JP5433467B2 - Wrinkle remover composition - Google Patents

Description

  The present invention relates to a wrinkle remover composition, a spray-type wrinkle remover, and a method for removing wrinkles from textiles.

  Dry cleaning clothes such as suits are difficult to wash with water at home, and their wrinkle removal method is generally performed by heat treatment such as ironing or steam press. However, such a heat treatment is a time-consuming operation and may impair the texture.

  Patent Document 1 discloses a composition for reducing wrinkles composed of silicone and a film-forming polymer, and Patent Document 2 discloses a wrinkle composed of an adhesive polymer and an uncomplexed cyclodextrin. And malodor reducing compositions are disclosed, but their wrinkle removal effect is insufficient.

  Patent Document 3 discloses a technique related to a fabric treatment composition comprising a cationic polymer and an anionic polymer, one of which is a silicone polymer. As anionic polymer, carboxymethyl cellulose and alginic acid-based polymers are disclosed. Are listed. Patent Document 4 discloses a technique related to a solid fabric care composition comprising a water-soluble carrier, a water-soluble polymer, and a fabric care compound. A cationic polymer is used as the fabric care compound, and a polyalkylene glycol is used as the water-soluble polymer. Are listed. These fabric treatment compositions also have the effect of reducing wrinkles, but the wrinkle removal effect has not reached the point where heat treatment can be omitted.

  In addition, Patent Document 5 discloses a technique related to a liquid finish composition for textiles, which includes silicone, a cationic water-soluble polymer, and an anionic surfactant. Patent Document 6 discloses a technique related to a fiber treating agent comprising a polymer containing a polyethylene glycol moiety or a polycarboxylic acid moiety in the molecular structure, and a cationic monomer for improving adhesion to polyester fibers. It is described that the following copolymer can be used. However, no mention is made of the wrinkle removal performance of these compositions.

  Under such circumstances, it is desired to develop a wrinkle removal composition that can remove wrinkles of a textile product without damaging the texture without performing heat treatment such as ironing or steam press on the textile product. It was.

Japanese Patent Laid-Open No. 10-508911 JP 2003-525356 A JP 2006-504001 A JP 2009-532593 A JP 2009-161865 A JP 2001-303447 A

  The subject of this invention is providing the wrinkle removal agent composition which can remove the wrinkle of a textile product, without performing heat processing, such as ironing and a steam press.

  As described above, the wrinkle removal effect of the prior art is insufficient. For example, the fabric treatment composition described in Patent Document 3 has an effect of reducing wrinkles due to the properties such as lubricity of the coacervate itself formed by the bases of the cationic polymer and the anionic polymer. However, the wrinkle removal effect is insufficient.

  The present application includes (a) a cationic polymer having a weight average molecular weight of 5000 to 10 million, and (b) a polymer having an anionic group (segment (I)) and a polyalkyleneoxy group (segment (B)) in the molecule. A wrinkle removing composition containing In the presence of water, the wrinkle remover composition is treated on the wrinkle portion of the textile produced by wearing or the like, so that (a) a cationic polymer and (b) an anionic group (segment (I) )) And a polymer having a polyalkyleneoxy group (segment (b)) not only electrostatically form a complex, but also a complex (hydrated gel) in which the complex actively takes in water and hydrates ) And is to propose a technique for extremely improving the lubricity when wet.

The present invention relates to a wrinkle remover composition containing the following component (a) and component (b).
(A) Cationic polymer having a weight average molecular weight of 5,000 to 10,000,000 (b) Polymer containing an anionic group (segment (I)) and a polyalkyleneoxy group (segment (B)) in the molecule

  The present invention also relates to a spray-type wrinkle removing agent obtained by filling the wrinkle-removing agent composition in a spray container, and a method for removing wrinkles from a textile product using the spray-type wrinkle removing agent.

  The problem to be solved by the present invention is that the fibers constituting the fiber product manufactured in a visually smooth state are fixed by friction between fibers in a state where the fibers are bent into a mountain shape or a valley shape by wearing or the like. Resolve wrinkles caused by Below, the technical idea regarding the extremely high wrinkle removal effect achieved by the present invention will be described.

  The component (b) is a polymer containing an anionic group (segment (I)) and a polyalkyleneoxy group (segment (B)) in the molecule. When the fiber product is wetted with water containing the component (b) and then dried, the polyalkyleneoxy group in the component (b) is hydrated and gel (hereinafter, Form a hydrated gel). This hydrated gel exhibits extremely high lubricity, and wrinkles are removed by improving the sliding between fibers fixed in a state of being bent in a mountain shape or a valley shape.

  Even if the fiber product wetted with water is in a slightly wet state in the process of removing water by drying, water is present between the fibers constituting the fiber product. At this time, when the component (b) is uniformly dispersed in the water existing between the fibers, sufficient lubricity is not provided. It is important that the component (b) that formed the hydrated gel is adsorbed on the surface of the fiber wetted with water, in order to extremely enhance the lubricity between the fibers and to exert a high wrinkle removing effect.

  In this respect, the cationic polymer which is another component of the present invention, that is, the component (a) electrostatically interacts with the component (b) having an anionic group in the molecule, and is slightly in the drying process. It plays a role of allowing the component (b) to be present on the surface of the wet textile product. Here, the component (a) does not only serve as a carrier for the component (b). Hydrophobic complex formed by interaction of component (a) and component (b), and the proportion of segment (b) derived from component (b) that forms a hydrated gel in the complex Is important, and by designing this within an appropriate range, a hydrated gel with better lubricity can be formed, and as a result, an extremely high wrinkle removal effect can be obtained.

  Since the wrinkle removing composition of the present invention can improve the fiber lubricity of the textile product, the wrinkle of the textile product can be removed without performing a heat treatment such as ironing or steam pressing.

Schematic of test piece used for evaluation of fiber lubricity of examples and comparative examples

  Below, in order to obtain the wrinkle removal agent composition excellent in the wrinkle removal effect of this application, the molecular design of each component and the design of a composition are explained in full detail.

