TW201439203A - Aqueous composition, method for stabilizing aqueous blocked polyisocyanate, fiber treatment agent composition, and fiber - Google Patents

Abstract

The purpose of the present invention is to provide: an aqueous composition which has excellent storage stability and is capable of providing good durability in terms of washing even after storage; a method for stabilizing an aqueous blocked polyisocyanate; a fiber treatment agent composition which contains the aqueous composition; and a fiber which is treated with the fiber treatment agent composition. An aqueous composition which contains: an aqueous blocked polyisocyanate that has an isocyanate group to which a hydrophilic group is added and a blocked isocyanate group wherein an isocyanate group is blocked with a blocking agent; an amine compound in an amount of 10-400% by mole relative to the blocked isocyanate group; and water.

Description

Aqueous composition, method for stabilizing aqueous blocked polyisocyanate, fiber treatment composition, and fiber

The present invention relates to an aqueous composition, a method for stabilizing an aqueous blocked polyisocyanate, a fiber treating agent composition comprising the aqueous composition, and a fiber treated with the fiber treating agent composition.

A blocked polyisocyanate in which an isocyanate group of a polyisocyanate is blocked with a blocking agent is a useful crosslinking agent which can be reacted at a high temperature without being reacted at a normal temperature. In recent years, in view of the energy saving of cross-linking, the industry is advancing research on the low temperature of cross-linking temperature. Further, a technique of using these blocked polyisocyanates in an aqueous medium has been studied (for example, refer to Patent Documents 1 to 3).

Since the aqueous blocking polyisocyanate is water, the storage stability is difficult to ensure in the solvent system. The reason for this is that in the aqueous blocked polyisocyanate composition, there is a possibility that water reacts with the blocked isocyanate group. Further, the resin used in combination with the aqueous blocking polyisocyanate has ionicity, and the ionicity of the resin used in combination promotes the blocking of the reaction between the isocyanate group and water, and it is difficult to ensure storage stability. Moreover, as the crosslinking temperature is lowered, it becomes more difficult to ensure storage stability.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-512772

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-511507

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2007-321150

In the techniques disclosed in Patent Documents 1 to 3, although a certain degree of storage stability can be ensured, it is eagerly desired to further improve storage stability. In particular, if the fiber treatment composition containing the aqueous blocked polyisocyanate is stored for a certain period of time and the properties of the fibers treated with the stored composition are compared, the properties of the fibers treated with the composition before storage are dialed. In the case of water and the like, the fibers treated with the stored composition tend to have poor water-repellent properties. This tends to be especially noticeable when stored at high temperatures. The reason is considered to be caused by a change in the resin component in the composition. Further, these compositions may become low in temperature during storage and transportation, and also need to be used as stability of the composition. Therefore, the industry is eagerly expecting an aqueous composition having stability at a low temperature and maintaining performance after storage at a high temperature, and a fiber treatment composition containing the same.

The present invention has been made in view of the above problems, and an object thereof is to provide an aqueous composition which is excellent in storage stability and which can impart washing durability to a fiber treatment composition after storage, and a method for stabilizing an aqueous blocked polyisocyanate. A fiber treating agent composition comprising the above aqueous composition, and a fiber treated by the fiber treating agent composition.

The present inventors have made an effort to solve the above problems, and as a result, have found that the above problems can be solved by using a specific amount of an amine compound in combination with a specific aqueous blocking polyisocyanate, thereby completing the present invention.

That is, the present invention is as follows.

[1]

An aqueous composition comprising an aqueous blocked polyisocyanate having a blocked isocyanate group obtained by blocking an isocyanate group with a blocking agent and an isocyanate group having a hydrophilic group added thereto, An amine compound having 10 to 400 mol% based on the blocked isocyanate group and water.

[2]

The aqueous composition according to the above [1], wherein the aqueous blocked polyisocyanate has an aliphatic diisocyanate monomer unit and/or an alicyclic diisocyanate monomer unit.

[3]

The aqueous composition according to the above [1] or [2] wherein the content of the above amine compound is from 25 to 400 mol% based on the blocked isocyanate group.

[4]

The aqueous composition according to any one of the above items [1] to [3] wherein the average number of isocyanate groups of the above-mentioned aqueous blocked polyisocyanate precursor polyisocyanate is from 3.0 to 20.

[5]

The aqueous composition according to any one of the above items [1] to [4] wherein the average number of isocyanate groups of the above-mentioned aqueous blocked polyisocyanate precursor polyisocyanate is 4.5 to 15.

[6]

The aqueous composition according to any one of [1] to [5] wherein the above blocking agent comprises an amine compound.

[7]

The aqueous composition according to any one of the above [1] to [6] wherein the above blocking agent comprises a pyrazole.

[8]

The aqueous composition according to any one of [1] to [7] wherein the hydrophilic group is a nonionic hydrophilic group and/or a cationic hydrophilic group.

[9]

The aqueous composition according to any one of the above [1] to [8] which further comprises a polymer having a perfluoro group.

[10]

The aqueous composition according to the above [9], wherein the content of the perfluoro group-containing polymer is from 1 to 30% by mass based on the total amount of the aqueous composition, and the content of the aqueous blocked polyisocyanate is relative to the above aqueous content. The total amount of the composition is 0.05 to 10% by mass.

[11]

The aqueous composition according to the above [9] or [10] wherein the perfluoro group has a carbon number of 4 to 6.

[12]

A fiber treatment composition comprising the aqueous composition according to any one of [1] to [11].

[13]

A fiber treated with the fiber treating agent composition of the above item [12].

[14]

A method for stabilizing an aqueous blocked polyisocyanate, which comprises an aqueous blocked polyisocyanate having a blocked isocyanate group blocked with an isocyanate group by a blocking agent and an isocyanate group having a hydrophilic group added thereto, water, The amine compound is mixed such that the amount of the amine compound added is 10 to 400 mol% based on the blocked isocyanate group.

[15]

The method for stabilizing an aqueous blocked polyisocyanate according to the above [14], wherein the aqueous blocked polyisocyanate has an aliphatic diisocyanate monomer unit and/or an alicyclic diisocyanate monomer unit.

[16]

The method for stabilizing an aqueous blocked polyisocyanate according to any one of the above [14], wherein the content of the amine compound is from 25 to 400 mol% based on the blocked isocyanate group.

[17]

The method for stabilizing an aqueous blocked polyisocyanate according to any one of [14] to [16] wherein the average number of isocyanate groups of the above-mentioned aqueous blocked polyisocyanate precursor polyisocyanate is from 3.0 to 20.

[18]

The method for stabilizing an aqueous blocked polyisocyanate according to any one of [14] to [17] wherein the average number of isocyanate groups of the above-mentioned aqueous blocked polyisocyanate precursor polyisocyanate is 4.5 to 15.

[19]

The method for stabilizing an aqueous blocked polyisocyanate according to any one of [14] to [18] wherein the above blocking agent comprises an amine compound.

[20]

The method for stabilizing an aqueous blocked polyisocyanate according to any one of [14] to [19] wherein the above blocking agent comprises a pyrazole.

[twenty one]

The method for stabilizing an aqueous blocked polyisocyanate according to any one of [14] to [20] wherein the hydrophilic group is a nonionic hydrophilic group and/or a cationic hydrophilic group.

[twenty two]

The method for stabilizing an aqueous blocked polyisocyanate according to any one of [14] to [21], which further comprises a polymer having a perfluoro group.

[twenty three]

The method for stabilizing an aqueous blocked polyisocyanate according to the above item [22], wherein the content of the above-mentioned perfluoro group-containing polymer is from 1 to 30% by mass based on the total amount of the above aqueous composition, and the above-mentioned aqueous blocked polyisocyanate The content is 0.05 to 10% by mass based on the total amount of the above aqueous composition.

[twenty four]

The method for stabilizing an aqueous blocked polyisocyanate according to the above [22] or [23], wherein the perfluoro group has a carbon number of 4 to 6.

According to the present invention, an aqueous composition excellent in storage stability and capable of imparting washing durability to a fiber treating agent composition after storage, a method for stabilizing an aqueous blocked polyisocyanate, and a fiber treating agent comprising the above aqueous composition can be obtained. A composition, and a fiber treated with a fiber treatment composition.

In the following, the present invention is not limited thereto, and various modifications can be made without departing from the spirit and scope of the invention.

[Aqueous composition]

The aqueous composition of the present embodiment comprises an aqueous blocking polyisocyanate having a blocked isocyanate group obtained by blocking an isocyanate group with a blocking agent and an isocyanate group having a hydrophilic group added thereto, and is a blocked isocyanate group with respect to the blocked isocyanate group. 10 to 400 mol% of an amine compound, and water.

Here, "aqueous" means a property in which a blocked polyisocyanate is dispersed and dissolved in a medium containing water. Regarding "aqueous", the blocked polyisocyanate was mixed in a medium containing water, and stored at 0 ° C for 2 weeks, and the state of the solution after the observation was visually observed and verified based on the presence or absence of precipitation. If there is no precipitation by visual observation, it can be judged that the blocked polyisocyanate has water. By blocking the polyisocyanate from having water, a more uniform film can be formed on the surface of the substrate.

