethane resin.
The O / W type aqueous dispersion of the polyurethane resin was used to prepare a mixed solution having the following formulation. O / W type aqueous dispersion of polyurethane resin: 2.5 parts Water: 97.5 parts 3 dyed in a dark gray color with a disperse dye in the above-mentioned compounded liquid
Cut pile moquette with 0/2 spun ester yarn as pile with 2.8 mm pile length (ground yarn 20/2, ester / rayon [65% / 35%], weight 620 g / m ² ).
After dipping, squeeze with a mangle roll and weigh 248 g / m ²
And adjusted to a napped condition with a roll brush. Next, heat treatment was performed with a pin tenter at 120 ° C. for 5 minutes and 160 ° C. for 5 minutes. The texture of the obtained mocket was good, but when traced with a finger, hair fell and whitening occurred, and finger marks remained. Furthermore, a weight of 500 g (ground area:
When 12.6 cm ² ) was placed and the pile state was observed after 2 hours at 80 ° C., whitening was heat set and was not recovered.

Comparative Example 2 Using the O / W type aqueous dispersion of the polyurethane resin obtained in Comparative Example 1, a compounded liquid having the following formulation was prepared. 0 / W type aqueous dispersion of polyurethane resin: 10.0 parts KR58: 2.0 parts LS-317: 5.0 parts M-3: 0.5 parts IPA: 3.0 parts Water: 79.5 parts Above The compounded liquid was dyed in dark gray with a disperse dye. 3
Cut pile moquette with 0/2 spun ester yarn as pile with 2.8 mm pile length (ground yarn 20/2, ester / rayon [65% / 35%], weight 620 g / m ² ).
After dipping, squeeze with a mangle roll and weigh 248 g / m ²
And adjusted to a napped condition with a roll brush. Next, heat treatment was performed with a pin tenter at 120 ° C. for 5 minutes and 160 ° C. for 5 minutes. The texture of the obtained mocket was good, but when traced with a finger, hair fell and whitening occurred, and finger marks remained. Furthermore, a weight of 500 g (ground area:
When 12.6 cm ² ) was placed and the pile state was observed after 2 hours at 80 ° C., whitening was heat set and was not recovered.

Comparative Example 3 PG-2000: 22 was added to a reaction can which was replaced with dry nitrogen gas.
0.0 parts, DMPA: 13.7 parts, IPDI: 66.0
Parts, DMK: 100 parts were charged, and the reaction system internal temperature was 50 ° C to 1
A urethane prepolymerization reaction was carried out at 30 ° C. for about 15 hours to obtain a urethane prepolymer solution having an NCO% of 1.79%. After cooling this to 40 ° C., TEA (7.7 parts) was charged and the mixture was stirred for 30 minutes and then ion-exchanged water (13) under high speed stirring.
Prepared 65 copies. Next, a distiller was attached, the temperature was raised to 50 ° C. and the pressure was gradually reduced to remove DMK by distillation and the resin concentration was 20.
5%, viscosity 10.8 cps / 20 ° C. [glass transition temperature:
-78 ° C.] to obtain an O / W type aqueous dispersion of polyurethane resin. The O / W type aqueous dispersion of the polyurethane resin was used to prepare a mixed solution having the following formulation. 0 / W type aqueous dispersion of polyurethane resin: 10.0 parts KR58: 2.0 parts LS-317: 5.0 parts M-3: 0.5 parts IPA: 3.0 parts Water: 79.5 parts Above 28 gauge, 75 denier ester filament yarn dyed beige with disperse dye, 63
An ester brushed knit (weight: 500 g / m ² ) having a total thickness of 2.3 mm knitted in the course was dipped, adjusted with a mangle roll to a squeezing weight of 200 g / m ^2, and napped with a roll brush. Next, heat treatment was performed with a pin tenter at 120 ° C. for 5 minutes and 160 ° C. for 5 minutes. The obtained knit had a good texture, but when it was traced with a finger, hair fell and whitening occurred, and finger marks remained. Furthermore, 50
0g of weight (ground area: 12.6cm ²⁾ the put 80 ℃
After 2 hours, the state of the pile was observed. As a result, the whitening was heat set and was not recovered. *: The glass transition temperatures shown in the above-mentioned Examples and Comparative Examples were obtained by drying each dispersion at 80 ° C. for 2 hours and then heat-treating at 150 ° C. for 30 minutes to form a film having a thickness of 0.1 mm as a measurement sample. Industrial DS robot DS
Measured by C model RDC220 at 10 ° C / min to -60 ° C and then heated at 20 ° C / min to measure JISK7121-1
987 Extrapolated glass transition temperature (Tig) value.