<(A) component>
The cationic polymer used in the component (a) of the present invention has a weight average molecular weight of 5,000 to 10,000,000, preferably a weight average molecular weight of 10,000 to 5,000,000, preferably a weight average molecular weight of 10,000 to 3,000,000. The weight average molecular weight is preferably 11,000 to 1,000,000, and most preferably the weight average molecular weight is 12,000 to 500,000. Here, the weight average molecular weight of the component (a) is a value measured using gel filtration type liquid chromatography. When the component (a) is considered to be relatively hydrophilic, it is calculated from the molecular weight in terms of polyethylene glycol. Moreover, when it is thought that (a) component is comparatively hydrophobic, it calculates by the molecular weight of polystyrene conversion.

  The component (a) is a cationic polymer having at least one structural unit derived from a quaternized product of a vinyl monomer represented by the following general formula (1) or (2). It is preferable in that it interacts well and exhibits higher lubricity.

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ are the same or different and represent a hydrocarbon group having 1 to 4 carbon atoms, and Y represents —O—, —NH— or —O —CH ₂ CH (OH) — represents a group, and Z represents a linear or branched alkylene group having 1 to 4 carbon atoms. ]

[Wherein, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

In the general formula (1), R ² and R ³ are each a straight chain having 1 to 4 carbon atoms in that a strong interaction with the component (b) is formed and the component (b) is efficiently present on the fiber surface. A branched alkyl group or an alkenyl group is preferable, and a linear or branched alkyl group having 1 to 3 carbon atoms is more preferable. Y is preferably —O— or —NH—, and Z is preferably a linear or branched alkylene group having 2 to 3 carbon atoms.

In the general formula (2), R ⁴ and R ⁵ are each preferably a hydrogen atom. R ⁶ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 3 carbon atoms.

  As the quaternized product of the vinyl monomer represented by the general formula (1), it is possible to interact with the component (b) to enhance the lubricity when wet and to remove wrinkles. The quaternized product of the formula (1-4)] aminoethyl (meth) acrylate and the quaternized product of di [alkyl (carbon number of 1 to 4)] aminopropyl (meth) acrylamide are preferred and represented by the general formula (2). As the quaternized product of the vinyl monomer, di [alkyl (carbon number 1 to 4)] diallylammonium halide is suitable.

As specific examples of the quaternized product of the vinyl monomer represented by the general formula (1) or (2) suitable for constituting the component (a) of the present invention, the following compounds are preferred.
・ Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di quaternized product of t-butylaminoethyl (meth) acrylate;
・ Dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di quaternized product of t-butylaminopropyl (meth) acrylamide; or
-Dimethyl diallylammonium chloride is preferred.

  Among them, quaternized product of dimethylaminoethyl (meth) acrylate, quaternized product of diethylaminoethyl (meth) acrylate, quaternized product of dimethylaminopropyl (meth) acrylamide, quaternized product of diethylaminopropyl (meth) acrylamide, or dimethyl Diallylammonium chloride is preferred.

  In the present specification, (meth) acrylate means acrylate or methacrylate, and (meth) acrylamide means acrylamide or methacrylamide.

  The quaternizing agent for obtaining the quaternized product is an alkyl halide having 1 to 3 carbon atoms, preferably methyl chloride, ethyl chloride, methyl bromide, methyl iodide, or 2 to 6 carbon atoms. And general alkylating agents such as dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate.

  The component (a) of the present invention is preferably a polymer comprising at least one quaternized vinyl monomer represented by the above general formula (1) or (2) as a constituent component, but copolymerized therewith. Other possible vinyl monomers can also be a constituent.

  Examples of such other vinyl monomers include linear or branched alkyl (C1 to C22) (meth) acrylate, optionally substituted aryl (meth) acrylate, linear or branched. Chain alkyl (C1-22) (meth) acrylamide, aryl (meth) acrylamide which may have a substituent, N- (meth) acryloylmorpholine or (meth) acrylamide is preferable.

  Suitable examples of linear or branched alkyl (C1-22) (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate , N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, cyclopentyl (meth) acrylate, n-hexyl (meth) acrylate , Cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) a Relate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, or behenyl (meth) acrylate.

  Preferable examples of the aryl (meth) acrylate that may have a substituent include phenyl (meth) acrylate, toluyl (meth) acrylate, xylyl (meth) acrylate, and benzyl (meth) acrylate.

  Preferable examples of linear or branched alkyl (C1-22) (meth) acrylamide include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) ) Acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, or N-isobutyl (meth) acrylamide.

  Preferable examples of the aryl (meth) acrylamide that may have a substituent include phenyl (meth) acrylamide, toluyl (meth) acrylamide, xylyl (meth) acrylamide, and benzyl (meth) acrylamide.

  N- (meth) acryloylmorpholine or (meth) acrylamide is also an example of a preferred vinyl monomer.

  The content of the quaternized product of the cationic group-containing vinyl monomer represented by the general formula (1) or (2) in all the constituent monomers of the component (a) is preferably 30 to 100 mol%, more preferably 50. It is -100 mol%, More preferably, it is 70-100 mol%.

<(B) component>
The component (b) of the present invention is a polymer containing an anionic group (segment (i)) and a polyalkyleneoxy group (segment (b)).

[Segment (I)]
The segment (a) is an anionic group (segment (a)) that electrostatically interacts with the cationic polymer of the component (a). The anionic group as used in this application represents the group which can become an anion depending on pH in water. A carboxylic acid group, a sulfonic acid group, a phosphoric acid group and / or a phosphonic acid group are preferred. These may be in an acid form or a salt thereof. In addition to electrostatically interacting with the component (a), the complex with the component (a) has a relatively hydrophobic property, so that even a hydrophobic interaction is easily adsorbed to the fiber surface. From the viewpoint, a carboxylic acid group or a salt thereof having a lower hydrophilicity than a sulfonic acid group or a phosphonic acid group is preferable.

  The polymer chain containing the segment (a) is preferably a (co) polymer of a vinyl monomer having a carboxylic acid group or a salt thereof in the molecule, and has a sulfonic acid group, a phosphoric acid group, a phosphonic acid group or a salt thereof. A site may be included. Here, in this specification, the (co) polymer refers to a single polymer or a copolymer.

  Examples of vinyl monomers having a carboxylic acid group or a salt thereof include (meth) acrylic acid (where (meth) acrylic acid refers to acrylic acid, methacrylic acid or a mixture thereof) and salts thereof, styrene carboxylic acid And a salt thereof, a maleic acid monomer [wherein the maleic acid monomer refers to maleic anhydride, maleic acid, a maleic acid monoester, and maleic acid monoamide or a mixture of two or more thereof] and salts thereof In addition, itaconic acid and salts thereof can be used, and one or more selected from these can be used.