[Aqueous Blocking Polyisocyanate]

The aqueous blocking polyisocyanate in the present embodiment has an isocyanate group in which an isocyanate group is blocked by a blocking agent, and an isocyanate group in which a hydrophilic group is added. In other words, the aqueous blocked polyisocyanate is a compound in which a part of the isocyanate group of the precursor polyisocyanate having a diisocyanate monomer unit as a constituent unit is a compound which blocks an isocyanate group and an isocyanate group to which a hydrophilic group is added.

(diisocyanate monomer unit)

The aqueous blocked polyisocyanate preferably has an aliphatic diisocyanate monomer unit and/or an alicyclic diisocyanate monomer unit. That is, the polyisocyanate (hereinafter also referred to as "precursor polyisocyanate") which is a precursor of the aqueous blocking polyisocyanate is preferably agglomerated with an aliphatic diisocyanate monomer unit and/or an alicyclic diisocyanate monomer unit. Isocyanate. The water-blocking polyisocyanate has such a structure, and tends to improve storage stability.

The "aliphatic diisocyanate monomer" used in the present embodiment means a diisocyanate compound having an aliphatic group and having no aromatic group in its structure. The aliphatic diisocyanate monomer is not particularly limited, and for example, it is preferably a carbon number of 4 to 30. The aliphatic diisocyanate monomer is not particularly limited, and examples thereof include tetramethylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, and hexamethylene diisocyanate. 2,4-Trimethyl-hexamethylene-1,6-diisocyanate, quaternary acid diisocyanate. The aliphatic diisocyanate monomer may be used alone or in combination of two or more.

In addition, the "alicyclic diisocyanate monomer" used in the present embodiment means a diisocyanate compound having a cyclic aliphatic group and having no aromatic group in its structure. The alicyclic diisocyanate monomer is not particularly limited, and for example, it is preferably a carbon number of 8 to 30. The alicyclic diisocyanate monomer is not particularly limited, and examples thereof include isophorone diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 4,4'-dicyclohexylmethane. Diisocyanate and the like. The alicyclic diisocyanate monomer may be used alone or in combination of two or more.

Among them, the aqueous blocked polyisocyanate preferably contains hexamethylene diisocyanate (hereinafter also referred to as "HDI"). By including HDI, there is a tendency to form a film which is more excellent in followability to a substrate having a large deformation.

(precursor polyisocyanate)

The precursor polyisocyanate may, for example, be selected from the group consisting of a biuret bond, a urea bond, an isocyanurate bond, a uretdione bond, a urethane bond, an allophanate bond, and an imido group. two One or more bonds in the group consisting of diketone bonds. For example, two or more kinds of bonds such as an isocyanurate bond, an allophanate bond, an isocyanurate bond, and a uretdione bond may be contained. Among these, it is preferred to contain an isocyanurate bond having heat resistance.

The polyisocyanate having a biuret bond can be obtained by subjecting a so-called urethanating agent such as water, a third butanol or urea to a diisocyanate monomer to a (biuretizing agent) / (diisocyanate monomer). The diisocyanate monomer is removed after the reaction is carried out under the conditions that the molar ratio of the isocyanate group is from about 1/2 to about 1/100. For example, Japanese Patent Application Laid-Open No. Sho 53-106797

The urea bond can be formed from an isocyanate group and water or an amine group. It is preferred that the content of the urea bond in the polyisocyanate is small. Thereby, there is a tendency that the cohesive force of the blocked polyisocyanate obtained is reduced.

The polyisocyanate having an isocyanurate bond can be obtained, for example, by performing an isocyanuration reaction of a diisocyanate monomer by a catalyst or the like, and stopping the reaction when the conversion ratio is from about 5 to about 80% by mass. And remove the unreacted diisocyanate monomer. At this time, an alcohol compound can be used in combination as a raw material. The alcohol compound is not particularly limited, and examples thereof include the same compounds as those having a hydroxyl group which can be used as a raw material of a polyisocyanate having a urethane bond. In the case where these alcohols are used in combination as a raw material, the obtained polyisocyanate has both an isocyanurate bond and an allophanate bond. Such techniques are disclosed, for example, in Japanese Patent Laid-Open No. 55-38380, and Japanese Patent Laid-Open No. 57- Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Kaiping No. 6-312969 and the like.

A polyisocyanate having a uretdione bond can be obtained by using a uretdione catalyst. Such a technique is disclosed in, for example, Japanese Patent Laid-Open Publication No. Hei. No. 2007-332133, Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei.

The polyisocyanate having a urethane bond can be obtained by reacting a compound having a hydroxyl group with a diisocyanate monomer in an equivalent ratio of a hydroxyl group to an isocyanate group of from about 1/2 to about 1/100, and then removing Diisocyanate monomer. As a compound having a hydroxyl group, there are compounds having a polymerization history and compounds having a polymerization history. As the compound having a hydroxyl group without a polymerization history, a monohydric alcohol to a hexahydric alcohol can be cited.

The monohydric alcohol is not particularly limited, and examples thereof include ethanol, isobutanol, n-butanol, and 2-ethylhexanol.

The diol is not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,2. -butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2- Methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2, 3-dimethyl-2,3-butanediol, 2-ethylhexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol , 2-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, and the like.

The trivalent alcohol is not particularly limited, and examples thereof include glycerin and trimethylolpropane. Further, the tetrahydric alcohol is not particularly limited, and examples thereof include pentaerythritol. Further, the pentavalent alcohol is not particularly limited, and examples thereof include glucose. Further, the hexahydric alcohol is not particularly limited, and examples thereof include sorbitol and the like.

The compound having a polymerization history of a hydroxyl group is not particularly limited, and for example, it can be listed. Examples thereof include polyester polyols, polyether polyols, acrylic polyols, polyolefin polyols, and polycarbonate polyols.

The polyester polyol is not particularly limited, and examples thereof include those obtained by a condensation reaction of a single dibasic acid or a mixture with a single polyol or a mixture, or the use of a polyol compound to ring open ε-caprolactone. Polycaprolactones and the like obtained by polymerization, among which a ring-opening polymer is preferred. The above-mentioned separate dibasic acid or mixture is not particularly limited, and examples thereof include, for example, succinic acid, adipic acid, sebacic acid, dimer acid, maleic anhydride, phthalic anhydride, and isophthalic acid. And a single one or a mixture of two or more of the group consisting of carboxylic acids such as terephthalic acid. The above-mentioned individual polyol or mixture is not particularly limited, and examples thereof include a single one selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, neopentyl glycol, trimethylolpropane, and glycerin. Kind or a mixture of two or more kinds.

The polyether polyol is not particularly limited, and includes, for example, using a hydroxide, a strong basic catalyst, a complex metal cyanide complex, or the like, and a separate alkylene oxide or mixture and a separate polyol compound or mixture. a polyether polyol obtained by random or block addition; a polyether polyol obtained by reacting an alkylene oxide with a polyamine compound such as ethylene diamine; and using the polyether polyol as a medium A so-called polymer polyol obtained by polymerizing acrylamide or the like.

The hydroxide is not particularly limited, and examples thereof include lithium, sodium, and potassium hydroxides. The strong basic catalyst is not particularly limited, and examples thereof include an alkoxide and an alkylamine. The complex metal cyanide compound complex is not particularly limited, and examples thereof include a metal porphyrin and a zinc hexacyanocobaltate complex. The above-mentioned individual alkylene oxide or mixture is not particularly limited, and examples thereof include propylene oxide, butylene oxide, epoxycyclohexane, and epoxyethylbenzene.

The above-mentioned individual polyol compound or mixture is not particularly limited, and examples of the alcohol compound exemplified above include non-saccharides, sugar alcohol-based compounds, monosaccharides, disaccharides, trisaccharides, and tetrasaccharides.

The non-saccharide is not particularly limited, and examples thereof include diglycerin, di(trimethylolpropane), pentaerythritol, and dipentaerythritol.

The sugar alcohol-based compound is not particularly limited, and examples thereof include erythritol, D-threitol, L-arabitol, ribitol, xylitol, sorbitol, mannitol, and galactitol. Rhamnitol and the like.

The monosaccharide is not particularly limited, and examples thereof include arabinose, ribose, xylose, glucose, mannose, galactose, fructose, sorbose, rhamnose, fucose, and deoxyribose.

The disaccharide is not particularly limited, and examples thereof include trehalose, sucrose, maltose, cellobiose, gentiobiose, lactose, and melibiose.

The trisaccharide is not particularly limited, and examples thereof include raffinose, gentiotriose, and raffinose.

The above-mentioned tetrasaccharide is not particularly limited, and examples thereof include stachyose.

The acrylic polyol is not particularly limited, and examples thereof include an acrylate such as 2-hydroxyethyl acrylate having active hydrogen, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, and the like, and active hydrogen-free. An acrylic polyol obtained by copolymerization of methyl acrylate or ethyl methacrylate.

