JP2022103124A - Water-repellent organic fine particles having effect of improving water pressure resistance - Google Patents

Abstract

To provide organic fine particles and a water pressure resistance improving composition which are capable of imparting excellent water pressure resistance and waterproofness to a substrate.SOLUTION: Organic fine particles comprise a polymer having a repeating unit formed from (I) a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3-40 carbon atoms, and, optionally, (II) a crosslinkable monomer having at least two ethylenically unsaturated double bonds. A water pressure resistance improving composition comprises (A) organic fine particles, and (B) an aqueous medium.SELECTED DRAWING: None

Description

The present disclosure relates to water-repellent organic fine particles having an effect of improving water pressure resistance, particularly non-fluorine organic fine particles.

Conventionally, superhydrophobicity is imparted to the surface of a base material by a method of forming a fine uneven structure on the surface of a base material or a method of combining the formation of such a fine uneven structure on the surface of a base material and the above-mentioned coating treatment. is doing. The method of using fine particles and the method of patterning such as etching are mainly used for creating the uneven structure. The range and substrate of the patterning method such as etching are limited.

When hydrophobic inorganic fine particles are used as the fine particles, a large amount of a dispersant such as an emulsifier is required to obtain an aqueous dispersion of the hydrophobic inorganic fine particles. If the hydrophobicity of the hydrophobic inorganic fine particles is lowered, that is, if the hydrophobic inorganic fine particles having a hydrophilic group left are used, the dispersion in water becomes a little easier, but the hydrophobicity of the fine particles themselves is lowered, so that it is used as a water repellent. Performance is reduced.

On the other hand, there are soap-free polymerization and organic fine particle synthesis methods with less emulsifier. Since these are dispersed in water without an emulsifier or with a small amount of emulsifier, hydrophilic monomers are generally used, and most of the fine particles thereof also show hydrophilicity. Since it is difficult to use a monomer having high hydrophobicity, it has been difficult to synthesize organic fine particles exhibiting water repellency by using soap-free polymerization or an organic fine particle synthesis method with a small amount of emulsifier.

In order to improve the water pressure resistance or waterproofness, it was mainly improved by increasing the density of the fabric and the structure of laminating or laminating.

Patent Document 1 discloses that a water-repellent fabric in which fine particles of 0.01 to 10.0 μm are fixed on the surface of the fabric has improved water pressure resistance. The fine particles used in Example 1 of Patent Document 1 are silica fine particles and inorganic fine particles.
Since the improvement of water pressure resistance is mainly improved by increasing the density of the fabric and the structure of laminating or laminating, there is almost no technique to improve the water pressure resistance only by the repellent.

Japanese Unexamined Patent Publication No. 2004-256939

The present disclosure provides organic fine particles capable of imparting excellent water pressure resistance and waterproofness to a substrate.

The present disclosure relates to organic fine particles that can exist on a base material in a state of having a particle shape and exhibit a water pressure resistant effect on the base material. The organic fine particles can adhere to the substrate in a state of having a particle shape.
In the present disclosure, the water pressure resistant effect exhibited is
When organic fine particles are attached to cloth, (i) water pressure resistance ratio (= water resistance of treated cloth with organic fine particles / water resistance of blank untreated cloth) is 1.03 or more, (ii) air permeability. It is preferable that the ratio (= the air permeability of the treated cloth to which the organic fine particles are attached / the air permeability of the blank untreated cloth) satisfies at least one of 0.9 or less.
In the present disclosure, the expressed water repellency is
(i) When the organic fine particles are attached to the cloth, the contact angle of the water of the cloth to which the organic fine particles are attached is 120 degrees or more, or
(ii) When the organic fine particles are attached to the cloth, the falling speed of the cloth to which the organic fine particles are attached is 100 mm / s or more, or
(iii) When the organic fine particles are attached to the cloth, the water repellency test of the cloth to which the organic fine particles are attached means at least one of 80 points or more.