  It is preferable that the site | part which has a sulfonic acid group or its salt consists of a (co) polymer of the vinyl monomer which has a sulfonic acid group or its salt. Examples of the monomer having a sulfonic acid group or a salt thereof include 2- (meth) acryloyloxyethanesulfonic acid, 2- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamide-2-alkyl (1 to 4 carbon atoms). ) Examples include sulfonic acid monomers such as propanesulfonic acid, vinyl sulfonic acid, and styrene sulfonic acid, and one or more selected from these can be used.

  The site having a phosphoric acid group, a phosphonic acid group or a salt thereof is preferably composed of a (co) polymer of a vinyl monomer having a phosphoric acid group, a phosphonic acid group or a salt thereof. Examples of the monomer having a phosphoric acid group, a phosphonic acid group or a salt thereof include (meth) acryloyloxyalkyl (1 to 4 carbon atoms) phosphoric acid, vinylphosphonic acid, and the like, and one or more selected from these are used. Can do.

  Examples of the salts include alkali metal salts, alkaline earth metal salts, ammonium salts, alkyl or alkenyl ammonium salts having 1 to 22 carbon atoms, alkyl or alkenyl substituted pyridinium salts having 1 to 22 carbon atoms, and 1 to 1 carbon atoms. 22 Alkanol ammonium salt or basic amino acid salt, and the like, and alkali metal salts such as sodium salt and potassium salt are preferable.

[Segment (b)]
The segment (b) is a polyalkyleneoxy group. In the segment (b), the polyalkyleneoxy group is preferably a polyethyleneoxy group and / or a polypropyleneoxy group, and the polymer having a polyethyleneoxy group and / or a polypropyleneoxy group as a constituent unit may be a homopolymer, a block, a random Copolymers may be used.

  The size of the segment (b) is important in that the composite formed by the component (a) and the component (b) forms a hydrated gel that is preferable in terms of lubricity, thereby achieving an extremely high wrinkle removal effect. . In other words, it is important to design the weight average degree of polymerization of the segment (b) that is not too small to be insufficiently hydrated, and is too hydrated to dissolve the composite in water. In that respect, the weight average polymerization degree of the segment (b) is preferably 10 to 200, more preferably 15 to 150, and still more preferably 20 to 150. Moreover, the terminal of the polyalkyleneoxy group is not limited, may have a hydroxyl group, and may be an ether with a hydrocarbon group having 1 to 12 carbon atoms. As a hydrocarbon group, a C1-C12 alkyl group and a C6-C12 aryl group are preferable, and a C1-C3 alkyl group and a phenyl group at the point which forms a hydration gel with high lubricity. Is more preferable. Specifically, an ether with a methyl group, an ethyl group, a phenyl group or the like is preferable, and an ether with a methyl group or an ethyl group is more preferable.

  From the viewpoint of wrinkle removal performance, the proportion of the segment (b) in all the constituent monomers of the component (b) is important. The proportion of the segment (b) in the total constituent monomer of the component (b) is preferably 50 to 95% by mass, more preferably 55 to 95% by mass, and still more preferably 60 to 95% by mass.

  From the viewpoint of wrinkle removal performance, it is important to control the amount of the segment (b) in the composite formed by the component (a) and the component (b) in terms of forming a hydrated gel having excellent lubricity. It is. Therefore, it is necessary to design the existing ratio of the segment (b) that interacts with the component (a) and the segment (b) that forms the hydrated gel in the molecule of the component (b) to an appropriate ratio. is there. In that respect, the mass ratio of the segment (A) to the segment (B) is preferably (A) / (B) = 40/60 to 1/99, more preferably 35/65 to 2/98, and 30/70 to 3/97 is more preferable, 25/75 to 3/97 is particularly preferable, and 20/80 to 3/97 is most preferable. When the proportion of the segment (b) constituting the component (b) is large, the amount of the component (b) relative to the component (a) Less. In this case, in order to balance the amount of the segment (b) in the complex formed by the component (a) and the component (b), it is preferable to increase the weight average polymerization degree of the polyalkyleneoxy group. When the proportion of the segment (b) is high, it is preferable to lower the weight average polymerization degree of the polyalkyleneoxy group in order to balance the amount of the segment (b) in the composite.

  Calculation of the mass ratio of segment (b) and segment (b) in component (b) is as follows. In the production of component (b), the charged mass of the structural unit containing segment (b) and segment (b) The product of the mass content of the segment (b) in the constituent unit to be obtained is obtained, and the charged mass of the constituent unit containing the segment (b) and the mass of the segment (b) in the constituent unit containing the segment (b) It can obtain | require by calculating ratio with the product with content rate. In addition, in the component (b) that already exists, the segment (b) and the segment (b) are identified by NMR and infrared absorption spectrum (IR), etc., and the molar ratio is calculated from the peak derived from each segment using NMR. It can be obtained by converting to a mass ratio. In the calculation described in the present application, the anionic group of the segment (A) is calculated as an acid type.

  Component (b) of the present invention is a polymer having an anionic group (segment (I)) and a polyalkyleneoxy group (segment (B)) in the molecule, but a vinyl monomer having other substituents. The derived structural unit can be a constituent component.

  As the other vinyl monomer, the same “other vinyl monomer” as described for the component (a) can be used.

  The total mass of the segment (a) and the segment (b) in the component (b) of the present invention is preferably 60 to 95% by mass, more preferably 85 to 95% by mass, and still more preferably 90 to 90% by mass.

  The component (b) of the present invention having the segment (b) and the segment (b) may be any polymer of random type, block type or graft type, but the segment (b) interacting with the component (a) And a block type polymer or graft type polymer in which the segment (b) forming the hydrated gel exists in a block type or graft type in the molecule is preferable because each function can be more clearly exhibited. A graft type polymer is more preferable in that it easily forms a hydrated gel.