The polyolefin polyol is not particularly limited, and examples thereof include polybutadiene having two or more hydroxyl groups, hydrogenated polybutadiene, polyisoprene, and hydrogenated polyisoprene.

The polycarbonate polyol is not particularly limited, and examples thereof include a polymer obtained by polymerizing a carbonate such as a carbonic acid diester such as ethylene carbonate or a dialkyl carbonate such as diethyl carbonate.

Preferred are polyols having a polymerization history. More preferably, it is a triol, and further preferably a polycaprolactone triol.

The number average molecular weight of the polyol is preferably from 300 to 1,000, and more preferably from 300 to 500.

The polyisocyanate having an allophanate bond is not particularly limited, and for example, it can be produced from an alcohol and a diisocyanate monomer which are the same as a compound having a hydroxyl group which can be used as a raw material of a polyisocyanate having a urethane bond. The allophanate bond is added to the urethane bond to form a bond having an isocyanate group, and the bond is formed by the use of a catalyst, heat, or the like. The allophanate linkage and the urethane linkage can coexist. By coexisting with the isocyanurate bond, crosslinkability and compatibility with a polymer can be improved at the same time, which is preferable.

Imino group two The polyisocyanate of the diketone bond is not particularly limited, and can be obtained, for example, by using a catalyst or the like. A technique related to this is disclosed, for example, in Japanese Laid-Open Patent Publication No. 2004-534870.

The content of the diisocyanate monomer in the precursor polyisocyanate obtained in the above manner is not particularly limited, but is preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less. By the above range, there is a tendency that the hardenability is further improved. These precursor polyisocyanates may be used alone or in combination of two or more.

(Precursor polyisocyanate viscosity at 25 ° C)

Further, the viscosity of the precursor polyisocyanate used in the present embodiment at 25 ° C is not particularly limited, and is preferably 50 to 2,000,000 mPa. s, more preferably 3,000~50,000mPa. s. The viscosity of the precursor polyisocyanate at 25 ° C is 50 mPa. In the above, it is easy to ensure a statistical average of the isocyanate groups (hereinafter referred to as "the average number of isocyanate groups") of one molecule of the polyisocyanate. Moreover, the viscosity of the precursor polyisocyanate at 25 ° C is 2,000,000 mPa. In the following, there is a tendency that the appearance of the film formed using the film becomes better. Further, the viscosity can be measured by the method described in the examples.

(the average number of isocyanate groups of the precursor polyisocyanate)

The average number of isocyanate groups of the precursor polyisocyanate is preferably 3.0 or more and 20 or less, more preferably 3.5 or more and 15 or less, still more preferably 4.0 or more and 15 or less, still more preferably 4.5 or more and 15 or less. Crosslinkability by an average number of isocyanate groups of 3.0 or more A more excellent tendency. In addition, when the average number of isocyanate groups is 20 or less, the reactivity of the blocked isocyanate group tends to be more excellent. Further, from the viewpoint of improving the washing durability after storage, the average number of isocyanate groups is preferably 4.5 or more and 15 or less.

Further, the higher the average number of isocyanate groups, the higher the crosslinkability, but on the other hand, generally, the polyisocyanate having a high crosslinkability tends to have poor storage stability. However, in the present embodiment, even when an aqueous blocked polyisocyanate having a polyisocyanate having a higher degree of crosslinkability of 3.0 or more is used as a precursor, the storage stability of the obtained aqueous composition is stabilized. Significantly improved the amazing effect. Further, the average number of isocyanate groups of the precursor polyisocyanate can be measured by the method described in the examples.

[blocking isocyanate groups]

The aqueous blocked polyisocyanate has a blocked isocyanate group blocked with a blocking agent. Here, the term "blocking agent" means a compound which reacts with an isocyanate group and at least partially volatilizes by heating. Moreover, "blocking" means blocking an isocyanate group with a blocking agent.

The blocking agent used in the present embodiment is not particularly limited, and examples thereof include methanol, ethanol, 2-propanol, n-butanol, second butanol, 2-ethyl-1-hexanol, and 2-methyl. An alcohol such as oxyethanol, 2-ethoxyethanol or 2-butoxyethanol; a monoalkylphenol having a carbon atom number of 4 or more as a substituent; and a dialkylphenol such as n-propyl Monoalkylphenols such as phenol, isopropylphenol, n-butylphenol, t-butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol , di-n-propyl phenol, diisopropyl phenol, isopropyl cresol, di-n-butyl phenol, di-tert-butyl phenol, di-second butyl phenol, di-n-octyl phenol, two (2-B Alkylphenols such as dialkylphenols such as phenol and di-n-nonylphenol; phenols such as phenol, cresol, ethylphenol, styrenated phenol, and hydroxybenzoate; for example, dimethyl malonate Active methylene groups such as ester, diethyl malonate, ethyl acetate, ethyl acetate, ethyl acetate, etc.; butanol, twelve Mercaptans such as mercaptans; ureas such as urea, thiourea, and ethylurea; quinone imines such as amber quinone imine and maleimide; formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl Anthraquinones such as ketone oxime and cyclohexanone oxime; amines such as diphenylamine, aniline, carbazole, di-n-propylamine, diisopropylamine and isopropylethylamine; pyrazole and 3-methylpyridyl Pyrazoles such as azole, 3,5-dimethylpyrazole; imidazoles such as imidazole and 2-methylimidazole; triazoles such as 1,2,4-triazole; ethylimine and polyethylene Imines such as imines; guanamines such as acetanilide, acetamide, ε-caprolactam, δ-valeroguanamine, and γ-butyrolactam.

Among them, an amine compound is preferred. Here, the "amine compound" means a compound which can react with an isocyanate group and has a hydrogen atom directly bonded to a nitrogen atom. Specifically, they are amines, pyrazoles, imidazoles, triazoles, imines, and guanamines. Further, it is preferably an amine or a pyrazole, more preferably a pyrazole, and most preferably 3,5-dimethylpyrazole. The blocked isocyanate group which is blocked by blocking the isocyanate group with such a blocking agent tends to be more excellent in low-temperature curability.

The reaction of blocking the isocyanate group with an amine compound can be carried out by a previously known method. Specifically, the method described in JP-A-2012-107091, JP-A-2011-208028, and the like can be cited.

[Addition of isocyanate groups having a hydrophilic group]

The aqueous blocked polyisocyanate has an isocyanate group to which a hydrophilic group is added. Hereinafter, a hydrophilic group which can be added to an isocyanate group will be described. The hydrophilic group is not particularly limited, and examples thereof include a nonionic hydrophilic group, a cationic hydrophilic group, and an anionic hydrophilic group.

(nonionic hydrophilic group)

The compound to which the nonionic hydrophilic group is introduced is not particularly limited, and examples thereof include a compound obtained by adding ethylene oxide to a hydroxyl group of an alcohol such as methanol, ethanol, butanol, ethylene glycol or diethylene glycol. . These have active hydrogen reactive with isocyanate groups. Among these, it is preferred to increase the water dispersibility of the blocked polyisocyanate in a small amount. alcohol. The addition number of ethylene oxide is preferably 4 to 30, more preferably 4 to 20. When the number of addition of ethylene oxide is 4 or more, it tends to be easy to ensure water formation. Further, when the number of addition of ethylene oxide is 30 or less, there is a tendency that the precipitate of the blocked polyisocyanate is less likely to be generated at the time of low-temperature storage.

(cationic hydrophilic group)

The introduction of the cationic hydrophilic group is carried out by a method of using a compound having a cationic group and a functional group having a hydrogen reactive with an isocyanate group, or a functional group such as a glycidyl group is added to an isocyanate group in advance. A method of reacting the functional group with a specific compound such as a sulfide or a phosphine. Among them, a method using a compound having both a cationic group and hydrogen reacted with an isocyanate group is relatively easy.

The functional group having the hydrogen reactive with the isocyanate group is not particularly limited, and examples thereof include a hydroxyl group and a thiol group. The compound having a cationic hydrophilic group and a functional group having hydrogen reactive with an isocyanate group is not particularly limited, and examples thereof include dimethylethanolamine, diethylethanolamine, diethanolamine, methyldiethanolamine, and N,N. - dimethylaminohexanol, N,N-dimethylaminoethoxyethanol, N,N-dimethylaminoethoxyethoxyethanol, N,N,N'-trimethyl Aminoethylethanolamine, N-methyl-N-(dimethylaminopropyl)aminoethanol, and the like. Further, the tertiary amino group (cationic hydrophilic group) introduced into the aqueous blocked polyisocyanate may be further classified by dimethyl sulfate, diethyl sulfate or the like.

Among them, the cationic hydrophilic group is preferably a tertiary amino group. When the aqueous blocking polyisocyanate has a tertiary amino group, the following compound such as an anionic compound for neutralization tends to be volatilized by heating, and as a result, the water repellency tends to be further improved.

The introduction of the cationic hydrophilic group can be carried out in the presence of a solvent. The solvent in this case is preferably one which does not contain a functional group reactive with an isocyanate group. The solvent is not particularly limited, and examples thereof include ethyl acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol dimethyl ether.

