JP7239158B2 - Water-repellent agent, method for producing water-repellent treated fiber base material, water-repellent textile article, water-repellent textile article with coating film, and method for producing water-repellent textile article with coating film - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water repellent agent, a method for treating a fiber substrate, a method for producing a water repellent treated fiber substrate, a textile article, and a method for producing a textile article.

In order to impart water repellency to the fibers, a hydrocarbon compound, a silicone compound, a fluorine compound, a chlorine compound, or the like may be oriented on the fiber surface to lower the surface tension of the fiber surface than that of water. Well known. Among these, fluorine-based compounds have been widely used as water-repellent components that can impart high water repellency to fibers. The development of water repellents that do not contain PFOA and further that do not contain fluorine compounds (fluorine-free water repellents) is underway.

As an example of a fluorine-free water repellent, Patent Document 1 below describes a water repellent made of a specific non-fluorine-based polymer containing a (meth)acrylic acid ester having 12 or more carbon atoms in the ester moiety as a monomer unit. Proposed. Further, in Patent Document 2, a structural unit derived from a (meth)acrylic acid ester monomer having 12 or more carbon atoms in the ester portion, and at least one monomer selected from vinyl chloride and vinylidene chloride Polymers containing structural units derived from

In addition to water repellency, the fabric treated with a water repellent agent has at least one or more performance improvements such as fluff prevention, batting prevention, windproof, waterproof, moisture permeable and waterproof, water resistance, and high water pressure resistance. A coating film may be provided on at least part of the fabric (especially at least one side) for the purpose of When the coating liquid is applied to form a coating film on the back side), the coating liquid permeates the opposite side (surface side) of the fabric, and the coating film is also formed on the surface side of the fabric, resulting in the appearance of the article. There is a problem of impairing the quality (through-out). In addition, the water repellent agent that does not contain a fluorine-based compound as in Patent Document 1 has the problem of impairing the appearance quality as described above, and the adhesion between the fabric treated with the water repellent agent and the coating film is insufficient. , and there is a problem that the coating film is easily peeled off.

Copolymerization of a (meth)acrylic acid ester monomer having 12 or more carbon atoms in the ester portion and at least one of vinyl chloride and vinylidene chloride as a water repellent agent having excellent peel strength during coating. (Patent Document 2) has been proposed, but the peel strength when an actual coating film is provided has not been evaluated. Also, there is no mention of backflow.

Also, a water repellent composition containing a non-fluorinated polymer and a hydrophobic compound has been proposed (Patent Document 3), but the peel strength when an actual coating film is provided has not been evaluated. Also, there is no mention of backflow.

In addition, a copolymer in which vinyl chloride is polymerized in the presence of a polymer mainly composed of long-chain alkyl acrylate (Patent Documents 4 and 5) has been proposed. no. Rather, there is a description that the peel strength decreases.

As described above, at present, no water repellent has been realized that provides sufficient peel strength, sufficient strike-through resistance, and sufficient water repellency.

JP 2006-328624 A JP 2017-025440 A JP 2017-222827 A JP 2017-165872 A JP 2017-165873 A

The present invention imparts excellent water repellency to fibers, and furthermore, when a coating film is formed on a fiber base material (such as a fabric) after water repellent treatment, the coating liquid is applied to the opposite side of the coated surface. The main object of the present invention is to provide a water repellent agent that suppresses the deterioration of the appearance quality due to permeation, can obtain a fiber base material that suppresses peeling of the coating film, and does not contain a fluorine compound and has a low environmental load. aim. Another object of the present invention is to provide a method for treating a fiber base material using the water repellent agent, a method for producing a water repellent treated fiber base material, a textile article, and a method for producing a textile article.

The present inventors have made extensive studies to solve the above problems. As a result, the proportion of polymer (I) is 0 to 55 parts by mass and the proportion of specific polymer (II) is is 10 to 85 parts by mass, and the water repellent does not contain a fluorine-containing component. The inventors have found that a fiber base material can be obtained in which deterioration of the appearance quality due to permeation of the coating liquid to the opposite side of the coated surface is suppressed and peeling of the coating film is suppressed. The present invention has been completed through further studies based on these findings.

［一般式（１）中、Ｒ¹¹は水素原子、メチル基、又は塩素原子であり、Ｒ¹²は炭素数１６～３０の直鎖状または分岐状の脂肪族炭化水素基である。］
＜重合体（ＩＩ）＞
下記一般式（２）で表される、ビニル単量体（ＩＩａ）の少なくとも１種から誘導された繰り返し単位を有する重合体。

［一般式（２）中、Ｒ²¹は水素原子、メチル基または塩素原子であり、Ｒ²²は塩素原子、または置換もしくは無置換の、フェニル基、またはシクロヘキシル基であり、１つ以上のフッ素ではないハロゲン原子または炭素数１～１０のアルキル基で置換されていてもよい。］
＜成分（ＩＩＩ）＞
下記一般式（３）で表されるアルコール（ＩＩＩａ）とイソシアネート化合物（ＩＩＩｂ）とを含む組成物、及び、上記アルコール（ＩＩＩａ）とイソシアネート化合物（ＩＩＩｂ）との反応生成物の少なくとも一方である。

［一般式（３）中、ｎ³¹は３～８の整数であり、ｎ³¹－ｎ³²はｎ³¹からｎ³²を引いた値を表し、１～７の整数であり、ｎ³²は１～７の整数であり、Ｒ³¹は炭素数１６～３２の直鎖状または分岐状の脂肪族炭化水素基、または炭素数１５～３１の直鎖状または分岐状の脂肪族炭化水素基を有するアシル基であり、Ａは３～６価の炭素数６以下の多価アルコールから水酸基を除いた残基、３～６価の炭素数６以下の多価アルコールの２～４量体から水酸基を除いた残基、単糖または二糖から水酸基を除いた残基、および５～６価の多価アルコールの分子内脱水環化物から水酸基を除いた残基からなる群より選択される少なくとも１種である。］
項２． 前記アルコール（ＩＩＩａ）のｎ³²が、２以上である、項１に記載の撥水剤。
項３． 前記イソシアネート化合物（ＩＩＩｂ）が、ブロックイソシアネートである、項１または２に記載の撥水剤。
項４． 前記重合体（ＩＩ）が、単独重合体のガラス転移点が６０℃以下のエチレン性不飽和単量体（ＩＩｂ）から誘導された繰り返し単位をさらに有する、項１～３のいずれか１項に記載の撥水剤。
項５． 前記重合体（Ｉ）が、水酸基、エポキシ基、アセトアセチル基、カルボニル基、クロロメチル基、アミド基、Ｎ－アルコキシメチルアミド基、ブロックドイソシアネート基、オキサゾリン基、カルボキシル基、アミノ基、スルホン酸基、アルコキシシリル基からなる群より選ばれる少なくとも１種を有する架橋性のエチレン性不飽和単量体（Ｉｂ）から誘導された繰り返し単位をさらに有する、項１～４のいずれか１項に記載の撥水剤。
項６． 前記重合体（Ｉ）が、下記一般式（４）で表される、オルガノポリシロキサン骨格を有するモノエチレン性不飽和単量体（Ｉｃ）から誘導された繰り返し単位をさらに有する、項１～５のいずれか１項に記載の撥水剤。

［一般式（４）中、Ｘはエチレン性不飽和基と炭素数１～１０のアルキレン基とを有する基であり、Ｙは一般式（４）で表されるシリコーン鎖またはＲ⁴¹であり、Ｒ⁴¹は互いに同一でも異なっていてもよい炭素数が１～３２であるアルキル基又はアリール基であり、ｎ⁴¹は０～２００の整数であり、式中にｎ⁴¹が複数存在する場合、ｎ⁴¹は互いに同一でも異なっていてもよく、合計が２００を超えない。]
項７． 前記重合体（Ｉ）が、ポリオキシエチレン基を有するモノエチレン性不飽和単量体（Ｉｄ）から誘導された繰り返し単位をさらに有する、項１～６のいずれか１項に記載の撥水剤。
項８． 水を含む液状媒体と界面活性剤をさらに含む、項１～７のいずれか１項に記載の撥水剤。
項９． 少なくとも前記重合体（Ｉ）を含む第１剤と、少なくとも前記重合体（ＩＩ）を含む第２剤と、少なくとも前記成分（ＩＩＩ）を含む第３剤とを備える撥水剤を調製するためのキットであって、前記重合体（Ｉ）と前記成分（ＩＩＩ）との合計１００質量部に対して、前記重合体（Ｉ）の割合が０～５５質量部、前記重合体（ＩＩ）の割合が１０～８５質量部であり、フッ素を含有する成分を含まない、キット。
項１０． 項１～８のいずれか１項に記載の撥水剤または項９に記載のキットで繊維基材を処理する、繊維基材の処理方法。
項１１． 項１～８のいずれか１項に記載の撥水剤または項９に記載のキットを繊維基材に適用することを含む、撥水処理された繊維基材の製造方法。
項１２． 項１～８のいずれか１項に記載の撥水剤または項９に記載のキットによって処理されてなる、繊維物品。
項１３． 繊維物品の少なくとも一方面に、項１～８のいずれかに記載の撥水剤または項９に記載のキットによって処理された撥水処理面を有し、前記繊維物品の一方面がさらにコーティング膜を有する、繊維物品。
項１４． 繊維物品の少なくとも一方面を、項１～８のいずれかに記載の撥水剤または項９に記載のキットによって処理して撥水処理面を形成し、前記繊維物品の一方面がさらにコーティング膜を形成する、繊維物品の製造方法。 That is, the present invention has the following aspects.
Section 1. The ratio of the polymer (I) is 0 to 55 parts by mass, and the ratio of the polymer (II) below is 10 to 85 parts by mass, based on the total 100 parts by mass of the polymer (I) and the component (III) below. department,
A water repellent that does not contain a fluorine-containing component.
<Polymer (I)>
A polymer having a repeating unit derived from at least one monoethylenically unsaturated carboxylic acid ester monomer (Ia) represented by the following general formula (1).

[In general formula (1), R ¹¹ is a hydrogen atom, a methyl group, or a chlorine atom, and R ¹² is a linear or branched aliphatic hydrocarbon group having 16 to 30 carbon atoms. ]
<Polymer (II)>
A polymer having a repeating unit derived from at least one vinyl monomer (IIa) represented by the following general formula (2).

[In general formula (2), R ²¹ is a hydrogen atom, a methyl group or a chlorine atom; R ²² is a chlorine atom, a substituted or unsubstituted phenyl group, or a cyclohexyl group; may be substituted with a non-halogen atom or an alkyl group having 1 to 10 carbon atoms. ]
<Component (III)>
At least one of a composition containing an alcohol (IIIa) represented by the following general formula (3) and an isocyanate compound (IIIb), and a reaction product of the alcohol (IIIa) and the isocyanate compound (IIIb).