  The method for synthesizing the block-type or graft-type polymer is not particularly limited. For example, a vinyl-based polymer using a macroazo initiator having an azo group in the polymer chain, using one or more liquids constituting the wrinkle removing composition as a solvent. A method of polymerizing monomers, etc. (macroazo initiator method), a method using a compound having a polymerizable group at one end of the polymer chain (macromonomer method), and radically polymerizing monomers in the presence of a polymer to newly generate A method in which a polymer chain is linked to a polymer chain coexisting in advance by a chain transfer reaction (chain transfer method), a method in which another polymer terminal is reacted with a functional group in the polymer chain and grafted, etc. Can be mentioned.

  Preferred examples of the polymer of component (b) include the following, among which 1 is particularly preferred because it forms a good hydrated gel.

1. A copolymer of a polyalkylene glycol and a vinyl monomer having a carboxylic acid group or a salt thereof (preferably a monoester) and a vinyl monomer having a carboxylic acid group or a salt thereof, and derivatives thereof.

  Among these, a copolymer of a polyalkylene glycol (meth) acrylic acid ester and a vinyl monomer having a carboxylic acid group or a salt thereof is more preferable, and a polyalkylene glycol (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof The copolymer is particularly preferred. For example, a copolymer of polyethylene glycol mono (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof, poly (ethylene glycol / propylene glycol) mono (meth) acrylic acid ester and (meth) acrylic acid or a salt thereof And the like are preferred.

2. A copolymer of a polyalkylene glycol ether having a reactive unsaturated group (an unsaturated group capable of radical polymerization) and a vinyl monomer having a carboxylic acid group or a salt thereof, and derivatives thereof.

  A copolymer of a polyalkylene glycol ether having a reactive unsaturated group and (meth) acrylic acid or a salt thereof and / or a maleic monomer is preferred. Examples thereof include a copolymer of polyethylene glycol allyl ether and maleic acid (or a salt thereof).

3. A copolymer obtained by grafting a monomer having a carboxylic acid group or a salt thereof onto polyalkylene glycol and a derivative thereof.

  For example, a graft polymer obtained by radical polymerization of acrylic acid and maleic acid or a salt thereof in polyethylene glycol, polypropylene glycol or poly (ethylene glycol / propylene glycol) is preferred.

  Above 1. ~ 3. Examples of the derivative include those having a hydrocarbon group such as a methyl group, an ethyl group or a phenyl group at the terminal of the polyalkyleneoxy group to form an ether bond. As a hydrocarbon group, Preferably they are a C1-C12 alkyl group and a C6-C12 aryl group, More preferably, they are a C1-C3 alkyl group and a phenyl group.

4). A (co) polymer of vinyl monomers having a carboxylic acid group or a salt thereof, prepared using a polyalkylene glycol macroazo initiator.

  A block polymer obtained by radical polymerization of (meth) acrylic acid or a salt thereof is preferable.

5. A graft polymer obtained by linking a polymer of a vinyl monomer having a carboxylic acid group or a salt thereof and a polyalkylene glycol having a hydroxyl group at a terminal by a dehydration reaction.

  Preferably, a graft polymer obtained by linking poly (meth) acrylic acid or a salt thereof and polyethylene glycol having a hydroxyl group at a terminal by a dehydration reaction can be used.

  From the viewpoint of wrinkle removal performance, the weight average molecular weight of the component (b) is preferably 3000 to 8 million, more preferably 4000 to 5 million, further preferably 5000 to 3 million, particularly preferably 6000 to 600,000, and 6000 to 600,000. 500,000 is particularly preferable, and 6000 to 300,000 is most preferable. Here, the weight average molecular weight of the component (b) is calculated from the molecular weight in terms of polyethylene glycol using gel permeation type liquid chromatography (GPC).

<Wrinkle remover composition>
The content of the component (a) and the component (b) in the wrinkle removing agent composition of the present invention can be appropriately adjusted depending on the usage form, the type of the textile product, and the level of wrinkles.

  The content of the component (a) in the composition is 0.01 to 1% by mass, preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0.3% by mass, and still more preferably 0. 0.01 to 0.2% by mass, particularly preferably 0.01 to 0.1% by mass.

  The content of the component (b) in the composition is 0.01 to 1% by mass, preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0.3% by mass, and still more preferably 0. 0.01 to 0.2% by mass, particularly preferably 0.01 to 0.1% by mass.

  From the viewpoint of wrinkle removal performance, the blending ratio (mass ratio) of the component (a) and the component (b) is preferably (a) / (b) = 1/10 to 10/1, and 1/8 to 8/1. Is more preferable, 1/6 to 6/1 is still more preferable, and 1/5 to 5/1 is particularly preferable.

  Furthermore, the molar ratio of the cationic group in the component (a) and the anionic group in the component (b) is [cationic group in the component (a)] / [(b) from the viewpoint of wrinkle removal performance. Anionic group in component] = 0.1-50 is preferable, 0.2-30 is more preferable, 0.5-20 is still more preferable, and 1-10 is particularly preferable.

  As described above, designing the content of the segment (b) of the component (b) relative to the total content of the components (a) and (b) in the composition is the water formed by hydration of the complex. The Japanese gel is important from the viewpoint of exhibiting wrinkle removal performance, and (b) / [(a) + (b)] = 20 to 65% by mass is preferable, 25 to 60% by mass is more preferable, and 30 to 55% by mass. % Is more preferable, and 35-50 mass% is especially preferable.

  In the wrinkle remover composition of the present invention, the component (a) and the component (b) coexist with water (hereinafter referred to as the component (c1)) to improve the fiber lubricity when wet, Can be removed.

  As the component (c1), distilled water obtained by removing ionic components from water such as tap water and ion-exchanged water are preferable. The content of the component (c1) in the composition is preferably 70% by mass or more, more preferably 70 to 99.9% by mass, and still more preferably 80 to 99.9% by mass.

  In addition to the component (c1), it is effective to use an organic solvent (hereinafter referred to as the component (c2)) in combination with the purpose of further enhancing the antiseptic, odor, or wrinkle removing effects of the wrinkle remover composition. (C2) As a component, C2-C4 monohydric alcohol, Preferably ethanol, isopropanol, etc. are used. A polyhydric alcohol having 2 to 12 carbon atoms, preferably ethylene glycol, propylene glycol, glycerin, sorbitol and the like. Monoethyl or monobutyl ether of ethylene glycol or propylene glycol, monoethyl or monobutyl ether of diethylene glycol or dipropylene glycol. Benzyl alcohol, benzyloxyethanol, an ethylene oxide or propylene oxide adduct of a phenolic compound, and the like are preferable, and ethanol, diethylene glycol, and dipropylene glycol are more preferable.