TEST EXAMPLE, COMPARATIVE TEST EXAMPLE The treated moquette fabric or knit fabric obtained in each of Examples 1 to 5 and Comparative Examples 1 to 3 and untreated moquette fabric and knit fabric were used as test pieces. Was tested and evaluated. The results are shown in Table 1. Finger mark prevention: The difference in lightness (DL value) between the surface condition of each test piece as it is and the surface condition after the hand brush has been brushed 5 times in a certain direction to cause whitening is measured using a colorimeter (Macbeth Co.). Manufactured) and comparatively evaluated. At the same time, a comparative evaluation was made by visual inspection. Prevention of hair falling under high temperature: Difference in brightness between the surface condition of each test cloth as it is and the surface condition after applying a weight of 500 g to each test cloth and applying a load and temperature at 80 ° C for 2 hours in a constant temperature dryer. The (DL value) was measured with a colorimeter (manufactured by Macbeth Co.) for comparative evaluation. At the same time, a comparative evaluation was made by visual inspection. In the above evaluation method, the larger the difference in lightness (DL value) measured by a colorimeter (manufactured by Macbeth Co.), the greater the occurrence of whitening due to hair collapse on the pile surface.

[0051]

[Table 1] In Table 1, ◯ of the visual observation indicates that hair is hardly flipped, and X indicates that hair fluff occurs. From Table 1, the treated products obtained in Examples 1 to 5 are compared with the treated products and untreated products obtained in Comparative Examples 1 to 3 by D
Since the L value is small, it can be seen that finger marks and hair fall are well prevented.

[0052]

The treatment agent for preventing hair fall and whitening of the present invention imparts effective deep coloration and impact resilience to the pile in a simple treatment process, and the pile after treatment is less likely to cause hair fall and causes hair fall. However, it becomes almost inconspicuous due to the deep color, so whitening and finger marks can be eliminated. In particular, since the impact resilience is imparted to the pile even under high temperature conditions where the temperature reaches 80 ° C., such as in a vehicle in the summer, hair fall and whitening caused by the load and heat of the seat belt fittings can be prevented. The hair fallen anti-whitening agent of the present invention exerts such an effect, therefore, chair upholstery,
It is useful for pile fabrics used for vehicle seat materials, automobiles, building interior materials, carpets and the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location D06M 15/643 D06Q 1/06

Claims (6)

[Claims] 1. A treatment agent for preventing a hair fall of a pile fabric, which comprises an aqueous dispersion (I) of a polyurethane resin having a glass transition temperature of 0 to 100 ° C. 2. The polyurethane resin comprises an aliphatic or alicyclic polyisocyanate (a) and a number average molecular weight of 50.
A diol (b1) having a cyclic group selected from hydrogenated bisphenols and / or alkylene oxide adducts of (hydrogenated) bisphenol, which is 0 or less, an active hydrogen compound (b2) having a number average molecular weight of 600 to 8000, and necessary. The processing agent according to claim 1, which is a polyurethane resin comprising an active hydrogen component (b) consisting of a chain extender (b3). 3. The treating agent according to claim 1 or 2, further comprising organopolysiloxane (II) in an amount of 100% by weight or less based on the resin solid content of (I). 4. A yarn used for a pile fabric, which comprises applying the treatment agent according to any one of claims 1 to 3 to a yarn used for a pile before forming a pile fabric or cotton as a raw material thereof and heat treating the yarn. Or the processing method of the raw material cotton. 5. A pile fabric comprising at least a pile portion,
A method for treating a pile fabric, which comprises applying the treatment agent according to any one of claims 1 to 3 and performing heat treatment. 6. A pile fabric in which at least a pile portion is treated with the treatment agent according to claim 1.