[In the general formula (3), n ³¹ is an integer of 3 to 8, n ³¹ −n ³² represents a value obtained by subtracting n ³² from n ³¹ , an integer of 1 to 7, and n ³² is 1 to an integer of 7, and R ³¹ is a linear or branched aliphatic hydrocarbon group having 16 to 32 carbon atoms, or an acyl having a linear or branched aliphatic hydrocarbon group having 15 to 31 carbon atoms A is a residue obtained by removing a hydroxyl group from a tri- to hexavalent polyhydric alcohol having 6 or less carbon atoms, and removing a hydroxyl group from a dimer to tetramer of a tri- to hexavalent polyhydric alcohol having 6 or less carbon atoms. at least one selected from the group consisting of a residue, a residue obtained by removing a hydroxyl group from a monosaccharide or a disaccharide, and a residue obtained by removing a hydroxyl group from an intramolecular dehydration product of a 5- to 6-hydric polyhydric alcohol. be. ]
Section 2. Item 2. The water repellent agent according to Item 1, wherein n ³² of the alcohol (IIIa) is 2 or more.
Item 3. Item 3. The water repellent agent according to Item 1 or 2, wherein the isocyanate compound (IIIb) is a blocked isocyanate.
Section 4. 4. Any one of items 1 to 3, wherein the polymer (II) further has a repeating unit derived from an ethylenically unsaturated monomer (IIb) having a homopolymer glass transition point of 60° C. or less. Water repellent as described.
Item 5. The polymer (I) contains a hydroxyl group, an epoxy group, an acetoacetyl group, a carbonyl group, a chloromethyl group, an amide group, an N-alkoxymethylamide group, a blocked isocyanate group, an oxazoline group, a carboxyl group, an amino group, and a sulfonic acid group. 5. Any one of items 1 to 4, further comprising a repeating unit derived from a crosslinkable ethylenically unsaturated monomer (Ib) having at least one selected from the group consisting of a group consisting of an alkoxysilyl group. water repellent.
Item 6. Items 1 to 5, wherein the polymer (I) further has a repeating unit derived from a monoethylenically unsaturated monomer (Ic) having an organopolysiloxane skeleton represented by the following general formula (4): The water repellent agent according to any one of the above.

[In the general formula (4), X is a group having an ethylenically unsaturated group and an alkylene group having 1 to 10 carbon atoms, Y is a silicone chain represented by the general formula (4) or R ⁴¹ , R ⁴¹ is an alkyl group or an aryl group having 1 to 32 carbon atoms which ^{may be the same or different; n 41 is} an integer of 0 to 200; ⁴¹ may be the same or different from each other and the total does not exceed 200. ]
Item 7. 7. The water repellent agent according to any one of items 1 to 6, wherein the polymer (I) further has a repeating unit derived from a monoethylenically unsaturated monomer (Id) having a polyoxyethylene group. .
Item 8. Item 8. The water repellent agent according to any one of Items 1 to 7, further comprising a liquid medium containing water and a surfactant.
Item 9. For preparing a water repellent agent comprising a first agent containing at least the polymer (I), a second agent containing at least the polymer (II), and a third agent containing at least the component (III) A kit, wherein the proportion of the polymer (I) is 0 to 55 parts by mass and the proportion of the polymer (II) is 100 parts by mass in total of the polymer (I) and the component (III) is 10 to 85 parts by mass and does not contain a fluorine-containing component.
Item 10. A method for treating a fiber substrate, comprising treating the fiber substrate with the water repellent agent according to any one of Items 1 to 8 or the kit according to Item 9.
Item 11. A method for producing a water-repellent-treated textile substrate, comprising applying the water repellent agent according to any one of Items 1 to 8 or the kit according to Item 9 to a textile substrate.
Item 12. A textile article treated with the water repellent agent according to any one of Items 1 to 8 or the kit according to Item 9.
Item 13. At least one surface of a textile article has a water repellent surface treated with the water repellent agent according to any one of Items 1 to 8 or the kit according to Item 9, and one surface of the textile article further has a coating film. A textile article.
Item 14. At least one surface of a textile article is treated with the water repellent agent according to any one of Items 1 to 8 or the kit according to Item 9 to form a water repellent treated surface, and one surface of the textile article is further coated with a coating film. A method for manufacturing a textile article, which forms a

According to the present invention, excellent water repellency is imparted to the fiber, and further, when a coating film is formed on the fiber base material after the water repellent treatment, the coating liquid does not penetrate to the opposite side of the coated surface. It is possible to obtain a fiber base material in which the deterioration of the derived appearance quality is suppressed and the peeling of the coating film is suppressed, and to provide a water repellent agent that does not contain a fluorine compound and has a low environmental load. Further, according to the present invention, it is possible to provide a method for treating a fiber base material using the water repellent agent, a method for producing a water-repellent treated fiber base material, a textile article, and a method for producing a textile article.

In the present specification, the fact that the water repellent does not contain a fluorine-containing component means that the content of fluorine atoms is below the detection limit when the water repellent is subjected to fluorine analysis (combustion-ion chromatography). (50 ppm or less).

As used herein, emulsifying and dispersing means emulsifying or dispersing in a medium.

As used herein, emulsified dispersion means an emulsion or dispersion in a medium.

As used herein, "(meth)acrylate" means "acrylate or methacrylate", and the same applies to other similar expressions.

In the present specification, the glass transition point of the homopolymer is obtained from the literature (Polymer Handbook Third Edition, published in 1990 by John Wiley & Sons) or the database PolyInfo (National Institute for Materials Science) provided by the independent administrative agency. http://polymer.nims.go.jp), and for monomers for which the glass transition point of the homopolymer is not described in the literature or database, a homopolymer is synthesized (by GPC The weight average molecular weight is in the range of 10,000 to 1,000,000), and the value measured by a differential scanning calorimeter (DSC) is adopted.

(Water repellent agent)
The water repellent agent of the present invention has a ratio of 0 to 55 parts by mass of the polymer (I) with respect to a total of 100 parts by mass of the polymer (I) described later and the component (III) described later. It is characterized in that the ratio of coalescence (II) is 10 to 85 parts by mass and that it does not contain a fluorine-containing component. By having such a specific composition, the water repellent agent of the present invention can impart excellent water repellency to fibers. Furthermore, the deterioration of the appearance quality due to the penetration of the coating liquid to the opposite side of the coated surface of the fiber base material (fabric etc.) after the water repellent treatment using the water repellent agent of the present invention is suppressed, and the coating film is improved. A fiber base material in which peeling is suppressed can be obtained. Moreover, since the water repellent agent of the present invention does not contain a fluorine-based compound, it has a low environmental impact.

<Polymer (I)>
The polymer (I) has a repeating unit derived from the monomer (Ia), and if necessary, the monomer (Ib), the monomer (Ic) described later, the monomer (Id ), a monomer (Ie) described later, a monomer (If) described later, a monomer (Ig) described later, and a monomer (Ih) described later. It is a polymer having repeating units. Moreover, the polymer (I) may have residues of a polymerization initiator and a molecular weight modifier, which will be described later, in the polymer.

[Monomer (Ia)]
Monomer (Ia) is a monoethylenically unsaturated carboxylic acid ester monomer represented by the following general formula (1). The monomer (Ia) constituting the polymer (I) may be of one type or two or more types.

In general formula (1), R ¹¹ is a hydrogen atom, a methyl group or a chlorine atom, and R ¹² is a linear or branched aliphatic hydrocarbon group having 16-30 carbon atoms.

In the monomer (Ia), R ¹¹ may be a hydrogen atom, a methyl group, or a chlorine atom. From the viewpoint of water repellency, a hydrogen atom or a chlorine atom (that is, is an acrylate ester monomer or an α-chloroacrylate ester monomer). Further, from the viewpoint of the texture of the fiber after treatment, a hydrogen atom or a methyl group (that is, the monomer (Ia) is a (meth)acrylate ester monomer) is preferable. As the monomer (1a), it is preferable to use both an acrylate ester monomer and a methacrylate ester monomer.

In the monomer (Ia), R ¹² is a linear or branched aliphatic hydrocarbon group having 16 to 30 carbon atoms, preferably a linear aliphatic hydrocarbon group having 16 to 30 carbon atoms. It is a hydrogen group. Further, the number of carbon atoms is more preferably 18-30. The aliphatic hydrocarbon group may be saturated or unsaturated, but is preferably a saturated aliphatic hydrocarbon group.

Preferred specific examples of the monomer (Ia) include cetyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, icosyl (meth)acrylate, henicosyl (meth)acrylate, behenyl (meth)acrylate, tetracosyl (meth)acrylate, hexacosyl (meth)acrylate, triacontyl (meth)acrylate, cetyl α-chloroacrylate, heptadecyl α-chloroacrylate, stearyl α-chloroacrylate, nonadecyl α-chloroacrylate, icosyl-α-chloroacrylate, henicosyl-α Chloroacrylate, behenyl α-chloroacrylate, tetracosyl α-chloroacrylate, hexacosyl α-chloroacrylate, triacontyl α-chloroacrylate and the like.

[Monomer (Ib)]
Monomer (Ib) is a monomer having a crosslinkable functional group. When the polymer (I) contains a structural unit derived from the monomer (Ib), the monomer (Ib) constituting the polymer (I) may be one type, or two or more types. There may be. Examples of crosslinkable functional groups include hydroxyl group, epoxy group, acetoacetyl group, carbonyl group, chloromethyl group, amino group (primary or secondary amino group), amide group, N-alkoxymethylamide group, blocked isocyanate. group, oxazoline group, carboxyl group, sulfonic acid group, alkoxysilyl group, hydroxyl group, epoxy group, acetoacetyl group, carbonyl group, chloromethyl group, primary or secondary amino group, amide group, N- Alkoxymethylamide groups and blocked isocyanate groups are preferred, and hydroxyl groups, epoxy groups, acetoacetyl groups, N-alkoxymethylamide groups and blocked isocyanate groups are particularly preferred.

(Meth)acrylates, acrylamides, vinyl ethers, or vinyl esters are preferred as the monomer (Ib).

Since the polymer (I) has a structural unit derived from the monomer (Ib), the adhesion between the water repellent agent and the fiber is improved, and the detachment of the water repellent agent during washing is preferably suppressed. .

Preferred specific examples of the monomer (Ib) include polycaprolactones of hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and hydroxyethyl (meth)acrylate. ester, glycerol (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, 2-acetoacetoxyethyl (meth)acrylate, diacetone (meth)acrylamide, monochlorovinyl acetate, N-methylol (Meth)acrylamide, N-butoxymethyl (meth)acrylamide, 3,5-dimethylpyrazole adduct of 2-isocyanatoethyl (meth)acrylate, 3,5-dimethylpyrazole adduct of 3-isocyanatopropyl (meth)acrylate phenylglycidylethylacrylate tolylene diisocyanate, 3-(methylethylketoxime)isocyanatomethyl-3,5,5-trimethylcyclohexyl (2-hydroxyethyl methacrylate) cyanate, tert-butylaminoethyl (meth)acrylate, etc. be done.

[Monomer Ic]
Monomer (Ic) is a monoethylenically unsaturated monomer (Ic) having an organopolysiloxane skeleton represented by the following general formula (4). When the polymer (I) contains a structural unit derived from the monomer (Ic), the monomer (Ic) constituting the polymer (I) may be one type, or two or more types. There may be.

In the general formula (4), X is a group having an ethylenically unsaturated group and an alkylene group having 1 to 10 carbon atoms, and the ethylenically unsaturated group includes a vinyl group, a styryl group, (meth)acryloyloxy and the like, and from the viewpoint of ease of copolymerization, ease of synthesis, and availability of commercial products, a (meth)acryloyloxy group is preferable, and the alkylene group has 1 to 10 carbon atoms. There is no particular limitation if any.