  (C2) Content in the composition of a component is 0.001 mass% or more normally, Preferably it is 0.005-30 mass%, More preferably, it is 0.01-10 mass%. The ratio (mass ratio) of the (c1) component and the (c2) component in the composition is preferably (c1) / (c2) = 1 to 1000, more preferably 1 to 500, from the viewpoint of wrinkle removal performance. -200 is more preferable.

  In addition, if necessary, the surfactant, a salt such as sodium sulfate or N, N, N-trimethylglycine, a deodorant, a pH adjuster, an antioxidant, an antiseptic, as long as the effects of the present invention are not impaired. Other components such as an agent, a bactericidal / antibacterial agent, a fragrance, a dye / pigment, and an ultraviolet absorber can be added.

  The surfactant (hereinafter referred to as component (d)) is not particularly limited and is selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. 1 type or more is mentioned. Among them, the nonionic surfactant is preferable in terms of optimizing the properties of the hydrated gel in which the component (a) and the component (b) form a complex, and improving wrinkle removability. Particularly preferred are the nonionic surfactants represented.

_{^{R 7 -Z - [(EO)}} s / (PO) t] -H (3)

[In the formula (3), R ⁷ is an alkyl group or alkenyl group having 10 to 22 carbon atoms, Z is —O— or —COO—, EO is an oxyethylene group, and PO is an oxypropylene group. (EO) and (PO) may be either random addition or block addition, and the addition order of (EO) and (PO) does not matter. s and t are average addition mole numbers, the sum of s + t is a number of 5-15, and t is a number of 2 or less. ]

From the viewpoint of adjusting the hydrated gel formed by the composite of the component (a) and the component (b) to a hydrated gel having better lubricity when wet and improving wrinkle removal performance, the general formula (3) R ³ therein is preferably an alkyl group or an alkenyl group having 10 to 18 carbon atoms, more preferably 10 to 16 carbon atoms, and still more preferably 10 to 14 carbon atoms.

  Moreover, the average addition mole number s in General formula (3) becomes like this. Preferably it is the number of 5-14, More preferably, it is 5-13, More preferably, it is 5-12, t is preferably 0.

  In order to adjust the hydrated gel of the complex formed by the component (a) and the component (b) to a state excellent in lubricity when wet, it has a relatively hydrophobic property among nonionic surfactants. The nonionic surfactant represented by the general formula (3) is preferably polyoxyethylene (n = 6 to 12) lauryl ether, polyoxyethylene (n = 5 to 12) monoalkyl (carbon). One or more selected from alkyl groups, which are residues obtained by removing hydroxyl groups from secondary alcohols of formulas 12 to 14, and ethers are preferred. Here, n is the average number of added moles of oxyethylene groups.

  The content of the component (d) in the composition can be appropriately contained depending on the type and content of the complex of the component (a) and the component (b), but is preferably from the viewpoint of wrinkle removal performance. 001 to 10% by mass, more preferably 0.01 to 5% by mass, further preferably 0.01 to 3% by mass, particularly preferably 0.01 to 2% by mass, and most preferably 0.01 to 1% by mass. is there.

  The pH at 25 ° C. of the wrinkle removing composition of the present invention is such that even if the segment (b) in the component (b) selects the carboxylic acid group, the carboxylic acid group is easily interacted with the component (a). From the viewpoint of wrinkle removal performance, it is preferable that the pH is generally about 4 or 4 or more, which is generally known as pKa, preferably 4 to 8, more preferably 4 to 7.5, and still more preferably 4 to 7. is there. The pH of the wrinkle remover composition can be adjusted by adding an acid such as hydrochloric acid or sulfuric acid and / or a basic compound such as sodium hydroxide or potassium hydroxide. In addition, pH of a wrinkle removal agent composition is the value which measured the wrinkle removal agent composition itself at 25 degreeC with the measuring method of JISZ8802.

  The viscosity at 25 ° C. of the wrinkle removing composition of the present invention is preferably 15 mPa · s or less, more preferably 1 to 10 mPa · s, still more preferably 1 to 8 mPa · s, from the viewpoint of sprayability in a spray container. is there. In the wrinkle removing composition of the present invention, when the viscosity at 25 ° C. is 15 mPa · s or less, the spray pattern is appropriate. The viscosity can be adjusted by adding an appropriate amount of the component (c2). Viscosity was measured using a B type viscometer (model type BM) manufactured by Tokyo Keiki Co., Ltd. Prepare one equipped with 1 rotor, fill the sample into a tall beaker, prepare it at 25 ° C in a thermostatic bath at 25 ° C, set the sample prepared at constant temperature in the viscometer, and rotate the rotor speed Is a viscosity measured at 60 seconds after starting rotation.

<Spray type wrinkle remover>
A spray type wrinkle removing agent can be obtained by filling the spray container with the wrinkle removing agent composition of the present invention. The wrinkle removing composition of the present invention is a mist type containing water, and it is preferable to fill this in a spray container and adjust the spray amount at a time to 0.1 to 1 ml. As a spray container to be used, a known spray container such as a trigger spray container (direct pressure or pressure accumulation type) or a dispenser type pump spray container can be used. Of these, a spray container having a trigger sprayer is preferable.

  As a spray container, the volume average particle diameter of a spray droplet at a point 10 cm away from the injection port in the injection direction is 10 to 200 μm, and the liquid droplet exceeds the volume average particle size 200 μm at a point 15 cm away from the injection port in the injection direction. The number of droplets is 1% or less of the total number of spray droplets, and the number of droplets having a volume average particle diameter of less than 10 μm at a point 10 cm away from the spray port in the spray direction is 1% or less of the total number of spray droplets The thing provided with is preferable. The particle size distribution of the spray droplets can be measured by, for example, a laser diffraction particle size distribution meter (manufactured by JEOL Ltd.).