The cationic hydrophilic group introduced into the blocked polyisocyanate is preferably used to have a negative The ionic group compound is neutralized. The anion group is not particularly limited, and examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a halogen group, and a sulfuric acid group. The compound having the above carboxyl group is not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, and lactic acid. Further, the compound having the above sulfonic acid group is not particularly limited, and examples thereof include ethanesulfonic acid and the like. Further, the compound having the above phosphoric acid group is not particularly limited, and examples thereof include phosphoric acid and acid phosphate. Further, the compound having the above halogen group is not particularly limited, and examples thereof include hydrochloric acid and the like. Further, the compound having the above sulfate group is not particularly limited, and examples thereof include sulfuric acid and the like. Among them, a compound having one carboxyl group is preferred, and acetic acid, propionic acid, and butyric acid are more preferred.

(anionic hydrophilic group)

The anionic hydrophilic group is not particularly limited, and examples thereof include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a halogen group, and a sulfuric acid group. The blocked polyisocyanate having an anionic hydrophilic group can be obtained, for example, by reacting active hydrogen of a compound having both an active hydrogen and an anionic group reactive with an isocyanate group and an isocyanate group of a precursor polyisocyanate.

The compound having both an active hydrogen and a carboxylic acid group is not particularly limited, and examples thereof include a monohydroxy group such as 1-hydroxyacetic acid, 3-hydroxypropionic acid, 12-hydroxy-9-octadecanoic acid, hydroxypivalic acid, and lactic acid. a carboxylic acid; a polyhydroxycarboxylic acid such as dimethylolacetic acid, 2,2-dimethylolbutanoic acid, 2,2-dihydroxymethylpentanoic acid, dihydroxysuccinic acid or dimethylolpropionic acid. Among them, hydroxypivalic acid and dimethylolpropionic acid are preferred.

The compound having both active hydrogen and a sulfonic acid group is not particularly limited, and examples thereof include isethionethane and the like.

The anionic hydrophilic group is not particularly limited, and for example, it can be neutralized using an amine compound as a basic substance. The amine compound is not particularly limited, and examples thereof include ammonia and a water-soluble amine compound. The water-soluble amine-based compound is not particularly limited, and examples thereof include monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, and isopropylamine. Diisopropylamine, triethanolamine, butylamine, dibutyl a primary or secondary amine such as an amine, 2-ethylhexylamine, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, morpholine; triethylamine, dimethylethanolamine A tertiary amine.

The hydrophilic group of the aqueous blocking polyisocyanate is preferably a nonionic hydrophilic group and/or a cationic hydrophilic group. The polymers used in the fiber treatment composition are generally cationic. Therefore, by having a nonionic hydrophilic group and/or a cationic hydrophilic group as the hydrophilic group of the aqueous blocking polyisocyanate, when the aqueous composition is used as a component of the fiber treating agent composition, there is a fiber treating agent composition. The dispersion stability of other polymers and water-blocking polyisocyanates is further improved.

[Ratio of addition of isocyanate groups having a hydrophilic group to blocked isocyanate groups]

The ratio (mol ratio) of the isocyanate group having a hydrophilic group to the blocked isocyanate group is preferably from 5 to 50, more preferably from 5 to 40, still more preferably from 5 to 30. When the ratio of the isocyanate group having a hydrophilic group to the blocked isocyanate group is within the above range, both the curability and the water dispersibility tend to be further improved. Further, the amount of the blocked isocyanate group and the amount of the isocyanate group to which the hydrophilic group is added can be measured by the method described in the examples.

Further, the total ratio of the blocked isocyanate group to the isocyanate group to which the hydrophilic group is added is preferably from 50 to 100 mol, more preferably 100 mol, based on 100 mol of the total isocyanate group of the precursor polyisocyanate. When the total ratio of the blocked isocyanate group to the isocyanate group to which the hydrophilic group is added is in the above range with respect to 100 mol of the total isocyanate group of the polyisocyanate of the precursor, the curability and the water dispersibility are further improved. .

[Aqueous poly-blocking isocyanate content]

The content of the aqueous blocking polyisocyanate in the aqueous composition is preferably from 10 to 40% by mass based on the total amount of the aqueous composition when the aqueous composition does not contain the polymer having a perfluoro group described below. More preferably, it is 20 to 40% by mass, and further preferably 20 to 35. quality%. When the content of the aqueous poly-blocking isocyanate is 10% by mass or more, transportation costs and the like tend to become more economical. Moreover, since the content of the aqueous poly-blocking isocyanate is 40% by mass or less, the storage stability of the aqueous composition at a high temperature tends to be further improved.

Further, when the aqueous composition contains the following polymer having a perfluoro group, the content of the aqueous poly-blocking isocyanate in the present embodiment is preferably 0.05 to 10% by mass, more preferably 1 to 5% by mass, and further It is preferably 1 to 3% by mass. When the content of the aqueous poly-blocking isocyanate of the present embodiment is within the above range, the water repellency of the fiber treated with the fiber treating agent containing the aqueous composition tends to be further improved.

When the aqueous blocking polyisocyanate has an ionic group (for example, a cationic or anionic hydrophilic group), the content of the aqueous blocking polyisocyanate is based on the mass of the ionic group containing the equivalent neutralizing agent.

[Amine compound]

The aqueous composition of the present embodiment contains an amine compound. The amine compound has a hydrogen atom which is directly bonded to a nitrogen atom which can react with an isocyanate group.

The amine-based compound is not particularly limited, and examples thereof include amines, pyrazoles, imidazoles, triazoles, imines, and guanamines exemplified in the blocking agent. Among them, preferred are pyrazoles and amines, more preferably 3,5-dimethylpyrazole or isopropylamine, and still more preferably 3,5-dimethylpyrazole. When the amine compound contains a pyrazole, the storage stability of the aqueous composition tends to be further improved. Further, the amine compound may be the same as or different from the amine compound used in the blocking agent. When the same amine compound is used, the production steps of the aqueous composition of the present embodiment can be simplified. The amine compound may be used alone or in combination of two or more.

(content of amine compound)

The content of the amine compound is from 10 to 400 mol%, preferably from 25 to 300 mol%, more preferably from 25 to 100 mol%, based on the blocked isocyanate group of the aqueous blocked polyisocyanate. Blocking isocyanate groups by the content of amine compounds relative to aqueous blocked polyisocyanate When it is 10 mol% or more, the high temperature stability tends to be good. When the content of the amine compound is 400 mol% or less with respect to the blocked isocyanate group of the aqueous blocking polyisocyanate, the low-temperature storage stability becomes better. Further, the content of the amine compound which is not reacted with the isocyanate group can be measured by the method described in the examples.

[water]

The aqueous composition of the present embodiment contains water. The water is not particularly limited, and tap water, distilled water, ion-exchanged water, or the like can be appropriately selected and used. Distilled water and ion-exchanged water are preferred. The content of water is preferably from 45 to 90% by mass, more preferably from 55 to 90% by mass, even more preferably from 65 to 90% by mass, based on the total amount of the aqueous composition. Further, water can be formulated when the aqueous blocked polyisocyanate or the polymer having a perfluoro group is produced and the components are prepared.

[polymer with perfluoro group]

The aqueous composition of the present embodiment preferably contains a polymer having a perfluoro group. The entire hydrogen of the "perfluoro group" hydrocarbon group is a group of a fluorine atom and is represented by the following formula (1).

CF ₃ (CF ₂ ) _n - (1)

(In the formula (1), C represents a carbon atom, F represents a fluorine atom, and n represents an integer of 3 to 8)

The content of the polymer having a perfluoro group is preferably from 1 to 30% by mass, more preferably from 5 to 30% by mass, even more preferably from 10 to 30% by mass, based on the total amount of the aqueous composition. When the content of the polymer having a perfluoro group is 1% by mass or more, the storage stability of the aqueous composition is further improved, and the transportation cost is further improved. When the content of the polymer having a perfluoro group is 30% by mass or less, precipitation or the like is less likely to occur, and the stability of the aqueous composition is further improved.

The polymer having a perfluoro group used in the present embodiment is not particularly limited, and examples thereof include polymerization of a acrylate having a perfluoro group and/or a methacrylate as a main monomer. The carbon number of the perfluoro group is preferably from 3 to 8, more preferably from 4 to 6. By the carbon number of the perfluoro group being 6 or less, there is further suppression of the accumulation of the environment or the human body. Consider the tendency to produce perfluorooctanoic acid. In addition, in general, the carbon number of the perfluoro group is 8 and the washing durability is excellent. However, in the aqueous composition of the present embodiment, the polyisocyanate is blocked with water and the carbon number is 6 or less. The perfluoro-based polymer further improves the washing durability.