In general formula (4), Y is the silicone chain shown in general formula (4) or R ⁴¹ . R ⁴¹ is an alkyl group or aryl group having 1 to 32 carbon atoms which may be the same or different, preferably an alkyl group or aryl group having 1 to 6 carbon atoms, a methyl group or an aralkyl group; is more preferable. Also, n ⁴¹ is an integer of 0-200, preferably an integer of 0-100. When multiple n ⁴¹ are present in general formula (4) (that is, when multiple types of repeating units represented by —Si(R ⁴¹ ) ₂ O— are included), n ⁴¹ may be the same or different. well, the total does not exceed 200.

Examples of preferable products of the monomer (Ic) include X-22-174ASX, X-22-174BX, KF-2012, X-22-2426, X-22-2404 and JNC stock manufactured by Shin-Etsu Chemical Co., Ltd. Silaplane FM-0711, Silaplane FM-0721, Silaplane FM-0725, Silaplane TM-0701T and the like manufactured by the company.

[Monomer (Id)]
Monomer (Id) is a monoethylenically unsaturated monomer (Id) having a polyoxyethylene group. When the polymer (I) contains a structural unit derived from the monomer (Id), the monomer (Id) constituting the polymer (I) may be one type, or two or more types. There may be. The monomer (Id) may have a (poly)oxyalkylene group consisting of an alkylene group having 3 to 10 carbon atoms in addition to the polyoxyethylene group.

Specific products of the monomer (Id) include Latemul PD-420, Latemul PD-430 and Latemul PD-450 manufactured by Kao Corporation, and Uniox PKA-5001 and Uniox PKA-5002 manufactured by NOF Corporation. , Uniox PKA-5003, Uniox PKA-5004, Uniox PKA-5005, Uniox PKA-5006, Uniox PKA-5007, Uniox PKA-5008, Uniox PKA-5009, Uniox PKA-5010, Unisafe PKA-5011, Unisafe PKA-5012, Unilube PKA-5013, Unisafe PKA-5015, Unisafe PKA-5016, Unisafe PKA-5017, Blenmer PE-90, Blenmer PE-200, Blenmer PE-350, Blenmer 50PEP-300, Blenmer 70PEP-350B, Blenmer 55PET-800, Blenmer AE-90U, Blenmer AE-200, Blenmer AE-400, Blenmer PME-100, Blenmer PME-200, Blenmer PME-400, Blenmer PME-1000, Blenmer PME-4000, Blenmer 50POEP-800B, Blenmer PLE-200, Blenmer PLE-1300, Blenmer PSE-1300, Blenmer 43PAPE-600B, Blenmer AME-400, Blenmer ALE-200, Blenmer 75ANEP-600, Blenmer AAE-300, Adeka manufactured by ADEKA Co., Ltd. Riasap ER-10, Adekaria Soap ER-20, Adekaria Soap ER-30, Adekaria Soap NE-10, Adekaria Soap NE-20, Adekaria Soap NE-30, Aqualon manufactured by Daiichi Kogyo Seiyaku Co., Ltd. RN-20, Aqualon RN-2025, Aqualon RN-30, Aqualon RN-50, Antox LMA-10, Antox LMA-20, Antox LMA-27 manufactured by Nippon Nyukazai Co., Ltd., and the like.

[Monomer (Ie)]
The monomer (Ie) is the same monomer as the monomer (IIa) described later, and the details are as described later. When the polymer (I) contains a structural unit derived from the monomer (Ie), the monomer (Ie) constituting the polymer (I) may be one type, or two or more types. There may be.

[Monomer (If)]
Monomer (If) is a monoethylenically unsaturated monomer (If) having only aliphatic hydrocarbon groups of 1 to 15 carbon atoms in the side chain. When the polymer (I) contains a structural unit derived from the monomer (If), the monomer (If) constituting the polymer (I) may be one type, or two or more types. There may be.

As the monomer (If), a monoethylenically unsaturated monomer having a linear or branched aliphatic hydrocarbon group in the side chain, a monoethylenic monomer having a cyclic aliphatic hydrocarbon group in the side chain and ( Meth)acrylates are particularly preferred.

Specific examples of monoethylenically unsaturated monomers having a linear or branched aliphatic hydrocarbon group in the side chain include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, methyl α-chloroacrylate, ethyl α-chloroacrylate, propyl α-chloroacrylate, butyl α-chloroacrylate, hexyl alpha-chloroacrylate, octyl-alpha-chloroacrylate, decyl-alpha-chloroacrylate, dodecyl-alpha-chloroacrylate and the like.

Further, specific examples of monoethylenically unsaturated monomers having a cyclic aliphatic hydrocarbon group in the side chain include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, di Cyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyladamantyl (meth)acrylate, 2-ethyladamantyl (meth)acrylate, tricyclopentanyl (meth)acrylate, cyclohexyl α-chloroacrylate, tert-butylcyclohexyl α-chloroacrylate, isobornyl α-chloroacrylate, dicyclopentenyl α-chloroacrylate, dicyclopentanyl α-chloroacrylate, adamantyl α-chloroacrylate, 2-methyladamantyl α-chloroacrylate, 2-ethyladamantyl α-chloroacrylate Chloroacrylate, tricyclopentanyl α-chloroacrylate, benzyl (meth)acrylate, phenyl (meth)acrylate and the like.

[Monomer (Ig)]
Monomer (Ig) is a monoethylenically unsaturated monomer whose side chain contains at least one O, N atom, different from monomer (Ib). When the polymer (I) contains a structural unit derived from the monomer (Ig), the monomer (Ig) constituting the polymer (I) may be one type, or two or more types. There may be.

Specific examples of the monomer (Ig) include dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminomethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, Diethylaminopropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, vinyl acetate, vinyl propionate, acryloylmorpholine and the like.

[Monomer (Ih)]
Monomer (Ih) is another monomer different from monomers (Ia) to (Ig).
When the polymer (I) contains a structural unit derived from the monomer (Ih), the monomer (Ih) constituting the polymer (I) may be one type, or two or more types. There may be. As the monomer (Ih), for example, a monomer having two or more ethylenically unsaturated groups may be used.

Monomers (Ih) are, for example, ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate and hexamethylene. Bifunctional (meth)acrylates such as reaction products of diisocyanate are included.

The proportion of the monomer (Ia) in the polymer (I) is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 100% by mass, based on 100% by mass of the polymer (I). % by mass or less, 95% by mass or less, 90% by mass or less, 85% by mass or less, and 80% by mass or less.

Further, when the polymer (I) contains a structural unit derived from at least one of the monomers (Ib) to (Ih), the monomer (Ia) per 100 parts by mass of the monomer The ratio of (Ib) is, for example, 0 to 30 parts by weight, preferably 0.5 to 6 parts by weight, and the ratio of monomer (Ic) is, for example, 0 to 100 parts by weight, preferably 1 to 50 parts by weight. The proportion of the monomer (Id) is, for example, 0 to 100 parts by mass, preferably 0.5 to 10 parts by weight, and the proportion of the monomer (Ie) is, for example, 0 to 80 parts by mass, preferably is 1 to 30 parts by mass, the proportion of the monomer (If) is, for example, 0 to 50 parts by mass, preferably 1 to 30 parts by mass, and the proportion of the monomer (Ig) is, for example, 0 to 12 parts by mass. parts by mass, preferably 1 to 10 parts by mass, and the proportion of the monomer (Ih) is, for example, 0 to 12 parts by mass, preferably 1 to 10 parts by mass.

The weight average molecular weight (Mw) of polymer (I) is preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 100,000 or more. If it is more than these lower limits, the water repellency by a water-repellent agent can be improved suitably. The upper limit of the weight average molecular weight (Mw) of the polymer (I) is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less, and particularly preferably 300,000 or less. . When the content is at most these upper limits, the film-forming properties can be improved when the water repellent is applied to the fiber base material. The number average molecular weight (Mn) of polymer (I) is preferably 10,000 or more, more preferably 20,000 or more, and particularly preferably 25,000 or more. If it is more than these lower limits, the water repellency by a water-repellent agent can be improved suitably. Although the upper limit of the number average molecular weight (Mn) is not particularly limited, it is preferably 200,000 or less, more preferably 100,000 or less, and particularly preferably 80,000 or less. When the content is at most these upper limits, the film-forming properties can be improved when the water repellent is applied to the fiber base material. Polymer (I) preferably satisfies at least one of the weight average molecular weight (Mw) range and the number average molecular weight (Mn) range, more preferably both.

<Polymer (II)>
Polymer (II) has a repeating unit derived from monomer (IIa), and optionally monomer (IIb), monomer (IIc), monomer (IId), monomer It is a polymer having repeating units derived from at least one or more selected from the group consisting of polymer (IIe) and monomer (IIf). Moreover, the polymer (II) may have residues of a polymerization initiator and a molecular weight modifier, which will be described later, in the polymer.

[Monomer (IIa)]
The monomer (IIa) is a vinyl monomer having at least one of a halogen atom other than a fluorine atom and an optionally substituted aromatic group represented by the following general formula (2). The monomer (IIa) constituting the polymer (II) may be of one type or two or more types.

In general formula (2), R ²¹ is a hydrogen atom, a methyl group or a chlorine atom. R ²² is a chlorine atom, a substituted or unsubstituted phenyl group, or a cyclohexyl group, which may be substituted with one or more non-fluorine halogen atoms or C 1-10 alkyl groups. Substituents include, for example, non-fluorine halogen atoms or non-fluorine halogenated methyl groups.

Preferred specific examples of the monomer (IIa) include styrene, methylstyrene, dimethylstyrene, ethylstyrene, tert-butylstyrene, chlorostyrene, chloromethylstyrene, chloroethylene, 1,1-dichloroethylene and the like, especially Chlorostyrene, chloromethylstyrene, chloroethylene, 1,1-dichloroethylene and the like are preferred.

[Monomer (IIb)]
The monomer (IIb) is a monomer other than the monomer (IIc), the monomer (IId), the monomer (IIe), and the monomer (IIf) described below, and is a homopolymer glass. It is an ethylenically unsaturated monomer having a transition point of 60° C. or less. The monomer (IIb) is not a monomer (IIc), a monomer (IId), a monomer (IIe), or a monomer (IIf) described later, but a homopolymer having a glass transition point of 60°C. Although there is no particular limitation as long as it is below, from the viewpoint of copolymerization with the monomer (IIa), (meth)acrylates, acrylamides, conjugated dienes, vinyl ethers, or vinyl esters are preferable. ) Acrylates and conjugated dienes are particularly preferred.

The monomer (IIb) is not a monomer (IIc), a monomer (IId), a monomer (IIe), or a monomer (IIf) described later, but a homopolymer having a glass transition point of 60°C. Although it is not particularly limited as long as it is below, the upper limit of the above glass transition point is , preferably 40° C. or lower, more preferably 30° C. or lower, particularly preferably 20° C. or lower.

Examples of the monomer (IIb) include (meth)acrylates having a linear or branched aliphatic hydrocarbon group in the side chain, conjugated dienes having a linear or branched aliphatic hydrocarbon group, (Meth)acrylates whose side chains contain at least one of O and N atoms. The number of carbon atoms is not particularly limited as long as the homopolymer has a glass transition point of 60° C. or lower.