  Thus, in this invention, the spray type wrinkle removal agent formed by filling the spray container with the wrinkle removal agent composition of this invention can be obtained. The wrinkle remover composition and spray-type wrinkle remover of the present invention are suitable for textile products, and such a wrinkle remover composition can be attached to a textile product by spraying to reduce wrinkles on the object. Preferably, the spray type wrinkle remover is suitably used in this method. The fiber product which is the object of the present invention is natural fiber, for example, cellulose fiber such as cotton, and animal hair fiber. Synthetic fibers, preferably regenerated cellulose fibers, semi-synthetic fibers, polyamide fibers, polyester fibers, acrylic fibers. A fiber assembly in which the above natural fiber or synthetic fiber is made into a woven fabric, a knitted fabric, a non-woven fabric or the like. Typical textile products include clothing such as shirts, trainers, suits, sweaters, curtains, sofas, towels, handkerchiefs, and the like.

<Wrinkle removal method for textile products>
The following are mentioned as a wrinkle removal method of the textiles by the wrinkle removal agent composition of this invention. From a spray-type wrinkle remover obtained by filling a wrinkle remover composition of the present invention into a spray container, the wrinkle remover composition of the present invention is attached to the fiber product by spraying, and the fiber product is naturally dried without heating and drying. This is a method for removing wrinkles of a textile product to be dried. At that time, the textile product may be in a substantially dry state.

  The use scene of the wrinkle remover composition of the present invention is caused by folding and storing in a wrinkle generated by wearing, chiffon, etc., rather than use in a scene of removing washing wrinkles generated by washing. It is preferable to use it in a scene that is closer to wearing, such as a scene where wrinkles are removed, in that it is easier to obtain satisfaction by removing wrinkles. The wrinkle-removing agent composition of the present invention is suitable for removing wrinkles caused by such wrinkles and storage because the active ingredient spreads evenly throughout the fiber product and an appropriate amount of water can be sprayed. is there.

  The use amount of the wrinkle removing composition of the present invention is preferably 5 to 120% by mass, more preferably 5 to 100% by mass, and still more preferably 10 to 100% by mass based on the dry mass of the fiber product.

  In the method for removing wrinkles of a textile product of the present invention, from the viewpoint of wrinkle removal performance, the total adhesion amount of the component (a) and the component (b) to the textile product is preferably 0.01 to 1 per dry mass of the textile product. Wrinkle remover composition so as to have a mass%, more preferably 0.01 to 0.8 mass%, still more preferably 0.02 to 0.5 mass%, and particularly preferably 0.02 to 0.3 mass%. It is preferable to spray the fiber product.

Each compounding component used in Examples and Comparative Examples is shown below.
<(A) component>
A-1: polydimethyldiallylammonium chloride (Mercoat 100, manufactured by Nalco Japan, weight average molecular weight: 150,000, molecular weight is the value described in the manufacturer's catalog)
A-2: Polydimethylaminoethyl methacrylate quaternized product prepared in Synthesis Example 1 below (weight average molecular weight: 94,000)
<(B) component>
B-1: Methoxypolyethylene glycol (ethylene oxide average addition mole number 23) monomethacrylic acid ester / methacrylic acid copolymer [75/25 (mass ratio) copolymer] (weight average molecular weight) produced in Synthesis Example 2 below : 25,000)
B-2: Methoxypolyethylene glycol (ethylene oxide average addition mole number 40) monomethacrylic acid ester / methacrylic acid copolymer [90/10 (mass ratio) copolymer] (weight average molecular weight) produced in Synthesis Example 3 below : 56,000)
B-3: Methoxypolyethylene glycol (ethylene oxide average addition mole number 40) monomethacrylic acid ester / methacrylic acid copolymer [80/20 (mass ratio) copolymer] (weight average molecular weight) produced in Synthesis Example 4 below : 49,000)
B-4: Methoxypolyethyleneglycol (ethylene oxide average addition mole number 90) monomethacrylic acid ester / methacrylic acid copolymer [65/35 (mass ratio) copolymer] (weight average molecular weight) produced in Synthesis Example 5 below : 40,000)
<Component (b ′)> (Comparative compound of component (b))
B′-1: sodium alginate 500-600 cp (manufactured by Wako Pure Chemical Industries)
B′-2: Carboxymethylcellulose C1120 (manufactured by Daicel Chemical Industries)
B'-3: polyacrylic acid (manufactured by Wako Pure Chemical Industries, weight average molecular weight: 25,000)
B′-4: Polyethylene glycol 4000 (manufactured by Wako Pure Chemical Industries, weight average molecular weight: 4000)

Synthesis Example 1: Synthesis of a-2 300 g of ion-exchanged water was placed in a glass reaction vessel equipped with a stirrer and a nitrogen introduction tube, and the air in the system was sufficiently purged with nitrogen, and kept at 70 ° C. with stirring. Here, 300 g of a 33.3% by mass aqueous solution of 2-methacryloyloxyethyltrimethylammonium chloride previously bubbled with nitrogen and 5.00 mass of 2,2′-azobis (2-amidinopropane) dihydrochloride A 105% aqueous solution was added dropwise simultaneously over 2 hours. During the dropwise addition, the solution in the reaction vessel was kept at 70 ° C. and kept stirring. The solution was held at 70 ° C. for an additional 5 hours with continued stirring and then cooled to room temperature. The obtained reaction mixture was diluted with 700 g of ion-exchanged water and added dropwise to an agitated mixture of 4 kg of isopropyl alcohol and 4 kg of isobutyl alcohol in an open state. The obtained precipitate was collected and dried under reduced pressure at 50 ° C. to obtain 168 g of polychlorinated 2-methacryloyloxyethyltrimethylammonium chloride. The weight average molecular weight in terms of pullulan was 94,000. The weight average molecular weight of the polymer was determined by gel filtration type liquid chromatography under the following conditions.