In addition to the perfluoro group acrylate and/or methacrylate, other monomers copolymerizable with the monomers may be used in combination. The monomer is not particularly limited, and examples thereof include lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, benzyl acrylate, benzyl methacrylate, and glycidyl acrylate. Glycidyl methacrylate, aziridine acrylate, aziridine methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, Acrylic acid or methacrylate such as alkanediol acrylate; acrylamide, methacrylamide, N-methylol acrylamide, N-methylol methacrylate such as alkanediol dimethacrylate Acrylamide or methacrylamide such as decylamine, diacetone acrylamide, diacetone methacrylamide, hydroxymethylated diacetone acrylamide, etc.; and butylene such as dibutyl maleate Alkyl diacids; olefins such as ethylene, propylene, butadiene, isoprene, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, chloroprene; carboxylic acids such as vinyl acetate Vinyl esters; styrene, α-methylstyrene, β-methylstyrene Styrene; ethyl vinyl ether, cyclohexyl vinyl ether, halogenated alkyl vinyl ether, vinyl ethers and the like.

The total content of the acrylate unit and the methacrylate unit having a perfluoroalkyl group is preferably 40% by mass or more, more preferably the total amount of all the monomer units in the polymer having a perfluoroalkyl group. It is 50 to 80% by mass.

The polymer having a perfluoroalkyl group can be produced by a known polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, or the like, and it is preferably produced by emulsion polymerization.

The content ratio (polymer having a perfluoro group: aqueous blocked polyisocyanate) is preferably 50:50 to 95:5, more preferably 70:30 to 95:5, still more preferably 70:30 to 90:10. When the content ratio is within the above range, the washing durability tends to be further improved.

The polymer having a perfluoro group used in the fiber treatment composition is not particularly limited, and is preferably cationic. When the polymer used in combination with the aqueous blocking polyisocyanate is ionic, especially cationic, the reactivity of the aqueous blocking polyisocyanate is further improved, but on the other hand, the storage stability of the aqueous composition is generally Reduce the tendency. However, the aqueous composition containing the aqueous blocking polyisocyanate, the water reactive with the isocyanate group, the amine compound, and the cationic polymer having a perfluoro group, for example, has higher storage stability and has higher storage stability. Amazing effect. Specifically, the aqueous composition of the present embodiment can also impart washing durability after being stored at 50 ° C for 4 weeks.

[Water-soluble organic solvent]

Further, the aqueous composition may optionally contain a water-soluble organic solvent. The water-soluble organic solvent is not particularly limited, and may have a hydroxyl group, and examples thereof include alcohols and ethers. More specifically, for example, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 3-methoxy- 3-methylbutanol and the like. Here, "water-soluble" means a solubility of 10 g of solvent / 100 g of water or more at 25 °C.

[Method for Producing Aqueous Composition]

The aqueous composition of the present embodiment can be obtained by blocking an isocyanate group obtained by blocking an isocyanate group with a blocking agent, and an aqueous blocked polyisocyanate having an aliphatic group-added isocyanate group, water, and The above-mentioned blocked isocyanate group is obtained by mixing an amine compound having 10 to 400 mol%.

The mixing method is not particularly limited, and for example, it can be carried out using a mixing tank having a stirring blade or the like. The temperature at the time of mixing is preferably from 10 to 90 degrees. The order of mixing the blocked polyisocyanate having an isocyanate group blocked with an isocyanate group by a blocking agent and the isocyanate group having a hydrophilic group added thereto, water, and an amine compound is not limited, and The amine-based compound is added and mixed immediately after the production of the aqueous blocking polyisocyanate, and immediately after the production, and water is added and mixed.

Further, when the amine compound is the same as the blocking agent, a predetermined amount of the amine compound can be simultaneously added by adding a blocking agent in an amount larger than the isocyanate group when the aqueous blocking isocyanate is produced.

Further, the water-blocking polyisocyanate, water, an amine compound, and a polymer having a perfluoro group as necessary may be the same as those described in the above aqueous composition.

[Stabilization method of aqueous blocked polyisocyanate]

The method for stabilizing the aqueous blocked polyisocyanate of the present embodiment is an aqueous blocked polyisocyanate having a blocked isocyanate group obtained by blocking an isocyanate group with a blocking agent and an isocyanate group having a hydrophilic group added thereto, and water. And the amine compound is mixed so that the amount of the amine compound added may be 10 to 400 mol% with respect to the blocked isocyanate group. As described above, by allowing the aqueous blocking polyisocyanate to coexist with the amine compound, the storage stability of the aqueous blocking polyisocyanate can be improved, and an aqueous composition excellent in storage stability can be obtained. Further, the mixing method is not particularly limited, and the same method as the above production method can be used.

[Fiber treatment composition]

The fiber treatment composition of the present embodiment contains an aqueous composition. In the fiber treatment composition of the present embodiment, an additive may be contained as needed. The additive is not particularly limited, and examples thereof include a flame retardant, a dye stabilizer, an anti-drug agent, an antibacterial agent, an antifungal agent, an insect repellent, an antifouling agent, an antistatic agent, an amine-based plastic resin, and an acrylic polymer. , Glyoxal resin, melamine resin, natural wax, polyoxyn resin, tackifier, polymer compound. The fiber treatment composition can be used by further dilution with water prior to use. The total content of all the polymers contained in the diluted fiber treatment composition is preferably from 0.5 to 5% by mass, more preferably from 0.5 to 3% by mass.

[fiber]

The fiber of the present embodiment is treated by a fiber treatment composition. use The treatment of the fibers of the fiber treatment composition can be carried out by attaching the fiber treatment composition to the fibers and then heating. The method of adhering the fiber treatment composition is not particularly limited, and examples thereof include a pad method, a dipping method, a spray method, a coating method, and a printing method.

Thereafter, it is adjusted to a specific immersion amount (polymer adhesion amount) by using a press or the like, and then heated at a temperature of 100 ° C or higher. It is preferably heated at a temperature of about 140 to 180 ° C for 10 seconds to 10 minutes, preferably 30 seconds to 3 minutes.

The type of the fiber to which the fiber treatment composition of the present embodiment can be applied is not particularly limited, and examples thereof include cotton, kapok, linen, ramie, jute, manila hemp, kenaf, wool, cashmere wool, and mohair. Natural fibers such as Alpaca, camel hair, raccoon, feathers; regenerated fibers such as strontium, multi-brain fiber, cuprammonium fiber, tencel; semi-synthetic fibers such as cellulose acetate fiber and promix; Amidamide fiber, polyester fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyurethane fiber, polyacetal fiber, polytetrafluoroethylene fiber, benzoate fiber, Poly-p-phenylene benzothiazole fiber, poly-p-phenylene benzoate Synthetic fibers such as azole fibers and polyamidene fibers; inorganic fibers such as asbestos, glass fibers, carbon fibers, alumina fibers, tantalum carbide fibers, boron fibers, kiranol fibers, inorganic whiskers, rock fibers, slag fibers, etc.; Composite fibers, blended fibers, and the like. Examples of the form thereof include a woven fabric, a knitted fabric, and a non-woven fabric.

[Examples]

Hereinafter, the present invention will be more specifically described using examples and comparative examples. The invention is not limited by the following examples.

(Measurement of the number average molecular weight)

The number average molecular weight of the aqueous composition, the precursor polyisocyanate, and the polyol is determined by gel permeation chromatography (hereinafter referred to as "GPC") using the following apparatus as the number average molecular weight based on polystyrene. Find out.

Device: Tosoh (share) HLC-802A

Pipe column: Tosoh (share) G1000HXL × 1 G2000HXL × 1 G3000HXL × 1

Carrier: tetrahydrofuran

Detection method: differential refractometer

(Measurement of unreacted diisocyanate monomer content)

The unreacted diisocyanate monomer content is represented by the following formula, and the peak area of the precursor polyisocyanate obtained in the above GPC measurement is equivalent to the molecular weight of the unreacted diisocyanate monomer (for example, if it is hexamethylene diisocyanate) Then, it is calculated as the peak area of 168).

(unreacted diisocyanate monomer content) = (peak area of unreacted diisocyanate) / {(peak area of precursor polyisocyanate) + (peak area of unreacted diisocyanate)} × 100

(Measurement of Isocyanate Group Concentration of Precursor Polyisocyanate)

The precursor polyisocyanate 1 to 3 g (Wg) was accurately weighed and placed in an Erlenmeyer flask, and then 20 mL of toluene was added to completely dissolve the precursor polyisocyanate. Thereafter, 10 mL of a toluene solution of 2 equivalents of di-n-butylamine was added, and after completely mixing, it was allowed to stand at room temperature for 15 minutes. Further, 70 mL of isopropyl alcohol was added to the solution and thoroughly mixed. This solution was titrated as an indicator with a 1% strength hydrochloric acid solution (coefficient F). The titration value was set to V2 mL, and the same operation was carried out without the precursor polyisocyanate. The titration value was set to V1 mL, and the isocyanate group concentration of the precursor polyisocyanate was calculated according to the following formula.

Isocyanate group concentration%=(V1-V2)×F×42/(W×1000)×100

(Measurement of the average number of isocyanate groups of precursor polyisocyanate)

The average number of isocyanate groups of the precursor polyisocyanate is based on the following formula: The isocyanate group concentration of the polyisocyanate and the number average molecular weight were determined.