Preferred specific examples of monomer (IIb) include methyl acrylate, ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, 2-octyldodecyl (meth) ) acrylate, 2-decyltetradecyl (meth)acrylate, butadiene, isoprene, piperylene, dimethylaminomethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminomethyl (meth)acrylate, Diethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, vinyl acetate, vinyl propionate and the like.

[monomer (IIc)]
Monomer (IIc) is a monomer having a crosslinkable functional group. The monomer (IIc) is the same monomer as the monomer (Ib) described above, and the details are as described above. When the polymer (II) contains a structural unit derived from the monomer (IIc), the monomer (IIc) constituting the polymer (II) may be one kind, or two or more kinds. There may be.

[monomer (IId)]
Monomer (IId) is a monoethylenically unsaturated monomer having an organopolysiloxane skeleton represented by the general formula (4). The monomer (IId) is the same monomer as the monomer (Ic) described above, and the details are as described above. When the polymer (II) contains structural units derived from the monomer (IId), the monomer (IId) constituting the polymer (II) may be of one type, or two or more types. There may be.

[monomer (IIe)]
Monomer (IIe) is a monoethylenically unsaturated monomer having a polyoxyethylene group. The monomer (IIe) is the same monomer as the monomer (Id) described above, and the details are as described above. When the polymer (II) contains a structural unit derived from the monomer (IIe), the monomer (IIe) constituting the polymer (II) may be one type, or two or more types. There may be.

[monomer (IIf)]
Monomer (IIf) is a monoethylenically unsaturated monomer having a cyclic aliphatic hydrocarbon group in its side chain. The details are as described above for the monomer (If).
When the polymer (II) contains structural units derived from the monomer (IIf), the monomer (IIf) constituting the polymer (II) may be one kind, or two or more kinds. There may be.

[Monomer (IIg)]
Monomer (IIg) is another monomer different from monomers (IIa) to (IIf). When the polymer (II) contains a structural unit derived from the monomer (IIg), the monomer (IIg) constituting the polymer (II) may be one kind, or two or more kinds. There may be.

The proportion of monomer (IIa) in polymer (II) is preferably 30% by mass or more, more preferably 40% by mass or more, and preferably 100% by mass, based on 100% by mass of polymer (II). % or less, 95 mass % or less, 90 mass % or less, 85 mass % or less, and 80 mass % or less.

Further, when the polymer (II) contains a structural unit derived from at least one of the monomers (IIb) to (IIg), the monomer (IIa) per 100 parts by weight of the monomer The ratio of (IIb) is, for example, 0 to 150 parts by weight, preferably 10 to 120 parts by weight, and the ratio of monomer (IIc) is, for example, 0 to 30 parts by weight, preferably 0.5 to 6 parts by weight. The proportion of the monomer (IId) is, for example, 0 to 10 parts by mass, preferably 0.5 to 6 parts by weight, and the proportion of the monomer (IIe) is, for example, 0 to 100 parts by mass, preferably is 0.5 to 10 parts by mass, the proportion of the monomer (IIf) is, for example, 0 to 50 parts by mass, preferably 1 to 30 parts by mass, and the proportion of the monomer (IIg) is, for example, 0 to 12 parts by mass, preferably 1 to 10 parts by mass.

The weight average molecular weight (Mw) of polymer (II) is preferably 1,000 or more, more preferably 5,000 or more, and particularly preferably 10,000 or more. If it is more than these lower limits, the water repellency by a water-repellent agent can be improved suitably. The upper limit of the weight average molecular weight (Mw) of the polymer (II) is not particularly limited, but is preferably 1,000,000 or less, more preferably 500,000 or less, and particularly preferably 300,000 or less. . When the content is at most these upper limits, the film-forming properties can be improved when the water repellent is applied to the fiber base material. The number average molecular weight (Mn) of polymer (III) is preferably 1,000 or more, more preferably 5,000 or more, and particularly preferably 25,000 or more. If it is at least these lower limits, the adhesion of the water repellent to the fibers can be enhanced. Although the upper limit of the number average molecular weight (Mn) is not particularly limited, it is preferably 200,000 or less, more preferably 100,000 or less, and particularly preferably 80,000 or less. When the content is at most these upper limits, the film-forming properties can be improved when the water repellent is applied to the fiber base material. The polymer (II) preferably satisfies at least one of the weight average molecular weight (Mw) range and the number average molecular weight (Mn) range, more preferably both.

<Component (III)>
Component (III) is a composition containing an alcohol (IIIa) represented by the following general formula (3) and an isocyanate compound (IIIb), and a reaction product of the alcohol (IIIa) and the isocyanate compound (IIIb). at least one. The isocyanate compound is a compound having at least one of an isocyanate group and a blocked isocyanate group. In addition, with regard to the reaction product of alcohol (IIIa) and isocyanate compound (IIIb), the reactive functional group on the isocyanate compound may react completely or partially with alcohol (IIIa). good. When partially reacted, the reaction product may have at least one of isocyanate groups and blocked isocyanate groups. Here, alcohol (IIIa) is involved in developing water repellency, and isocyanate compound (IIIb) reacts with alcohol (IIIa) and/or polymer (I) and/or polymer (II) and/or fiber. , is involved in improving the initial water repellency and washing durability of the water repellency.

Alcohol (IIIa) is a compound having a hydroxyl group represented by the following general formula (3). The alcohol (IIIa) constituting the component (III) may be of one type or two or more types.

In general formula (3), n ³¹ is an integer of 3-8. n ³¹ -n ³² represents a value obtained by subtracting n ³² from n ³¹ and is an integer of 1-7. n ³² is an integer of 1-7. R ³¹ is a linear or branched aliphatic hydrocarbon group having 16 to 32 carbon atoms or an acyl group having a linear or branched aliphatic hydrocarbon group having 15 to 31 carbon atoms. A is a residue obtained by removing a hydroxyl group from a tri- to hexavalent polyhydric alcohol having 6 or less carbon atoms, and a residue obtained by removing a hydroxyl group from a dimer to tetramer of a tri- to hexavalent polyhydric alcohol having 6 or less carbon atoms. , a residue obtained by removing a hydroxyl group from a monosaccharide or a disaccharide, and a residue obtained by removing a hydroxyl group from an intramolecular dehydration product of a pentahydric to hexavalent polyhydric alcohol.

In alcohol (IIIa), R ³¹ has a linear or branched aliphatic hydrocarbon group with 16 to 32 carbon atoms or a linear or branched aliphatic hydrocarbon group with 15 to 31 carbon atoms It is an acyl group, and the number of carbon atoms is preferably 16 to 22 for the aliphatic hydrocarbon group and 15 to 21 for the acyl group having the aliphatic hydrocarbon group, because of the availability of raw materials. , acyl groups are particularly preferred.

Examples of polyhydric alcohols that become residue A of alcohol (IIIa) include trihydric alcohols such as 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-hydroxymethyl-2-methyl-1,3-propanediol (trimethylolethane), 2-ethyl-2-hydroxymethyl-1,3-propanediol (trimethylolpropane), 3-hydroxyethyl-3-methyl -1,5-pentanediol (triethylolethane), 3-ethyl-3-hydroxyethyl-1,5-pentanediol (triethylolpropane), 2,2-bis(hydroxymethyl)- 1,3-propanediol (pentaerythritol) and the like, and trihydric or higher polyhydric alcohols other than the above include sugar alcohols such as glycerin, erythritol, threitol, arabinitol, xylitol, ribitol, iditol, allitol, and galactitol. , glucitol (sorbitol), mannitol, talitol, inositol, boremitol, perseitol and the like. Among others, glycerin, 2-ethyl-2-hydroxymethyl-1,3-propanediol, 3-ethyl-3-hydroxyethyl-1,5-pentanediol, 2,2-bis(hydroxymethyl)-1,3- Propanediol and erythritol are preferred.

Examples of multimers of polyhydric alcohols that become residue A of alcohol (IIIa) include di- to tetra-mers obtained by arbitrarily combining trihydric to hexahydric polyhydric alcohols described above. It is preferable that the hydric alcohols are the same. Among them, pentaerythritol dimer, trimethylolpropane dimer, glycerin dimer, glycerin trimer, and glycerin tetramer are preferable.

Examples of monosaccharides that become residue A of alcohol (IIIa) include glucose, fructose, galactose, mannose and ribose. Among them, glucose is preferred.

Examples of disaccharides that become residue A of alcohol (IIIa) include lactose, sucrose and maltose. Among them, sucrose is preferred

Examples of dehydrated cyclized polyhydric alcohols that become residue A of alcohol (IIIa) include 1,4-anhydrosorbitol, 1,5-anhydrosorbitol, 1,4,3, 6-dianhydrosorbitol can be mentioned. Among them, 1,4-anhydrosorbitol and 1,5-anhydrosorbitol are preferred.

Examples of alcohol (IIIa) include any combination of R ³¹ as described above and A as described above. Examples include esters of glycerin and long-chain fatty acids, pentaerythritol and long-chain fatty acids, trimethylolpropane dimers and long-chain fatty acid esters, pentaerythritol dimers and long-chain fatty acid esters, glycerin 4 and long-chain fatty acid esters, sucrose and long-chain fatty acid esters, and sorbitan and long-chain fatty acid esters. Glycerin tristearate, Tetraglycerin pentasterate, Sucrose tristearate, Sucrose tetrastearate, Sucrose pentastearate, Sucrose hexastearate, Sucrose heptasterate, Sucrose tribehenate, Sucrose tetrabehenate, Sucrose penta behenate, sucrose hexabehenate, sucrose heptabhenate, sorbitan dipalmitate, sorbitan tripalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan dioleate , sorbitan trioleate, sorbitan monobehenate, sorbitan dibehenate, sorbitan tribehenate, and the like. Among them, those in which n ³² is 2 or more are preferable.

[Isocyanate compound (IIIb)]
As the isocyanate compound (IIIb), known compounds can be used, and those having two or more isocyanate groups in one molecule are preferred. Examples of isocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. Examples of aliphatic polyisocyanates include 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4- trimethylhexamethylene diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc. Examples of alicyclic polyisocyanates include 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone diisocyanate), bis-(4-isocyanatocyclohexyl)methane (hydrogenated MDI), norbornane diisocyanate, etc. Examples of aromatic polyisocyanates include , 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, crude MDI, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 3,3′-dimethyl- 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate and the like. Examples of araliphatic polyisocyanates include 1 ,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate and the like, and reactions of these compounds, such as adduct type polyisocyanate and uretdiionization reaction , isocyanurate reaction, carbodiimidation reaction, uretonimimination reaction, isocyanate modification by biuret reaction, and mixtures thereof can be preferably used.

From the viewpoint of product stability, it is preferable to use a blocked isocyanate, and the blocked isocyanate in which 50 mol% or more of the isocyanate groups of the isocyanate compound is blocked with a blocking agent may be used singly or in combination of two or more. can be done. The blocked isocyanate can be prepared by reacting the above various isocyanate compounds with various known blocking agents.

The blocking agent is a compound having one or more active hydrogens in the molecule, and can be used singly or in combination of two or more. Examples include alcohol compounds, alkylphenol compounds, phenol compounds, Active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, imidazoline compounds, triazole compounds, carbamic acid compounds, urea compounds, oxime compounds, amine compounds, imide compounds compounds, imine compounds, pyrazole compounds, bisulfites, and the like. Among them, acid amide compounds, active methylene compounds, oxime compounds, and pyrazole compounds are preferred, such as ε-caprolactam, acetylacetone, diethyl malonate, methyl ethyl ketone oxime, cyclohexanone oxime, 3-methylpyrazole, and 3,5-dimethylpyrazole. can be preferably used.