Column: 2 KD-806M manufactured by Showa Denko KK Eluent: 50 mmol / L Lithium bromide N, N-dimethylformamide solution Detector: Differential refractometer Flow rate: 1.0 ml / min Temperature: 40 ° C
Standard: Polyethylene glycol Measurement concentration: 0.20%
Injection volume: 100 μl

Synthesis Example 2: Synthesis of b-1 When 122 g of ion-exchanged water and 122 g of propylene glycol were heated to 80 ° C. in a nitrogen atmosphere, methoxypolyethylene glycol (EO addition mole number 23) monomethacrylate (NK-ester M) -900G, manufactured by Shin-Nakamura Chemical Co., Ltd.) 225 g, methacrylic acid 75 g, 2-mercaptoethanol 4.2 g dissolved in a mixture of 50 g of ion-exchanged water and 100 g of propylene glycol, and sodium persulfate 4.2 g and 35 % Hydrogen peroxide solution dissolved in 50 g of ion-exchanged water was added dropwise over 2 hours while maintaining the temperature at 80 to 85 ° C., and then stirred for another 4 hours while maintaining at 80 ° C. . This was cooled to obtain a polymer solution.

  The weight average molecular weight of the obtained polymer was 25,000 (in terms of polyethylene glycol). Here, the molecular weight was measured by gel permeation liquid chromatography (GPC), and the following conditions were used. Both eluents and added salts were prepared from grades for liquid chromatography.

Column: Two manufactured by Tosoh Corporation G4000PWXL + G2500PWXL Eluent: 0.2M phosphate buffer (pH 6.9) / acetonitrile = 9/1 (volume ratio)
Detector: differential refractometer temperature: 40 ° C
Standard: Polyethylene glycol Measurement concentration: 5 mg / ml
Injection volume: 100 μl

  In addition, as a result of the residual monomer quantification by the following high performance liquid chromatography (HPLC) measurement, the residual monomer amount was methacrylic acid (220 ppm), methoxypolyethylene glycol (EO addition mole number 23) monomethacrylate (not detected). It was confirmed that the polymerization was completed.

<HPLC measurement conditions>
Column: L-column ODS 150 mm x 4.6 mm, manufactured by the Chemical Substance Evaluation Research Organization
Mobile phase A: 0.1% phosphoric acid / distilled water Mobile phase B: 0.1% phosphoric acid / acetonitrile gradient condition Min. A% B%
0.0 60 40
15.0 20 20
Detector: UV205nm
Temperature: 40 ° C
Injection volume: 10 μl
Flow rate: 1.0 mL / min.
(Lower limit of calibration curve: 0.25%)

  The products were separated by high performance liquid chromatography, and the presence of segment (a) and segment (b) was confirmed by NMR from the peak derived from each segment. Furthermore, it was confirmed that the target compound was produced by infrared absorption spectrum measurement.

Synthesis Example 3: Synthesis of b-2 In place of 225 g of methoxypolyethylene glycol (EO addition mole number 23) monomethacrylate ester, 270 g of methoxypolyethylene glycol (EO addition mole number 40) monomethacrylate ester was changed to 75 g of methacrylic acid. A polymer solution was obtained in the same manner as in Synthesis Example 2 except that 30 g of methacrylic acid was used.

  The weight average molecular weight of the obtained polymer was 56,000 (in terms of polyethylene glycol), and it was confirmed that the target compound was produced in the same manner as in Synthesis Example 2.

Synthesis Example 4: Synthesis of b-3 In place of 225 g of methoxypolyethylene glycol (EO addition mole number 23) monomethacrylate ester, 240 g of methoxypolyethylene glycol (EO addition mole number 40) monomethacrylate ester was changed to 75 g of methacrylic acid. A polymer solution was obtained in the same manner as in Synthesis Example 2 except that 60 g of methacrylic acid was used.

  The weight average molecular weight of the obtained polymer was 49,000 (in terms of polyethylene glycol), and it was confirmed that the target compound was produced in the same manner as in Synthesis Example 2.

Synthesis Example 5: Synthesis of b-4 In place of 225 g of methoxypolyethylene glycol (EO addition mole number 23) monomethacrylic acid ester, 195 g of methoxypolyethylene glycol (90 moles of EO addition) monomethacrylic acid ester was replaced with 75 g of methacrylic acid. A polymer solution was obtained in the same manner as in Synthesis Example 2 except that 105 g of methacrylic acid was used.

  The weight average molecular weight of the obtained polymer was 40,000 (in terms of polyethylene glycol), and it was confirmed that the target compound was produced in the same manner as in Synthesis Example 2.

Examples 1-8 and Comparative Examples 1-6
A wrinkle remover composition having the formulation shown in Table 1 was prepared. (Here, in blending the component (b) into the wrinkle remover composition, it was assumed that the polymerization reaction had completely proceeded and the polymer in the polymer solution The content was determined and blended in terms of polymer weight.) The composition was adjusted to pH 5 (25 ° C.) with a 1/10 N aqueous sodium hydroxide solution or 1N hydrochloric acid as a pH adjuster. For any composition of the formulation, the viscosity was in the range of 3-7 mPa · s (25 ° C.).

The mass ratio of segment (b) to segment (b) of component (b), that is, (a) / (b) was calculated by the following method.
(B) / (b) = {[Mass charged amount of monomer containing segment (b) in all constituent monomers of component (b)] × [Content of segment (b) in monomer containing segment (b)) Ratio (mass ratio)]} / {[preparation mass of monomer containing segment (b) in all constituent monomers of component (b)] × [inclusion of segment (b) in monomer containing segment (b)) Rate (mass ratio)]}

The content of the segment (b) of the component (b) relative to the total content of the component (a) and the component (b), that is, (b) / [(a) + (b)] was calculated by the following method.
(B) / [(a) + (b)] = {[(b) component content (mass)] × [(b) of the monomer containing the segment (b) in all constituent monomers at the time of component production Content (mass ratio)] × [content (mass ratio) of segment (b) in the monomer containing segment (b)]} / {[content of component (a)] + [(b) of component Content〕}

Also, the molar ratio of the cationic group in component (a) to the anionic group in component (b), that is, [cationic group in component (a)] / [anionic group in component (b) ] Was calculated by the following method.
[Cationic group in component (a)] / [anionic group in component (b)] = {[content (mass) of component (a)] × [containing cationic group in component (a) Charged monomer mass ratio] / [Molecular weight of monomer containing cationic group in component (a)]} / {[Content of component (b) (mass)] × [Anionic property in component (b) Charged mass ratio of monomer containing group] / [Molecular weight of monomer containing anionic group in component (b)]}

  About the obtained wrinkle removal agent composition, fiber lubricity was evaluated along the evaluation method shown below. The results are shown in Table 1.