Average number of isocyanate groups = number average molecular weight × isocyanate group concentration / 100 / 42

(Measurement of the amount of blocked isocyanate groups)

The amount of the blocked isocyanate group (the ratio of the blocked isocyanate group to the total of 100 moles of the isocyanate group of the precursor polyisocyanate) was measured by proton nuclear magnetic resonance measurement, and the integrated value of the specific absorption peak was measured and calculated. The measurement conditions are as follows.

Device: JNM-ECS400 of the Japan Electronics Co., Ltd.

Determination conditions:

Resonance frequency: 400MHz

Cumulative number: 128

Solvent: Deuterated chloroform

Sample concentration: about 40mg/mL

(Measurement of the amount of isocyanate groups added to the hydrophilic group)

The amount of isocyanate group added to the hydrophilic group (the ratio of the amount of the isocyanate group added to the hydrophilic group to the total of 100 moles of the isocyanate group of the precursor polyisocyanate) is used in the measurement of the amount of the blocked isocyanate group. The proton nuclear magnetic resonance measurement was carried out under the same measurement conditions as the proton nuclear magnetic resonance, and the integrated value of the specific absorption peak was measured and calculated. The hydrophilic group type was confirmed and added to the isocyanate group.

(Average number of isocyanate groups of water-blocking polyisocyanate precursor polyisocyanate)

The proton NMR measurement is carried out by the same measurement conditions as the proton nuclear magnetic resonance used in the measurement of the blocked isocyanate group amount, and the hydrophilic group-added isocyanate group and the blocked isocyanate contained in the aqueous blocking polyisocyanate are specified. The type of the base was quantified in the form of % molar concentration in 1 g of the aqueous blocked polyisocyanate.

Further, in the above GPC measurement, the number average molecular weight of the aqueous blocking polyisocyanate was determined, and the average number of isocyanate groups of the aqueous blocking polyisocyanate precursor polyisocyanate was calculated according to the following formula. Furthermore, if the sample is determined to be mixed with a water-blocking polyisocyanate The aqueous composition of the component other than the ester, the molecular weight of the diisocyanate monomer blocked from the lowest molecular weight of the aqueous blocked polyisocyanate, that is, blocked by the blocking agent, to the lowest molecular weight of the polymer having the perfluoro group described below. The molecular weight was set to be an aqueous blocking polyisocyanate component, and the number average molecular weight was determined.

The average number of isocyanate groups of the precursor polyisocyanate = the number average molecular weight of the aqueous blocked polyisocyanate × the blocked isocyanate base molar % / 100 + the number average molecular weight of the aqueous blocked polyisocyanate × the isocyanate group with the hydrophilic group added Ear concentration%/100

(Measurement of the content of an amine compound which is not reacted with an isocyanate group in an aqueous composition)

The unreacted amine compound (not linked to the aqueous blocked polyisocyanate bond) was determined by measurement of the aqueous composition after the calibration curve of the amine compound based on the peak area was prepared using the following liquid chromatography apparatus and measurement conditions. The concentration of the amine compound of the knot (reaction). The content (equivalent %) of the amine compound which is not reacted with the isocyanate group with respect to the blocked isocyanate group is determined from the concentration of the unreacted amine compound and the above-mentioned blocked isocyanate group concentration.

Liquid chromatography device

Device: Agilent technologie company's trade name 1100series

Column: Imtax company's trade name Cadenza CD-C18 (diameter 2mm × length 30mm)

Measuring condition

Mobile phase: gradient of water and methanol

Initial: water / methanol = 10 / 90 (volume)

After 5 minutes: water / methanol = 98 / 2 (volume)

(Confirmation of aliphatic and / or alicyclic diisocyanate monomer units)

The confirmation of the aliphatic and/or alicyclic diisocyanate monomer unit is carried out by performing proton nuclear magnetic resonance measurement using the same measurement conditions as the proton nuclear magnetic resonance used for the measurement of the blocked isocyanate group amount. Specific absorption peaks.

(viscosity)

The viscosity of the precursor polyisocyanate is an E-type viscometer (VISCONIC RE-85R type manufactured by Tokimec Co., Ltd.), and the rotor is set to 1°34 ' × R24, and the number of revolutions corresponding to the viscosity (if it is described in the specification) The range of 1300 to 2600 mPa.s is 5 rpm, and the measurement is carried out at 25 °C.

(Measurement of Resin Component Concentration in Aqueous Composition)

After accurately weighing the aluminum pan with a bottom diameter of 38 mm (W1), accurately weigh about 1 g of the aqueous composition on an aluminum pan (W2), and adjust the aqueous composition to a uniform thickness, in an oven at 105 ° C. Dry for 1 hour. After the aluminum pan was cooled to room temperature, the total mass (W3) of the dried aqueous composition and the aluminum pan was accurately weighed. The resin component concentration in the aqueous composition was determined from W2A and W3A obtained by subtracting the mass of the amine compound from the above W2 and W3, using the following formula.

Resin component concentration (% by mass) = (W3A-W1) / W2A × 100

In addition, the "resin component concentration" obtained here is a total amount of the aqueous blocking polyisocyanate and the polymer having a perfluoro group.

(Measurement of the content of a polymer having a perfluoro group)

The content of the polymer having a perfluoro group is determined by measuring the GPC measurement result of the aqueous composition and the concentration of the resin component in the aqueous composition according to the following formula. In addition, the "total peak area of the GPC of the polymer having a perfluoro group" means the lowest molecular weight of the polymer having a perfluoro group in the GPC measurement of the aqueous composition, and the peak of the molecular weight larger than the lowest molecular weight. The total area. Moreover, the "total peak area of GPC" means the total area of peaks of higher molecular weight than the diisocyanate monomer blocked by a blocking agent. Further, when the polymer having a perfluoro group is cationic, triethylamine is added to the carrier, and it is confirmed that the area % of each peak shows a fixed value of triethylamine concentration, and the use has the three The carrier of the concentration of the base amine was measured.

Polymer concentration with perfluoro group (% by mass) = GPC of polymer with perfluoro group Total peak area / total peak area of GPC × resin component concentration

Whether or not the compound in the component fractionated from GPC contains a perfluoro group and the carbon number in the case of containing the perfluoro group can be confirmed by thermal decomposition, gas chromatography, and mass analysis.

Thermal decomposition:

. Device: Pyrotech from Frontier Laboratories, Inc. Product Code PY-2020D

. Measurement conditions: 600 ° C

Gas chromatography:

. Device: Agilent Technologies, trade name 6890

. Column: Agilent Technologies' trade name J & W

DB-1 (0.25mm inner diameter × 30m), liquidus thickness 0.25μm

. Determination conditions:

. Column temperature: 40 ° C (for 5 minutes), the temperature was raised at 20 ° C / min, and held at 320 ° C for 11 minutes.

. Injection temperature: 320 ° C, ion source temperature: 230 ° C, split ratio 1/50

Quality Analyzer:

. Device: Agilent Technologies trade name MSD5975C

. Ionization method: electronic ionization

(Determination of the content of the aqueous blocked polyisocyanate in the aqueous composition)

The content of the aqueous blocked polyisocyanate in the aqueous composition was determined from the GPC measurement results of the aqueous composition and the resin component concentration in the aqueous composition, and was determined according to the following formula. In addition, the "total area of the aqueous blocked polyisocyanate" means the lowest molecular weight of the aqueous blocked polyisocyanate, that is, the peak of the diisocyanate monomer blocked by the blocking agent to be smaller than the polymer having the perfluoro group. The total area of the peak of the aqueous blocked polyisocyanate up to the molecular weight of the lowest molecular weight. Moreover, the "total peak area of GPC" means the total area of peaks of higher molecular weight than the diisocyanate monomer blocked by a blocking agent.

Aqueous poly-blocking isocyanate concentration (% by mass) = total area of aqueous blocked polyisocyanate / total peak area of GPC × resin component concentration

(low temperature storage stability)

The evaluation of the low-temperature storage stability was carried out by storing the aqueous composition or the fiber treatment composition at 0 ° C for 2 weeks, and visually observing the appearance thereof, and confirming the presence or absence of precipitation. The case where no precipitation was observed was indicated as ○ (good), and the case where precipitation was observed was indicated as × (bad).

(washing durability)

The aqueous composition after storage for 4 weeks at 50 ° C was prepared with the unstored aqueous composition. Water was added to the two aqueous compositions to be diluted, and the total of the polymer having a perfluoro group and the aqueous blocked polyisocyanate was 2% by mass to obtain two kinds of treatment liquids.

Nylon cloth (Nippon Standards Association No. 670108) was separately immersed in the two kinds of treatment liquids, and then extruded by a roll so that the amount of immersion was 50%. This was dried at 120 ° C for 60 seconds, and further dried at 170 ° C for 60 seconds to obtain two kinds of test cloths.