The isocyanate compound (including blocked isocyanate) may have self-emulsifying properties. A nonionic hydrophilic group having an oxyethylene group can preferably be introduced from the viewpoint of water repellency. Examples of the hydrophilic compound that reacts with the isocyanate compound to impart self-emulsifying properties include polyoxyalkylenes such as polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol polypropylene glycol monomethyl ether, and polypropylene glycol polyethylene glycol monobutyl ether. Monoalkyl ethers; ethylene glycol or (poly)ethylene glycols such as diethylene glycol, triethylene glycol, and polyethylene glycol; block copolymers, random copolymers, and ethylene oxide of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol and propylene oxide, random copolymers and block copolymers of ethylene oxide and butylene oxide; polyoxyalkylene monoamines, polyoxyalkylene diamines; Used. The above nonionic hydrophilic compounds may be used singly or in combination of two or more. Self-emulsifiability can be imparted to the isocyanate compound by introducing about 1 to 50 mol % of these compounds relative to the isocyanate groups. The self-emulsifiable isocyanate compound having an isocyanate group is preferably added to the treatment bath immediately before the water-repellent treatment from the viewpoint of water stability.

The ratio of the alcohol (IIIa) and the isocyanate compound (IIIb) in the component (III) is preferably 20 to 90% by mass of the alcohol (IIIa) and 10 to 80% by mass of the isocyanate compound (IIIb). Alcohol (IIIa) is preferably 30 to 85% by mass, isocyanate compound (IIIb) is 15 to 70% by mass, more preferably alcohol (IIIa) is 40 to 80% by mass, and isocyanate compound (IIIb) is 20 to 60% by mass. , Particularly preferably, the alcohol (IIIa) is 55 to 80% by weight and the isocyanate compound (IIIb) is 20 to 45% by weight. When the alcohol (IIIa) is within the above range, sufficient water repellency can be obtained, and when the isocyanate compound (IIIb) is within the above range, excellent water repellency and washing durability can be obtained without impairing the water repellency. .

<Method for Producing Polymer (I), Emulsified Dispersion of Polymer (I)>
Polymer (I) of the present invention can be produced, for example, by the following method.
The monomer component (Ix) containing the monomer (Ia) is chain-polymerized in a medium in the presence of a surfactant, a polymerization initiator, and optionally a water-repellent aid to obtain a polymer A method of obtaining a solution of (I), an emulsified dispersion. The monomer component (Ix) may optionally include the monomer (Ib), the monomer (Ic), the monomer (Id), the monomer (Ie), the monomer ( If), the above monomer (Ig), and one or more selected from the group consisting of the above monomer (Ih). Examples of the polymerization method include an emulsion polymerization method, a dispersion polymerization method, a suspension polymerization method, and the like. Moreover, it may be batch polymerization, continuous polymerization, or multi-stage polymerization.

As a method for producing the polymer (I), in the presence of a surfactant and a polymerization initiator, the monomer component (Ix) is emulsion-polymerized in an aqueous medium to obtain an emulsified dispersion of the polymer (I). is preferred. From the viewpoint of improving the yield of the polymer (I), it is preferable to pre-emulsify a mixture consisting of a monomer, a surfactant, an aqueous medium and optionally a water repellent aid prior to emulsion polymerization. preferable. For example, a mixture comprising a monomer, a surfactant, an aqueous medium and optionally a water repellent aid is mixed, emulsified and dispersed using a homomixer or a high-pressure emulsifier.

The temperature at the time of mixing and emulsifying and dispersing is preferably at least the temperature at which all of the monomer, surfactant, aqueous medium, and optional water repellent auxiliary agent melt or soften.

The content ratio of each monomer in the monomer component (Ix) is the same as the content ratio of the constituent units based on the respective monomers described above, since almost no monomers remaining after polymerization are detected. A preferred embodiment is also the same.

<Method for Producing Polymer (II), Emulsified Dispersion of Polymer (II)>
Polymer (II) of the present invention can be produced, for example, by the following method. In the presence of a polymerization initiator and optionally an organic solvent, the monomer component (IIx) containing the monomer (IIa) is polymerized to obtain the polymer (II) or a solution of the polymer (II) , the polymer (II) obtained by the above method or a solution of the polymer (II), a surfactant to be added as necessary, water is added and mixed, and if necessary, an organic solvent and residual A method of obtaining an emulsified dispersion of polymer (II) by removing the monomer that The monomer component (IIx) may optionally include the monomer (IIb), the monomer (IIc), the monomer (IId), the monomer (IIe), the monomer ( IIf), and one or more selected from the group consisting of the monomers (IIg). For example, the polymer (II) obtained by polymerizing at least the monomer (IIa) and a monomer having a tertiary amino group among the monomers (IIb) is acid-neutralized. An emulsified dispersion of the polymer (II) may be obtained without using a surfactant by adding water to the polymer and mixing. Further, by using the monomer (IIe) instead of the monomer having a tertiary amino group and the neutralizing acid among the monomers (IIb) in the above example, the surfactant can be added in the same procedure. An emulsified dispersion of polymer (II) may be obtained without using it. In the presence of an emulsified dispersion of the polymer (II) obtained by the above method and a polymerization initiator, the monomer component (IIx) containing the monomer (IIa) is polymerized in a medium to obtain a polymer A method for obtaining the emulsified dispersion of (II). In this case, an emulsified dispersion containing two types of polymer (II) is obtained. Instead of the emulsified dispersion of polymer (II) obtained by the above method, a surfactant may be used to obtain an emulsified dispersion of polymer (II) by the same procedure. In that case, the polymerization method includes an emulsion polymerization method, a dispersion polymerization method, a suspension polymerization method, and the like. Moreover, it may be batch polymerization, continuous polymerization, or multi-stage polymerization.

As a method for producing the polymer (II), an emulsified dispersion obtained by neutralizing the polymer (II) described above with an acid, in the presence of a polymerization initiator, in a medium, after adding the monomer component (IIx) , to obtain an emulsified dispersion containing two types of polymers (II) by polymerization. Remaining monomers are preferably removed. From the viewpoint of improving the stability during production of the emulsified dispersion, at least a portion of the tertiary amino groups possessed by the emulsified dispersion obtained by acid-neutralizing the first polymer (II) is previously added before emulsion polymerization. Quaternization is preferred.

(Polymerization initiator for chain polymerization)
A polymerization initiator is used when polymerizing the monomer component (Ix) or the monomer component (IIx). Examples of polymerization initiators include thermal polymerization initiators, photopolymerization initiators, radiation polymerization initiators, radical polymerization initiators, ionic polymerization initiators, etc. Water-soluble or oil-soluble radical polymerization initiators are preferred. As the radical polymerization initiator, general-purpose initiators such as azo-based polymerization initiators, peroxide-based polymerization initiators and redox-based initiators are used depending on the polymerization temperature. As the radical polymerization initiator, an azo compound is particularly preferred, and a salt of an azo compound is more preferred when the polymerization is carried out in an aqueous medium. The polymerization temperature is preferably 20 to 150°C. The amount of the polymerization initiator to be added is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the monomer component (Ix).

(Molecular weight modifier for chain polymerization)
A molecular weight modifier may be used in the polymerization of the monomer component (Ix) or the monomer component (IIx). As the molecular weight modifier, aromatic compounds, mercapto alcohols, mercaptocarboxylic acids or mercaptans are preferable, and mercaptocarboxylic acids or alkylmercaptans are particularly preferable. Molecular weight modifiers include mercaptoethanol, mercaptopropionic acid, n-octylmercaptan, n-dodecylmercaptan, t-dodecylmercaptan, stearylmercaptan, α-methylstyrene dimer (CH ₂ =C(Ph)CH ₂ C(CH ₃ ) 2Ph, Ph is a phenyl group.) and the like. The amount of the molecular weight modifier to be added is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the monomer component (Ix).

(Water repellent aid)
Paraffin wax, microcrystalline wax, α-olefin wax, polyisobutylene, silicone oil, modified silicone oil, long-chain alkyl-modified silicone, long-chain alkyl/aralkyl-modified silicone, higher fatty acid amide-modified silicone, hydrophobic silica , a hydrophobic silicone resin, or the like can be used. These may be added in the process of producing an emulsified dispersion of one or more of polymer (I), polymer (II), and component (III), or an emulsified dispersion of water repellent aid alone may be produced. However, it may be blended with a water repellent agent.

<Component (III), method for producing emulsified dispersion of component (III)>
It may be produced by a known method, for example, a method of dispersing by adding water after mixing various components and a surfactant, or a method of mechanically dispersing using a known disperser or the like. A homomixer, a homogenizer, a colloid mill, a line mixer, a bead mill or the like can be used as the dispersing machine. In addition, a known organic solvent may be added when dispersing in an aqueous system.

The alcohol (IIIa) and the isocyanate compound (IIIb) may be an aqueous dispersion dispersed in water. The dispersion can be easily produced by mixing an aqueous dispersion of alcohol (IIIa) and an aqueous dispersion of isocyanate compound (IIIb). An aqueous dispersion of particles containing the alcohol (IIIa) and the isocyanate compound (IIIb) in one particle is prepared in a liquid containing the alcohol (IIIa), the isocyanate compound (IIIb), an organic solvent, and optionally a surfactant. can be produced by adding water to and mixing, and then removing the organic solvent.

The reaction product of alcohol (IIIa) and isocyanate compound (IIIb) is obtained by adding alcohol (IIIa) and unblocked or partially blocked isocyanate compound (IIIb) to an NCO content of 0%. It can be easily produced by reacting. The reaction product of the alcohol (IIIa) and the isocyanate compound (IIIb) may be an aqueous dispersion dispersed in water, and the reaction product of the alcohol (IIIa) and the isocyanate compound (IIIb) and an organic solvent In some cases, it can be produced by adding water to a liquid containing a surfactant, mixing it, and then removing the organic solvent.

<Method for producing water repellent agent>
The water repellent agent in the present invention contains 0 to 55 parts by mass of the polymer (I) with respect to the total 100 parts by mass of the polymer (I) and the component (III), ) is 10 to 85 parts by mass, and it can be produced by appropriately preparing a composition that does not contain a fluorine-containing component, but the form is preferably an emulsified dispersion.

When the water repellent in the present invention is an emulsified dispersion, the forms of polymer (I), polymer (II) and component (III) are not particularly limited.

For example, the emulsified dispersion may contain particles in which two or more of the group selected from polymer (I), polymer (II) and component (III) are present in the same particle. Such an emulsified dispersion can be produced, for example, by the following procedure.
(a) any one of polymer (I) and polymer (II) in an emulsified dispersion containing one selected from the group consisting of polymer (I), polymer (II) and component (III); Add the monomers that make up that component, or component (III). Said monomer or component (III) may optionally contain a vehicle or surfactant.
(a) polymerize the monomer added as necessary; Moreover, an organic solvent is removed as needed.

By obtaining an emulsified dispersion in this way, an emulsified dispersion containing particles in which two or more from the group selected from polymer (I), polymer (II) and component (III) are present in the same particle A water repellent agent consisting of a body is preferably obtained.