<Evaluation method for fiber lubricity>
(1) Specimen Cotton broad # 60 (Firefly dyeing, manufactured by Tanigami Shoten Co., Ltd.) 1.8 kg of commercially available weak alkaline detergent (Kao Co., Ltd. Attack Microparticles), a two-tank washing machine (Toshiba Galaxy) VH-360S1) was repeatedly washed 5 times (detergent concentration of 0.0667% by mass, use of 36 L of tap water (20 ° C.), 10 minutes of washing-dehydration 3 minutes-rinse 8 minutes (rinsing with running water, 15 L / min of water)). After washing the washed cotton broad cloth in an environment of 25 ° C./50% RH for 12 hours, one thread at the center is placed on the test piece according to the yarn drawing method described in JIS L1096 (FIG. 44 of Method A). The same thing except having cut and leaving was produced, and it used as a test piece in this test. An outline of the test piece is shown in FIG.

(2) Evaluation of fiber lubricity With respect to the test piece prepared by the above method, the wrinkle removing composition shown in Table 1 was applied to the mass when the test cloth was dried using a spray vial (Marem Co., No. 6). 2 minutes after spraying 50% by mass using a Tensilon universal tester (RTC-1210A, manufactured by Orientec Co., Ltd.), when the test speed is 5 mm / min, the load range is 5 N, and the distance between chucks is 50 mm. The maximum static friction force was measured. The measurement was performed 10 times for each sample, and the average score was obtained. The fiber lubricity was expressed as the difference in the maximum static frictional force between the sample sprayed with ion-exchanged water (control) and each sample according to the following formula. The maximum static friction force of the control was 2.5 [N]. The fiber lubricity in this evaluation is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, and particularly preferably 0.9 or more. Evaluation of fiber lubricity was performed in an environment of 25 ° C./50% RH.

Fiber lubricity = [maximum static friction force of control (N)] − [maximum static friction force of sample (N)]

  From Table 1, the compositions of Comparative Examples 1 to 6 have poor fiber lubricity, whereas the wrinkle remover compositions of Examples 1 to 8 exhibited excellent fiber lubricity.

  Moreover, the wrinkle removal effect of the wrinkle removal composition was evaluated along the evaluation method shown below.

<Evaluation of wrinkle removal effect>
(1) Wrinkleing method Two-bath washing machine (Toshiba) using 1.8 kg of cotton broad # 60 (fired dye bleach, manufactured by Tanigami Shoten Co., Ltd.) using a commercially available weak alkaline detergent (Kao Attack Microparticles Co., Ltd.) Laundry was repeated 5 times in Galaxy VH-360S1) (detergent concentration 0.0667% by mass, use of 36 L of tap water (20 ° C.), 10 minutes of washing-dehydration 3 minutes-rinse 8 minutes (rinsing with running water, amount of water 15 L / min)) . After drying the washed cotton broad cloth, two test cloths cut to 25 cm × 15 cm are put into a plastic bag with a chuck (Unipack A-4, 70 × 50 mm, manufactured by Nippon Shokubai Co., Ltd.) at 25 ° C. By leaving it at / 50% RH for 3 hours, this was used as a wrinkle removal evaluation model.

(2) Spray treatment with wrinkle-removing composition Using the spray container (T-7500, manufactured by Canyon), the wrinkle-removing agent composition shown in Table 1 is applied to the test cloth with the model wrinkle created by the above method. After spraying 100% by mass with respect to the mass at the time of drying the test cloth, it was pulled lightly twice, hung and dried, and then allowed to stand in a temperature-controlled room at 25 ° C./50% RH for 12 hours to be naturally dried.

(3) Evaluation of wrinkle removal performance After completion of drying, the degree of wrinkle removal of the test cloth was determined. For the determination, five skilled panelists scored the cloth sprayed with the wrinkle-removing agent composition and the cloth (control) before the treatment according to the following criteria to obtain an average score. The wrinkle removal performance in this evaluation is preferably 3 or less, and more preferably 2 or less.

Evaluation criteria:
1: No wrinkles 2: Almost no wrinkles 3: Slight wrinkles remain 4: Corresponding wrinkles remain 5: Remarkably wrinkles remain

(4) Wrinkle removal performance evaluation results The wrinkle removal performances of Examples 4, 6, and 8 and Comparative Examples 2 and 3 are Example 4 (1.5), Example 6 (2.2), and Example 8 ( 3.0), Comparative Example 2 (4.0) and Comparative Example 3 (3.6), and it was confirmed that the wrinkle removing composition of the present invention exhibits an excellent wrinkle removing effect.

  Further, as described in Patent Document 2 or Patent Document (WO1999 / 055814), it is known that the wrinkle removal performance is improved by improving the lubricity of the fiber. It was also confirmed that there was a correlation between fiber lubricity and wrinkle removal performance.

Claims (6)

A wrinkle remover composition containing the following component (a) and component (b) and water ,
(A) a cationic polymer having a weight average molecular weight of 5,000 to 10,000,000 comprising at least one structural unit derived from a quaternized product of a vinyl monomer represented by the following general formula (1) or (2)

[Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² and R ³ are the same or different and represent a hydrocarbon group having 1 to 4 carbon atoms, and Y represents —O—, —NH— or —O —CH ₂ CH (OH) — represents a group, and Z represents a linear or branched alkylene group having 1 to 4 carbon atoms. ]

[Wherein, R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or a methyl group, and R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]
(B) A polymer containing an anionic group (segment (I)) and a polyalkyleneoxy group (segment (B)) in the molecule
The wrinkle removing agent, wherein the content of the segment (b) of the component (b) with respect to the total amount of the component (a) and the component (b) is (b) / [(a) + (b)] = 20 to 65% by mass. Composition. (A) component and the component (b) weight ratio of a (a) / (b) = 1 / 10~10 / 1, claim 1 wrinkle-removing composition according. The wrinkle removing composition according to claim 1 or 2 , wherein the mass ratio of the component (b) to the segment (b) is (b) / (b) = 40/60 to 1/99. The spray type wrinkle removal agent formed by filling the wrinkle removal agent composition in any one of Claims 1-3 in a spray container. The spray type wrinkle removing agent according to claim 4 , wherein the spray container comprises a trigger type sprayer. Claim 4 or 5 wrinkle removal method of textile products using spray wrinkle removal agent according.

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