The evaluation of the washing durability was carried out by evaluating the water repellency of the two test cloths obtained after washing 10 times in accordance with JIS L 1092 in five grades. A score of 5 indicates the highest water repellency and a score of 1 indicates the lowest water repellency. Further, the lotion used for washing was carried out under the trade name Attack of Kao Co., Ltd., and the washing was carried out in accordance with JIS L 0217, Schedule 1, No. 103.

[Manufacturing Example 1: Production of precursor polyisocyanate]

A four-necked flask equipped with a stirrer, a thermometer, a reflux cooling tube, a nitrogen gas injection tube, and a dropping funnel was placed in a nitrogen atmosphere, and 600 g of hexamethylene diisocyanate (hereinafter also referred to as "HDI") was added as a triol. The polycaprolactone-based polyester triol "PLACCEL 303" (trade name: molecular weight: 300, manufactured by Daicel Chemical Co., Ltd.) was 30 g, and the temperature in the reactor was maintained at 90 ° C for 1 hour while stirring. Thereafter, the temperature in the reactor was maintained at 80 ° C, and tetramethylammonium octylate as an isocyanurate catalyst was added. When the rate became 54%, phosphoric acid was added to stop the reaction. After the obtained reaction liquid was filtered, unreacted HDI was removed using a thin film evaporator to obtain a precursor polyisocyanate before Production Example 1. The viscosity of the obtained precursor polyisocyanate at 25 ° C is 9,500 mPa. s, the isocyanate group concentration was 19.2% by mass, the number average molecular weight was 1,100, the average number of isocyanate groups was 5.1, and the residual HDI concentration was 0.2% by mass.

[Production Example 2: Production of precursor polyisocyanate]

A four-necked flask equipped with the same apparatus as in Production Example 1 was placed in a nitrogen atmosphere, and 600 g of HDI was added, and the temperature in the reactor was maintained at 70 ° C under stirring. The tetramethylammonium octylate as an isocyanurate catalyst was added, and phosphoric acid was added at a time point when the yield became 40% to stop the reaction. After the obtained reaction liquid was filtered, unreacted HDI was removed using a thin film evaporator to obtain a precursor polyisocyanate before Production Example 2. The viscosity of the obtained precursor polyisocyanate at 25 ° C is 2,700 mPa. s, the isocyanate group concentration was 21.7%, the number average molecular weight was 660, the average number of isocyanate groups was 3.4, and the residual HDI concentration was 0.2% by mass.

[Example 1: Synthesis of nonionic aqueous pyrazole-blocking polyisocyanate composition]

In the same apparatus as in Production Example 1, a nitrogen atmosphere was used, and 100 g of the precursor polyisocyanate and 25 g of dipropylene glycol dimethyl ether obtained in Production Example 1 were added, and mixed at 50 ° C to obtain a homogeneous solution. Thereafter, the temperature was raised to 80 ° C, and 46.6 g of methoxypolyethylene glycol (molecular weight 680, resin component hydroxyl value: 82 mgKOH/g) was added, followed by mixing for 2 hours. It was confirmed that the residual isocyanate group concentration after mixing for 2 hours was 11.1% by mass based on the resin component (15 mol% of the isocyanate group of the precursor polyisocyanate reacted).

Thereafter, 52.7 g of 3,5-dimethylpyrazole (1.5 equivalents of 3,5-dimethylpyrazole relative to the residual isocyanate group) was added to the obtained reaction liquid, and they were mixed for 1 hour. Thereafter, the infrared spectrum of the reaction liquid (product name FT/IR-4000 manufactured by JASCO Corporation) was measured, and it was confirmed that no absorption of the isocyanate group was observed. Water was finally added to obtain the aqueous composition of Example 1. The solid content concentration (aqueous blocking polyisocyanate component) of the solution is 30% by mass (water content: 66.9 mass%), and the amine compound which is not reacted with the isocyanate group The content is 50 mol% relative to the total blocked isocyanate groups. The results are shown in Table 1.

[Example 2: Synthesis of nonionic aqueous pyrazole-blocking polyisocyanate composition]

Using 100 g of the polyisocyanate of the precursor of Production Example 2, the amount of methoxypolyethylene glycol (molecular weight 680, resin component hydroxyl value 82 mgKOH/g) was 52.7 g, and 3,5-dimethylpyrazole was used. The aqueous composition of Example 2 was obtained by the same operation as in Example 1 except that the amount of addition was 74.4 g. The results are shown in Table 1.

[Example 3: Synthesis of cationic pyrazole-blocking polyisocyanate composition]

In the same apparatus as in Production Example 1, a nitrogen atmosphere was used, and 100 g of the precursor polyisocyanate and 50 g of dipropylene glycol dimethyl ether obtained in Production Example 1 were added, and mixed at 50 ° C to obtain a homogeneous solution. After maintaining at 60 ° C, 8.1 g of 2-(dimethylamino)ethanol having 1 cationic group and 1 hydroxyl group was added to the obtained mixture (20 mol% of the isocyanate group of the precursor polyisocyanate) ) and mix for 30 minutes. It was confirmed that all of 2-(dimethylamino)ethanol reacted.

Thereafter, 53.4 g of 3,5-dimethylpyrazole (the mass of 1.5 equivalent of 3,5-dimethylpyrazole of the residual isocyanate group) was added to the obtained mixture, and the mixture was mixed for 30 minutes. The infrared absorption spectrum of the reaction liquid obtained was measured, and it was confirmed that the absorption of the isocyanate group disappeared. Further, 6.2 g of acetic acid (1.2 equivalents to the amine) was further added to the reaction mixture and mixed. Thereafter, ion-exchanged water was added to obtain an aqueous composition of Example 3 having a solid content concentration of 30% by mass. The results are shown in Table 1.

[Example 4: Synthesis of nonionic aqueous pyrazole-blocking polyisocyanate composition]

The aqueous composition of Example 4 was obtained by the same operation as in Example 1 except that the amount of 3,5-dimethylpyrazole added was 43.9 g (1.25 equivalents of the residual isocyanate group). The results are shown in Table 1.

[Example 5: Synthesis of nonionic aqueous pyrazole-blocking polyisocyanate composition]

The amount of 3,5-dimethylpyrazole added was set to 35.1 g (1.0 times equivalent of the residual isocyanate group), and after the characteristic absorption of the isocyanate group disappeared, diisopropylamine was further added. The aqueous composition of Example 5 was obtained by the same operation as in Example 1, except that g (50 mol% with respect to the blocked isocyanate group). The results are shown in Table 1.

[Comparative Example 1: Synthesis of nonionic aqueous pyrazole-blocking polyisocyanate composition]

The aqueous composition of Comparative Example 1 was obtained by the same operation as in Example 1 except that the amount of the 3,5-dimethylpyrazole was changed to 36.9 g (1.05 equivalent of the residual isocyanate group). The results are shown in Table 1.

[Comparative Example 2: Synthesis of nonionic aqueous pyrazole-blocking polyisocyanate composition]

The aqueous composition of Comparative Example 2 was obtained by the same operation as in Example 1 except that the amount of the 3,5-dimethylpyrazole added was 211 g (6.0 times equivalent of the residual isocyanate group). The results are shown in Table 1.

[Comparative Example 3: Synthesis of nonionic aqueous pyrazole-blocking polyisocyanate composition]

3,5-dimethylpyrazole was added in an amount of 35.1 g (1.0 times equivalent of the residual isocyanate group), and 2,400 g of dipropylene glycol monomethyl ether (an alcohol having a hydroxyl group) was added (50 with respect to the blocked isocyanate group). An aqueous composition of Comparative Example 3 in which the solid content was 30% by mass was obtained by the same operation as in Example 1 except for the above. The results are shown in Table 1.

[Comparative Example 4: Blocking polyisocyanate composition for water dispersion using an external emulsifier]

In the same apparatus as in Production Example 1, a nitrogen atmosphere was used, and 100 g of the precursor polyisocyanate and 25 g of dipropylene glycol dimethyl ether obtained in Production Example 1 were added, and mixed at 50 ° C to obtain a homogeneous solution. To the obtained mixed liquid, 65.9 g of a 3,5-dimethylpyrazole (1.5 times the equivalent of the isocyanate group) was added and mixed. The disappearance of the characteristic absorption of the isocyanate group was confirmed by infrared spectroscopy. Thereafter, 3 g of dialkyl (hydrogenated tallow) dimethyl ammonium chloride and 30 g of a polyoxyethylene polyoxypropylene block polymer were added to the obtained mixed liquid and mixed. Thereafter, ion-exchanged water was slowly added to the obtained mixed liquid, and the solid content concentration was 30% by mass to obtain an aqueous composition of Comparative Example 4. There is no hydrophilic group added to the polyisocyanate, and the concentration of the amine compound which does not react the isocyanate group is 50 mol% with respect to the total blocked isocyanate group. The results are shown in Table 1. Furthermore, in Comparative Example 4, blocking There is no addition of a hydrophilic group in the polyisocyanate, and the blocked polyisocyanate is water-dispersed by an external additive.