Further, the emulsified dispersion may contain particles composed of the polymer (I), particles composed of the polymer (II), and particles composed of the component (III). In this form, polymer (I), polymer (II) and component (v) are contained in separate particles, and three types of particles are present in the emulsified dispersion. Such an emulsified dispersion is suitably obtained, for example, by mixing an emulsified dispersion of polymer (I), an emulsified dispersion of polymer (II), and an emulsified dispersion of component (III).

In the present invention, the polymer (I), the polymer (II) and the component (III) are prepared as a 2- or 3-liquid type kit, each of which is dispersed in water at the time of use, and the water repellent agent of the present invention is added as an aqueous dispersion. It may be in the form of a kit for preparation. Furthermore, the polymer (I), the polymer (II), the alcohol (IIIa) and the isocyanate compound (IIIb) are made into a 2- to 4-liquid kit, each of which is dispersed in water at the time of use to form an aqueous dispersion of the repellent of the present invention. It may be in the form of a kit for preparing a liquid medicine. Each of the 2- to 4-liquid type kits of the present invention is used for preparing the aforementioned water repellent agent of the present invention. Therefore, the polymer (I), the polymer (II), the component (III), and the types and contents of other components are the same as those of the water repellent agent of the present invention.

In the case of using the kit of the present invention, the water repellent agent of the present invention is prepared in advance from the kit of the present invention, and then the water repellent agent (more specifically, the water repellent agent is applied to the fiber base material with water). A diluted working fluid) may be applied to treat the textile substrate with a water repellent agent, or the polymer (I), polymer (II), and component (III) constituting the kit of the present invention may be , in any order to the fibrous substrate (that is, the kit of the present invention is applied to the fibrous substrate) to prepare the water repellent from the kit in the presence of the fibrous substrate. In the latter method, along with treatment of the fiber base material with the kit of the present invention, preparation of the water repellent agent of the present invention using the kit of the present invention and further treatment of the fiber base material with the water repellent agent of the present invention are performed. will be

The water repellent agent of the present invention may contain a liquid medium. Examples of liquid media include water, alcohols, glycols, glycol ethers, glycol esters, halogen compounds, hydrocarbons, ketones, esters, ethers, nitrogen compounds, sulfur compounds, inorganic solvents, and organic acids. An aqueous medium is preferred, and water is particularly preferred, from the viewpoint of load reduction and ease of handling. An aqueous medium means water, a water-soluble organic solvent, and a mixed medium thereof. As the water-soluble organic solvent, one or more water-soluble organic solvents selected from the group consisting of water-soluble monoalcohols, water-soluble glycols, water-soluble glycol ethers and water-soluble glycol esters are preferred.

The content of the liquid medium in the water repellent agent of the present invention is, for example, 30 to 99.9% by mass, preferably 50 to 99% by mass, more preferably 55 to 95% by mass. In the present invention, when polymer (I), polymer (II), and component (III) are prepared as an emulsified dispersion, even if the liquid medium contained in the emulsified dispersion is included in the water repellent, Alternatively, a liquid medium may be added separately as a water repellent. As will be described later, when applying the water repellent agent of the present invention to an object to be treated such as fibers, the amount of the liquid medium can be adjusted (for example, diluted with water) to obtain a working liquid.

The water repellent agent of the present invention may contain a surfactant. Surfactants are not particularly limited, and for example, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymer surfactants and the like can be used. These surfactants may be used alone or in combination of two or more. It is particularly preferable to use only a cationic surfactant, only a nonionic surfactant, or a combination of a cationic surfactant and a nonionic surfactant in treating textile articles with the aqueous emulsified dispersion.

Examples of anionic surfactants include various fatty acid salts, alkylbenzenesulfonates, alkanesulfonates, alkylsulfuric acid ester salts, alkylphosphoric acid ester salts, polyoxyethylene alkyl ether sulfates, and polyoxyethylene-substituted phenyl ether sulfates. , polycarboxylates, etc., and counterions include, but are not limited to, sodium, potassium, calcium, ammonium, triethanolamine, and the like.

Examples of nonionic surfactants include nonionic surfactants not having (poly)oxyethylene groups and nonionic surfactants having (poly)oxyethylene groups. Examples of nonionic surfactants having no (poly)oxyethylene group include sorbitan fatty acid esters, fatty acid glycerides, and sucrose fatty acid esters. Examples of nonionic surfactants having a (poly)oxyethylene group include poly Oxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxyalkylene alkyl ether such as polyoxyethylene polyoxybutylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene alkenyl ether, poly Polyoxyethylene polyoxyalkylene alkenyl ethers such as oxyethylene polyoxybutylene alkenyl ether, polyoxyethylene fatty acid esters, fatty acid alkanolamides, pluronic active agents and the like can be used, but are not limited to these.

Examples of cationic surfactants include quaternary salts such as various alkyltrimethylammonium salts, alkyldimethylbenzylammonium salts, dialkyldimethylammonium salts, alkylpyridinium chloride salts, and quaternized polyoxyethylenealkylamines. Amine salts such as alkylamine salts, alkyldimethylamine salts, polyoxyethylenealkylamine salts and the like obtained by neutralizing amines with a suitable acid can be used. Counter ions include, but are not limited to, chloride ion, bromide ion, sulfate ion, formate ion, acetate ion, methyl sulfate ion, ethyl sulfate ion, and the like.

Examples of amphoteric surfactants include alkylamine oxides, alanines, imidazolinium betaines, amidobetaines, and betaine acetate. Specific examples include long-chain amine oxides, laurylbetaine, stearylbetaine, Laurylcarboxymethylhydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, fatty acid amidopropyldimethylaminoacetic acid betaine, etc., but not limited thereto.

The ratio of the surfactant to the solid content (components other than the liquid medium) of the water repellent agent of the present invention is not particularly limited, but is, for example, 0 to 20% by mass, preferably 0 to 10% by mass, more preferably 2%. ~8% by mass.

The water repellent agent of the present invention may further contain additives as required. Additives include cross-linking agents, film-forming aids, texture modifiers (softeners and hard finishing agents), slip modifiers (slip improvers, anti-slip agents), wear resistance improvers, tear strength improvers, Antistatic agents, flame retardants, fragrances, antifoaming agents, viscosity adjusters (thickeners and reducers), pH adjusters, stabilizers (ultraviolet absorbers, antioxidants, discoloration inhibitors, antifungal agents, antiseptic agents, anti-algae agents, antibacterial agents, bactericides, antifreeze agents). Additives contained in the water repellent agent of the present invention may be of one type, or may be of two or more types.

The solid content concentration of the water repellent agent of the present invention is not particularly limited, and is, for example, 3 to 80% by mass, preferably 10 to 60% by mass, more preferably 15 to 50% by mass.

(water repellent treatment)
Using the water repellent agent of the present invention, a fiber base material (such as a fabric made of fibers) can be subjected to water repellent treatment by a known method. Examples of treatment methods include continuous methods and batch methods.

As a continuous method, first, the water repellent agent of the present invention is diluted with water to prepare a working liquid. When preparing the working liquid, it is preferable to optionally add various agents such as a cross-linking agent in addition to water. Next, the object to be treated (fiber base material) is continuously fed into the impregnation device filled with the working liquid, and after impregnating the object to be treated with the working liquid, unnecessary working liquid is removed. The impregnation device is not particularly limited, and a padder, a kiss roll type applicator, a gravure coater type applicator, a spray type applicator, a foam type applicator, a coating type applicator and the like can be preferably employed, and a padder type applicator is particularly preferred. Subsequently, an operation of removing water remaining on the object to be processed is performed using a dryer. The dryer is not particularly limited, and a spreading dryer such as a hot flue or a tenter is preferable. The continuous method is preferably employed when the object to be treated is a fabric such as a woven fabric.

The batch method comprises a step of immersing an object to be treated in a working liquid and a step of removing water remaining on the treated object. The batch method is preferably used when the material to be treated is not in the form of fabric, such as loose hair, top, sliver, skein, tow, yarn, etc., or when the continuous method is not suitable for knitting. In the step of immersion, for example, a cotton dyeing machine, a cheese dyeing machine, a jet dyeing machine, an industrial washing machine, a beam dyeing machine, or the like can be used. In the operation of removing water, a warm air dryer such as a cheese dryer, a beam dryer, a tumble dryer, a high frequency dryer, or the like can be used. It is preferable to perform a dry heat treatment on the object to be treated to which the water repellent agent of the present invention is adhered. The temperature of the dry heat treatment is preferably 120 to 180°C, more preferably 160 to 180°C. The dry heat treatment time is preferably 10 seconds to 3 minutes, particularly preferably 1 to 2 minutes. The dry heat treatment method is not particularly limited, but a tenter is preferable when the object to be treated is in the form of fabric. It is believed that in the heat treatment step, the blocking agent of the blocked isocyanate is thermally dissociated, and the regenerated isocyanate group reacts with the water repellent agent or fiber and bonds.

(Fibrous article with coating film)
The textile article of the present invention has a water-repellent surface treated with the water repellent agent on at least one surface, and may be a textile article with a coating film provided with a coating film on one surface. Examples thereof include a fabric having a water-repellent surface on one side and a coating film on the other non-water-repellent surface, and clothing articles obtained by using the fabric. Moreover, both surfaces of the fabric may be water-repellent treated surfaces, and a fabric having a coating film on one of the water-repellent treated surfaces, or a clothing article obtained by using the fabric may be used. The textile article of the present invention is particularly preferably a textile article having water-repellent treated surfaces on both sides of the treated textile article and the coating film on one of the water-repellent treated surfaces. The coating film includes a microporous polyurethane resin film, a nonporous polyurethane resin thin film, an acrylic resin film, and the like, and may or may not have moisture permeation and waterproofness.

Further, in the present invention, at least one surface of a textile article is treated with the water repellent agent to form a water repellent treated surface, and then one surface of the textile article is coated with a coating liquid containing a material for a moisture-permeable and waterproof film. A method for manufacturing a textile article by coating to form a coating film. According to this method, a textile article having a water-repellent surface and a coating film is obtained. Specifically, for example, one surface of a textile article is treated for water repellency and then a coating film is formed on the non-water repellent surface; A textile article having a water-repellent surface and a coating film is manufactured by a method of forming a coating film on the other surface. In particular, a method of forming water-repellent treated surfaces on both sides of a textile article and then forming a coating film on one of the water-repellent treated surfaces is preferred. As the coating film, a microporous polyurethane resin film and a nonporous polyurethane resin film are preferable.

(coating liquid)
The coating liquid contains a coating film material and a solvent, and if necessary, a filler, a cross-linking agent, a pigment, a viscosity modifier, and the like. The resin used to form the coating film is not particularly limited, but examples include polyester copolymer-based, polyether copolymer-based, or polycarbonate copolymer-based polyurethane resins, silicones, fluorine, amino acids, and the like. Polyurethane resins, acrylic resins, synthetic rubbers, vinyl resins such as polyvinyl chloride, and the like can be preferably used.
In the present invention, a conventionally known polyurethane resin obtained by reacting a polyisocyanate component and a polyol component is preferred because it is easy to process. As the polyisocyanate component, an aromatic diisocyanate, an aliphatic diisocyanate, an alicyclic diisocyanate, or the like may be used singly or in combination. Specifically, tolylene-2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexane diisocyanate, 1,4-cyclohexane diisocyanate, etc., are used as main components, and if necessary, trifunctional or higher poly Isocyanates may also be used. Polyether polyol, polyester polyol, etc. are used as the polyol component. As the polyether polyol, polyethylene glycol, polypropylene glycol, polytetraethylene glycol and the like are used. As the polyester polyol, a reaction product of a diol such as ethylene glycol or propylene glycol and a dibasic acid such as adipic acid or sebacic acid, or a ring-opening polymer such as caprolactone can be used. Alternatively, a polymer of its prepolymer can also be used.

As a solvent for the coating liquid, in addition to toluene and methyl ethyl ketone, polar organic solvents are preferably used. phosphonamide and the like. Auxiliaries such as water repellents and cross-linking agents may be added to the coating resin solution.

The coating liquid may be an emulsified dispersion containing a coating resin and water, and preferably contains a viscosity modifier (especially a thickener). A hydrophilic or emulsified filler, cross-linking agent, or pigment may be included as necessary. Examples of the emulsified dispersion containing the coating resin and water include conventionally known aqueous polyurethane resins and aqueous acrylic resins. functional groups (especially tertiary or quaternary amino groups or carboxyl groups) are preferably introduced.

The coating film can be formed, for example, by applying a coating liquid to one surface of a fiber base material, which is a fabric, then allowing it to stand for a predetermined period of time, then immersing it in water for a predetermined period of time to remove the solvent, and then drying it. . Alternatively, the coating film can also be formed, for example, by applying a coating liquid to one surface of the fiber base material, which is a fabric, and then drying it. The former method is preferable when the coating film is a moisture-permeable waterproof film. As the coating method, various coating methods such as knife coating, knife over roll coating and reverse roll coating can be used.

The water repellent agent of the present invention is suitably used for imparting water repellency to a fiber substrate (preferably a fabric made of fibers). More specifically, it is particularly suitable as a water repellent agent for coating, in which a fiber base material is treated with a water repellent agent and then subjected to the coating treatment. The water repellent agent of the present invention can impart excellent water repellency to fibers, further suppress deterioration of appearance quality due to permeation of the coating liquid to the opposite side of the coated surface, and It is possible to obtain a fiber base material in which peeling of is suppressed. Moreover, the water repellent agent of the present invention can provide a water repellent agent that does not contain a fluorine-based compound and has a low environmental impact.

The water repellent agent of the present invention can impart water repellency to a wide range of natural fibers such as cotton, silk, linen and wool, and synthetic fibers such as polyester, nylon, acrylic and spandex. There are no particular restrictions on the form and shape of the fiber, and it is not limited to raw material forms such as staples, filaments, tows, threads, etc., and fibers in various processed forms such as woven fabrics, knitted fabrics, wadding, non-woven fabrics, paper, sheets, films, etc. Substrates, and textile articles such as clothes obtained by processing the fiber substrates are objects that can be treated with the water repellent agent of the present invention.

The method for treating a fiber base material of the present invention is a method of treating a fiber base material with the water repellent agent of the present invention. The details of the method are as described above.

In addition, the method for producing a water-repellent-treated fiber substrate of the present invention includes applying the water-repellent agent of the present invention to a fiber substrate. The details of the method of applying the agent to the fiber substrate are as described above.

The textile article of the present invention is a textile article treated with the water repellent agent of the present invention. be. Further, the textile article of the present invention has a water-repellent surface treated with the water repellent agent of the present invention on at least one surface of the textile article, and one surface of the textile article further has a coating film. may The details of the coating film are also as described above. The textile article of the present invention provided with a coating film is processed by treating at least one surface of the fiber with the water repellent agent of the present invention to form a water repellent treated surface, and one surface of the textile article is further formed with a coating film. can be manufactured by

The present invention will be described in detail below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Abbreviations in each table are as follows.
[Abbreviation]
STA: stearyl acrylate BeA: behenyl acrylate GMA: glycidyl methacrylate AAEM: acetoacetoxyethyl methacrylate HEMA: 2-hydroxyethyl methacrylate MS1: one-end methacryl-modified silicone with a functional group equivalent weight of 420 g/mol (manufactured by Shin-Etsu Chemical Co., Ltd., X-22 -2404)
MS2: One-end methacryl-modified silicone with a functional group equivalent weight of 4600 g/mol (manufactured by Shin-Etsu Chemical Co., Ltd., KF-2012)
BMA: butyl methacrylate STMAC: stearyltrimethylammonium chloride PEO-9: polyoxyethylene oleyl ether (ethylene oxide average 9 mol adduct)
PEO-13: polyoxyethylene oleyl ether (ethylene oxide average 13 mol adduct)
DPG: dipropylene glycol nDoSH: n-dodecylmercaptan VA-086: 2,2′-azobis[2-methyl-N-(2-hydroxyethyl)propionamide] (VA-086, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
St: styrene DMAEMA: dimethylaminoethyl methacrylate, glass transition point of homopolymer 19°C
IPA: isopropanol AIBN: azobisisobutyronitrile ECH: epichlorohydrin VC: vinyl chloride EA: ethyl acrylate, homopolymer glass transition point -40°C
V-50: 2,2′-azobis(2-methylpropionamidine) dihydrochloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-50)
TGPS: Tetraglycerin pentastearate (Sakamoto Yakuhin Kogyo Co., Ltd., SY Glister PS-3S)
STS: Sorbitan tristearate (manufactured by Kao Corporation, Emsol S-30V, hydroxyl value 68.6 mgKOH/g)
SMS: Sorbitan monostearate (manufactured by Kao Corporation, Rhedol SP-10V, hydroxyl value 247.5 mgKOH/g)
HBR-P: Biuret form of hexamethylene diisocyanate completely blocked by 3,5-dimethylpyrazole PEOSA-30: Stearylamine ethylene oxide average 30 mol adduct AcOH: Acetic acid (90 wt% aqueous solution)
MIBK: methyl isobutyl ketone

[Synthesis of emulsified dispersion containing polymer (I)]
[Emulsified Dispersion I-1]
117.6 g of STA, 2.4 g of GMA, 1.2 g of STMAC, 3.0 g of PEO-9, 3.0 g of PEO-13, 20 g of DPG and 225 g of deionized water are placed in a 500 mL flask, The mixture was emulsified and dispersed by high-speed stirring at 60° C. to obtain a mixed liquid. Then, while maintaining the temperature at 40° C., the mixture was treated at 40 MPa using a high-pressure homogenizer to obtain an emulsion. The resulting emulsion was transferred to a 500 mL flask, the gas phase was replaced with nitrogen, and the temperature was raised to 80° C. while stirring. 0.16 g of nDoSH was added, and after 5 minutes, 0.44 g of VA-086 was added, and the polymerization reaction was carried out at 80°C for 15 hours while stirring in a nitrogen atmosphere, and cooled to 40°C or lower. The solid content was adjusted with ion-exchanged water to obtain an emulsified dispersion I-1 containing the polymer (I) with a solid content concentration of 30% by mass.

[Emulsified dispersions I-2 to I-12]
Emulsified dispersions (I-2) to (I-12) containing polymer (I) were obtained in the same manner as in Example I-1, except that the amount of each raw material charged was changed to the amount shown in Table 1. . Table 2 shows the ratio (mass ratio) of the monomers constituting the polymer (I).

[Synthesis of emulsified dispersion II-1 containing polymer (II)]
A 500 mL flask was charged with 75 g of St, 15.8 g of DMAEMA, and 25 g of IPA, and after nitrogen substitution, the temperature was raised to 85°C. 1.0 g of AIBN was added while stirring under a nitrogen atmosphere, and the polymerization reaction was carried out at 85° C. for 6 hours. Next, 7.3 g of 90% acetic acid and 250 g of ion-exchanged water were sequentially added while stirring, and then IPA was distilled off under reduced pressure. Then, 9.2 g of ECH was added and reacted at 80° C. for 2 hours. The obtained emulsified dispersion was transferred to an autoclave, and after adding 220 g of ion-exchanged water, the autoclave was replaced with nitrogen. After raising the temperature to 60° C. while stirring under a nitrogen atmosphere, 50 g of VC, 50 g of EA and 2.4 g of V-50 were added in order, and the polymerization reaction was carried out until the internal pressure reached 0 MPa. The monomers remaining after the polymerization were distilled off under reduced pressure, and then cooled to 40° C. or lower. The solid content was adjusted with ion-exchanged water to obtain an emulsified dispersion II-1 containing the polymer (II) having a solid content concentration of 25% by mass.

[Synthesis of emulsified dispersion containing component (III)]
[Emulsified Dispersion III-1]
25.2 g of HBR-P, 71.0 g of STS and 40 g of MIBK were added to a 1 L flask and melted at 60.degree. 4.0 g of PEOSA-30 and 1.3 g of AcOH were dissolved in 256 g of deionized water at 60° C. and added dropwise. The mixture was emulsified with a high-pressure homogenizer (400 bar) while maintaining the temperature. After that, MIBK was distilled off under reduced pressure, and ion-exchanged water was added to obtain an emulsified dispersion III-1 containing component (III) having a solid concentration of 25% by mass.

[Emulsified dispersions III-2 to III-3]
Emulsified dispersions III-2 to III-3 containing component (III) were obtained in the same manner as for emulsified dispersion III-1, except that the amount of each raw material charged was changed to the amount shown in Table 3.

<Preparation of working fluid>
After preparing the emulsified dispersion of the polymer (I) obtained above, the emulsified dispersion of the polymer (II), and the emulsified dispersion of the component (III) as a kit, the mass shown in Tables 5 to 7, respectively Each emulsified dispersion was mixed so as to obtain a water repellent agent, and the water repellent agent was further diluted with the amount of water shown in Tables 5 to 7 to prepare a working liquid.

The following various tests were performed using each working fluid obtained in Examples and Comparative Examples. The results are shown in Tables 5-7.

[Fibrous base material]
Polyester taffeta cloth 1 (basis weight: 60 g/m ² , yarn used: 56 dtex (50 d))
Nylon taffeta cloth 1 (basis weight: 57.5 g/m ² , yarn used: 44 dtex (40 d))
Nylon taffeta cloth 2 (basis weight: 61.4 g/m ² , yarn used: 44 dtex (40 d))

[Conditions for processing with a water-repellent agent]
In a continuous method, each of the above-mentioned fiber base materials is passed through each processing liquid (a water repellent agent diluted with water so as to have the composition shown in Table 1), and the unnecessary solution is removed by mangle at a constant pressure. was squeezed out, dried at 110°C for 1.5 minutes, and cured at 170°C for 1 minute. The pickup was 30% polyester taffeta cloth 1, 42% nylon taffeta cloth 1, and 52% nylon taffeta cloth 2. As shown in Table 1, depending on the conditions, a cross-linking agent (Meikanate PRO: blocked isocyanate, manufactured by Meisei Chemical Industry Co., Ltd., solid content 20%) was used in combination.

[Preparation of coating liquid]
Preparation of coating liquid 1: 170 g of DMF solution of polyurethane resin 1, 8.5 g of white pigment, 2.55 g of cross-linking agent and 73 g of DMF were mixed to obtain coating liquid 1.