[Embodiment 6]

Fluoropolymer for water repellent (AsahiGuard AG-E061, 20% solid content, weakly cationic, aqueous dispersion of polymer with a carbon number of 6 perfluorocarbon) 85.4 g was mixed with 6.3 g of the aqueous composition of Example 1 (the polymer / the aqueous blocked polyisocyanate = 9 / 1 (resin component mass ratio)). Further, the mixture was diluted with water, and the concentration of the polymer in the mixed solution was adjusted to 20% by mass to obtain the aqueous composition of Example 6. The content of the polymer having a perfluoro group is 18% by mass, the content of the aqueous blocked polyisocyanate is 2% by mass, and the content of 3,5-dimethylpyrazole which is not reacted with the isocyanate group is relative to the blocked isocyanate group. 50% by mole. The aqueous composition was evaluated for low temperature storage stability and water repellency evaluation. The results are shown in Table 2.

[Embodiment 7]

The aqueous composition of Example 7 was obtained by the same operation as in Example 6 except that the aqueous composition of Example 4 was used instead of the aqueous composition of Example 1. The results are shown in Table 2.

[Embodiment 8]

An aqueous composition of Example 8 was obtained by the same operation as in Example 6 except that 0.56 g of 3,5-dimethylpyrazole was further added. The content of 3,5-dimethylpyrazole which was not reacted with the isocyanate group was 200 mol% with respect to the blocked isocyanate group. The results are shown in Table 2.

[Embodiment 9]

The aqueous composition of Example 9 was obtained by the same operation as in Example 6 except that the aqueous composition of Example 5 was used instead of the aqueous composition of Example 1. The content of the diisopropylamine which is not reacted with the isocyanate group is 50 mol% with respect to the blocked isocyanate group. The results are shown in Table 2.

[Embodiment 10]

The aqueous composition of Example 10 was obtained by the same operation as in Example 6 except that the aqueous composition of Example 2 was used instead of the aqueous composition of Example 1. The results are shown in Table 2.

[Example 11]

The aqueous composition of Example 11 was obtained by the same operation as in Example 6 except that the aqueous composition of Example 3 was used instead of the aqueous composition of Example 1. The results are shown in Table 2.

[Comparative Example 5]

The aqueous composition of Comparative Example 5 was obtained by the same operation as in Example 6 except that the aqueous composition of Comparative Example 1 was used instead of the aqueous composition of Example 1. The content of 3,5-dimethylpyrazole which was not reacted with the isocyanate group was 5 mol% with respect to the blocked isocyanate group. The results are shown in Table 2.

[Comparative Example 6]

The aqueous composition of Comparative Example 6 was obtained by the same operation as in Example 6 except that the aqueous composition of Comparative Example 2 was used instead of the aqueous composition of Example 1. The content of 3,5-dimethylpyrazole which was not reacted with the isocyanate group was 500 mol% with respect to the blocked isocyanate group. The results are shown in Table 2.

[Comparative Example 7]

The aqueous composition of Comparative Example 7 was obtained by the same operation as in Example 6 except that the aqueous composition of Comparative Example 3 was used instead of the aqueous composition of Example 1. The results are shown in Table 2. The content of dipropylene glycol monomethyl ether which is reactive with the isocyanate group is 50 mol% relative to the blocked isocyanate group.

[Comparative Example 8]

The aqueous composition of Comparative Example 8 was obtained by the same operation as in Example 6 except that the aqueous composition of Comparative Example 4 was used instead of the aqueous composition of Example 1. Will result Shown in Table 2. The content of 3,5-dimethylpyrazole which was not reacted with the isocyanate group was 50 mol% with respect to the blocked isocyanate group. The results are shown in Table 2.

*1: The content of the amine compound (which is not reacted with isocyanate groups) relative to the blocked isocyanate group of 100 moles (% by mole)

*1-1: Concentration of DIPA which is not reacted with isocyanate groups with respect to blocked isocyanate groups (% by mole)

*1-2: Concentration of DPM which is not reacted with isocyanate groups with respect to blocked isocyanate groups (% by mole)

Pz: 3,5-dimethylpyrazole

DIPA: diisopropylamine

DPM: dipropylene glycol monomethyl ether

External emulsifier: dialkyl (hydrogenated tallow) dimethyl ammonium chloride, and polyoxyethylene polyoxypropylene block polymer

*2: Relative to the total amount of the aqueous composition

This application is based on a Japanese patent application (Japanese Patent Application No. 2012-277141) filed on Dec. 19, 2012 with the Japan Patent Office, and Japanese Patent Application (Japanese Patent Application) filed on Dec. 19, 2012, to the Japan Patent Office. The content of the Japanese Patent Application No. 2012-277133, the entire contents of which is incorporated herein by reference.

[Industrial availability]

The aqueous composition of the present invention has industrial applicability as a fiber treatment composition of natural fibers, regenerated fibers, semi-synthetic fibers, synthetic fibers, inorganic fibers, composite fibers, blended fibers, and the like.

Claims (24)

An aqueous composition comprising an aqueous blocked polyisocyanate having a blocked isocyanate group blocked with an isocyanate group by a blocking agent and an isocyanate group having a hydrophilic group added thereto, and 10 of the blocked isocyanate group ~400 mol% of the amine compound, and water. The aqueous composition of claim 1, wherein the aqueous blocked polyisocyanate has an aliphatic diisocyanate monomer unit and/or an alicyclic diisocyanate monomer unit. The aqueous composition according to claim 1 or 2, wherein the content of the above amine compound is from 25 to 400 mol% based on the blocked isocyanate group. The aqueous composition according to any one of claims 1 to 3, wherein the average number of isocyanate groups of the above-mentioned aqueous blocked polyisocyanate precursor polyisocyanate is from 3.0 to 20. The aqueous composition according to any one of claims 1 to 4, wherein the average number of isocyanate groups of the above-mentioned aqueous blocked polyisocyanate precursor polyisocyanate is from 4.5 to 15. The aqueous composition according to any one of claims 1 to 5, wherein the above blocking agent comprises an amine compound. The aqueous composition of any one of claims 1 to 6, wherein the above blocking agent comprises a pyrazole. The aqueous composition according to any one of claims 1 to 7, wherein the hydrophilic group is a nonionic hydrophilic group and/or a cationic hydrophilic group. The aqueous composition of any one of claims 1 to 8, which further comprises a polymer having a perfluoro group. The aqueous composition of claim 9, wherein the content of the perfluoro group-containing polymer is from 1 to 30% by mass based on the total amount of the aqueous composition, and The content of the above aqueous blocking polyisocyanate is 0.05 to 10% by mass based on the total amount of the aqueous composition. The aqueous composition of claim 9 or 10, wherein the perfluoro group has a carbon number of 4 to 6. A fiber treatment composition comprising the aqueous composition of any one of claims 1 to 11. A fiber treated with the fiber treating agent composition of claim 12. A method for stabilizing an aqueous blocked polyisocyanate, which comprises an aqueous blocked polyisocyanate having a blocked isocyanate group blocked with an isocyanate group by a blocking agent and an isocyanate group having a hydrophilic group added thereto, water, The amine-based compound is mixed so that the amount of the amine-based compound added is 10 to 400 mol% based on the blocked isocyanate group. The method for stabilizing an aqueous blocked polyisocyanate according to claim 14, wherein the aqueous blocked polyisocyanate has an aliphatic diisocyanate monomer unit and/or an alicyclic diisocyanate monomer unit. The method for stabilizing an aqueous blocked polyisocyanate according to any one of claims 14 or 15, wherein the content of the above amine compound is from 25 to 400 mol% based on the blocked isocyanate group. The method for stabilizing an aqueous blocked polyisocyanate according to any one of claims 14 to 16, wherein the average number of isocyanate groups of the above-mentioned aqueous blocked polyisocyanate precursor polyisocyanate is from 3.0 to 20. The method for stabilizing an aqueous blocked polyisocyanate according to any one of claims 14 to 17, wherein the average number of isocyanate groups of the above-mentioned aqueous blocked polyisocyanate precursor polyisocyanate is from 4.5 to 15. The method for stabilizing an aqueous blocked polyisocyanate according to any one of claims 14 to 18, wherein the above blocking agent comprises an amine compound. The method for stabilizing an aqueous blocked polyisocyanate according to any one of claims 14 to 19, wherein the above blocking agent comprises a pyrazole. The method for stabilizing an aqueous blocked polyisocyanate according to any one of claims 14 to 20, wherein the hydrophilic group is a nonionic hydrophilic group and/or a cationic hydrophilic group. The method for stabilizing an aqueous blocked polyisocyanate according to any one of claims 14 to 21, which further comprises a polymer having a perfluoro group. The method for stabilizing an aqueous blocked polyisocyanate according to claim 22, wherein the content of the perfluoro group-containing polymer is from 1 to 30% by mass based on the total amount of the aqueous composition, and the aqueous blocked polyisocyanate The content is 0.05 to 10% by mass based on the total amount of the above aqueous composition. The method for stabilizing an aqueous blocked polyisocyanate according to claim 22 or 23, wherein the perfluoro group has a carbon number of 4 to 6.