Preparation of coating liquid 2: 50 g of urethane prepolymer (product name: Rezamin CU-4700, manufactured by Dainichiseika Kogyo Co., Ltd., polyethylene adipate/MDI prepolymer), cross-linking agent (product name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.) 0.5 g of, 1.0 g of coloring agent (product name: Seika Seven ALT # 8000, manufactured by Dainichiseika Kogyo Co., Ltd.), and 25 g of N,N-dimethylformamide (DMF) are mixed to form a moisture-permeable waterproof membrane. A coating liquid 2 was obtained for forming.

[Coating conditions]
(Coating liquids 1 and 2)
Using a baker applicator (coating thickness 0 to 254 μm), coating speed: 0.4 m / sec, coating liquid temperature 25 ° C. so that the thickness after drying is 100 μm, with a water repellent A coating liquid was applied to the back surface of the processed fiber base material. After the coated fiber substrate was allowed to stand for 30 or 45 seconds, it was immersed in water at 20°C for 2 minutes, then immersed in water at 40°C for 2 minutes, dried at 110°C for 60 seconds, and further dried at 150°C for 60 seconds. It was dried for a second and aged at 80° C. overnight to obtain a test cloth with a coating film. The test cloth was subjected to the following evaluations of visual strike-through resistance, strike-through resistance, peel strength, and water repellency (initial water repellency and durable water repellency).

[Visual strike-through resistance]
After forming the coating film, the degree of permeation of the coating liquid to the surface of the test cloth on which the coating film was not formed was visually evaluated. Evaluation was performed according to the following criteria, and when the performance was slightly inferior, the grade was given "-".
O: No permeation of the coating liquid is observed.
Δ: Slight permeation of the coating liquid is observed throughout.
x: Penetration of the coating liquid is clearly observed throughout.

[Strike-through resistance]
Using a color difference meter (Konica Minolta, CR310), before forming the coating film, measure the brightness of the surface of the test cloth on the side where the coating film is not formed, and after forming the coating film, the coating film is formed. The lightness of the surface of the test cloth on the non-treated side was measured and the difference between them (ΔL) was determined.

[Peel strength]
A heat-sealing tape was attached to the coating film of the test cloth by a hot press. Using a Tensilon universal tester (AGS-X, manufactured by Shimadzu Corporation), the force (peel strength) applied when a 2.5 cm tape was peeled off was measured. The measurement was performed three times in total, and the average value of the peel strength was obtained. A higher peel strength indicates that the coating film formed by the coating liquid is less likely to be peeled off.

[Water repellency]
The water repellency (initial water repellency) of the fiber substrate before forming the coating film was evaluated according to JIS L 1092:2009, 7.2 Water repellency test (spray test). Evaluation was carried out according to the following criteria, and a grade of "+" was given when the performance was slightly good, and a grade of "-" was given when the performance was slightly poor.
5: No wetting or adhesion of water droplets on the surface 4: No wetting of the surface but showing adhesion of small droplets 3: Wetting on the surface of small individual droplets 2: Wetting on half of the surface , with small individual wetting penetrating the fabric 1: Wetting over the entire surface

[Evaluation of washing durability of water repellency]
After the initial water repellency evaluation, the fiber substrate was washed 10 times according to the washing method described in JIS L 1092 (2009), then tumble dried at 80 ° C. for 40 minutes, and similarly water repellent (durable water repellent). evaluated.

As is clear from the results shown in Tables 5 to 7, the water repellents of Examples 1 to 23 were added to 100 parts by mass of polymer (I) and component (III). The proportion is 0 to 55 parts by mass, the proportion of polymer (II) is 10 to 85 parts by mass, and the water repellent does not contain a fluorine-containing component. The water repellent agents of Examples 1 to 23 impart excellent water repellency to fibers, further suppress the deterioration of the appearance quality due to the penetration of the coating liquid to the opposite side of the coated surface, and the coating film It can be seen that the peeling of is suppressed. Moreover, since the water repellents of Examples 1 to 23 do not contain a fluorine-based compound, the environmental load is low.

Claims (14)

The ratio of the polymer (I) is 0 to 55 parts by mass, and the ratio of the polymer (II) below is 10 to 85 parts by mass, based on the total 100 parts by mass of the polymer (I) and the component (III) below. department,
A water repellent that does not contain a fluorine-containing component.
<Polymer (I)>
A polymer having a repeating unit derived from at least one monoethylenically unsaturated carboxylic acid ester monomer (Ia) represented by the following general formula (1).

[In general formula (1), R ¹¹ is a hydrogen atom, a methyl group, or a chlorine atom, and R ¹² is a linear or branched aliphatic hydrocarbon group having 16 to 30 carbon atoms. ]
<Polymer (II)>
A polymer having a repeating unit derived from at least one vinyl monomer (IIa) represented by the following general formula (2), wherein the vinyl monomer (IIa) in the polymer (II) ) is 30% by mass or more and 100% by mass or less based on 100% by mass of the polymer (II) .

[In general formula (2), R ²¹ is a hydrogen atom, a methyl group or a chlorine atom; R ²² is a chlorine atom or a substituted or unsubstituted phenyl group; It may be substituted with up to 10 alkyl groups. ]
<Component (III)>
At least one of a composition containing an alcohol (IIIa) represented by the following general formula (3) and an isocyanate compound (IIIb), and a reaction product of the alcohol (IIIa) and the isocyanate compound (IIIb).

[In the general formula (3), n ³¹ is an integer of 3 to 8, n ³¹ −n ³² represents a value obtained by subtracting n ³² from n ³¹ , an integer of 1 to 7, and n ³² is 1 to an integer of 7, and R ³¹ is a linear or branched aliphatic hydrocarbon group having 16 to 32 carbon atoms, or an acyl having a linear or branched aliphatic hydrocarbon group having 15 to 31 carbon atoms A is a residue obtained by removing a hydroxyl group from a tri- to hexavalent polyhydric alcohol having 6 or less carbon atoms, and removing a hydroxyl group from a dimer to tetramer of a tri- to hexavalent polyhydric alcohol having 6 or less carbon atoms. at least one selected from the group consisting of a residue, a residue obtained by removing a hydroxyl group from a monosaccharide or a disaccharide, and a residue obtained by removing a hydroxyl group from an intramolecular dehydration product of a 5- to 6-hydric polyhydric alcohol. be. ] 2. The water repellent according to claim 1, wherein ⁿ³² of said alcohol (IIIa) is 2 or more. The water repellent according to claim 1 or 2, wherein the isocyanate compound (IIIb) is a blocked isocyanate. 4. Any one of claims 1 to 3, wherein the polymer (II) further has a repeating unit derived from an ethylenically unsaturated monomer (IIb) whose homopolymer glass transition point is 60° C. or less. The water repellent agent described in . The polymer (I) contains a hydroxyl group, an epoxy group, an acetoacetyl group, a carbonyl group, a chloromethyl group, an amide group, an N-alkoxymethylamide group, a blocked isocyanate group, an oxazoline group, a carboxyl group, an amino group, and a sulfonic acid group. group, further comprising a repeating unit derived from a crosslinkable ethylenically unsaturated monomer (Ib) having at least one selected from the group consisting of an alkoxysilyl group, according to any one of claims 1 to 4 Water repellent as described. Claims 1 to 3, wherein the polymer (I) further has a repeating unit derived from a monoethylenically unsaturated monomer (Ic) having an organopolysiloxane skeleton, represented by the following general formula (4): 6. The water repellent agent according to any one of 5.

[In the general formula (4), X is a group having an ethylenically unsaturated group and an alkylene group having 1 to 10 carbon atoms, Y is a silicone chain represented by the general formula (4) or R ⁴¹ , R ⁴¹ is an alkyl group or an aryl group having 1 to 32 carbon atoms which ^{may be the same or different; n 41 is} an integer of 0 to 200; ⁴¹ may be the same or different from each other and the total does not exceed 200. ] The water repellent according to any one of claims 1 to 6, wherein the polymer (I) further has a repeating unit derived from a monoethylenically unsaturated monomer (Id) having a polyoxyethylene group. agent. The water repellent according to any one of claims 1 to 7, further comprising a liquid medium containing water and a surfactant. A water repellent agent comprising a first agent containing at least the following polymer (I), a second agent containing at least the following polymer (II), and a third agent containing at least the following component (III) is prepared. wherein the ratio of the polymer (I) is 0 to 55 parts by mass with respect to the total 100 parts by mass of the polymer (I) and the component (III); ) in a ratio of 10 to 85 parts by mass, and does not contain a fluorine-containing component.
<Polymer (I)>
A polymer having a repeating unit derived from at least one monoethylenically unsaturated carboxylic acid ester monomer (Ia) represented by the following general formula (1).

[In general formula (1), R ¹¹ is a hydrogen atom, a methyl group, or a chlorine atom, and R ¹² is a linear or branched aliphatic hydrocarbon group having 16 to 30 carbon atoms. ]
<Polymer (II)>
A polymer having a repeating unit derived from at least one vinyl monomer (IIa) represented by the following general formula (2), wherein the vinyl monomer (IIa) in the polymer (II) ) is 30% by mass or more and 100% by mass or less based on 100% by mass of the polymer (II).

[In general formula (2), R ²¹ is a hydrogen atom, a methyl group or a chlorine atom; R ²² is a chlorine atom or a substituted or unsubstituted phenyl group; It may be substituted with up to 10 alkyl groups. ]
<Component (III)>
At least one of a composition containing an alcohol (IIIa) represented by the following general formula (3) and an isocyanate compound (IIIb), and a reaction product of the alcohol (IIIa) and the isocyanate compound (IIIb).

[In the general formula (3), n ³¹ is an integer of 3 to 8, n ³¹ −n ³² represents a value obtained by subtracting n 32 from n 31 , an integer of 1 to 7, ^and n 32 ^{is 1} to an integer of 7, and R ³¹ is a linear or branched aliphatic hydrocarbon group having 16 to 32 carbon atoms, or an acyl having a linear or branched aliphatic hydrocarbon group having 15 to 31 carbon atoms A is a residue obtained by removing a hydroxyl group from a tri- to hexavalent polyhydric alcohol having 6 or less carbon atoms, and removing a hydroxyl group from a dimer to tetramer of a tri- to hexavalent polyhydric alcohol having 6 or less carbon atoms. at least one selected from the group consisting of a residue, a residue obtained by removing a hydroxyl group from a monosaccharide or a disaccharide, and a residue obtained by removing a hydroxyl group from an intramolecular dehydration product of a 5- to 6-hydric polyhydric alcohol. be. ] A method for treating a fiber substrate, comprising treating the fiber substrate with the water repellent agent according to any one of claims 1 to 8 or the kit according to claim 9. A method for producing a water repellent treated textile substrate, comprising applying the water repellent agent according to any one of claims 1 to 8 or the kit according to claim 9 to a textile substrate. A textile article treated with the water repellent agent according to any one of claims 1 to 8 or the kit according to claim 9. At least one surface of a textile article has a water repellent surface treated with the water repellent agent according to any one of claims 1 to 8 or the kit according to claim 9, and one surface of the textile article is further A textile article having a coating film. At least one surface of a textile article is treated with the water repellent agent according to any one of claims 1 to 8 or the kit according to claim 9 to form a water repellent treated surface, and one surface of the textile article is further A method for manufacturing a textile article, comprising forming a coating film.