This disclosure is
The present invention relates to a water repellent composition comprising (A) organic fine particles and (B) an aqueous medium.
In addition, this disclosure is
(I) Containing a polymer having repeating units formed from a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms. Regarding organic fine particles.
In addition to the hydrophobic monomer (I), the polymer constituting the organic fine particles is added to the hydrophobic monomer (I).
(II) Crosslinkable monomer having at least two ethylenically unsaturated double bonds,
It may also have repeating units formed from.
The polymer constituting the organic fine particles is further added.
(III) A reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or a hydrophilic group, or one ethylenically unsaturated double bond and at least one. A short-chain hydrocarbon-containing monomer having one or two hydrocarbon groups with one or two carbon atoms,
(IV) It also has repeating units formed from at least one monomer selected from (meth) acrylic monomers having a linear hydrocarbon group or polydimethylsiloxane group with 3-40 carbon atoms. You can do it.

または

［式中、Ｒ^３１およびＲ^３３は、それぞれ独立的に直接結合、炭素数１～２０の炭化水素基（－OH基を有する炭化水素部位を含んでもよい）、－（ＣＨ_２ＣＨ_２Ｏ）ｒ－（ｒは１～１０の整数）、－Ｃ_６Ｈ_４－、－Ｏ－、または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）から選ばれる少なくとも１つ以上で構成される２～４価の基であり、
Ｒ^３２、Ｒ^３４、Ｒ^３５およびＲ^３６は、それぞれ独立的に水素原子、一価の有機基、またはハロゲン原子であり、
Ｙ^３１は、－Ｏ－、または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）であり、
ｐは、２～４であり、
ｑは１～５である。］
で示される単量体であり、
反応性・親水性単量体（III）が、式：
式：
ＣＨ_２＝Ｃ(－Ｒ^４２)－Ｃ(＝Ｏ)－Ｙ^４１－（Ｒ^４３）_ｏ（Ｒ^４１)_ｔ
または
ＣＨ_２＝Ｃ(－Ｒ^４５)－Ｙ^４２－(Ｈ)_５－ｎ（Ｒ^４４)_ｕ
［式中、Ｒ^４１およびＲ^４４は、それぞれ独立的に反応性基または親水性基であり、
Ｒ^４２およびＲ^４５は、水素原子、一価の有機基、またはハロゲン原子であり、
Ｙ^４１は、直接結合、－Ｏ－、または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）であり、
Ｒ^４３は、直接結合、－Ｏ－、または２～４価の炭素数１～１０（－OH基を有する炭化水素部位を含んでもよい）の炭化水素基を有する基であり、
Ｙ^４２はベンゼン環であり、
Ｈは水素原子であり、
ＨおよびＲ^４４はＹ^４２にそれぞれ直接結合しており、
ｔおよびｕは１～３であり、
ｏは、０または１である。］
で示される単量体、または、
短鎖炭化水素含有単量体（III）が、式：
ＣＨ_２＝Ｃ(－Ｒ^４７)－Ｃ(＝Ｏ)－Ｙ^４３－Ｒ^４６
［式中、Ｒ^４６は、炭素数１または２の炭化水素基であり、
Ｒ^４７は、水素原子、一価の有機基、またはハロゲン原子であり、
Ｙ^４３は、直接結合、－Ｏ－、または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）である。］
で示される単量体であり、
（メタ）アクリル単量体（IV）が、式：
ＣＨ_２＝Ｃ(－Ｒ^５２)－Ｃ(＝Ｏ)－Ｙ^５１（Ｒ^５１)_ｓ
［式中、Ｒ^５１は、それぞれ独立的に、炭素数３～４０の直鎖状の炭化水素基であり、
Ｒ^５２は、水素原子、一価の有機基、またはハロゲン原子であり、
Ｙ^５１は、２～４価の炭素数１の炭化水素基（特に、－ＣＨ_２－、－ＣＨ＝および－Ｃ≡）、－Ｃ_６Ｈ_４－、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ（＝Ｏ）_２－または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）から選ばれる少なくとも１つ以上で構成される２～４価の基（但し、２価の炭化水素基のみの場合を除く）であり、
ｓは１～３である。］
で示される、炭素数３～４０の直鎖状の炭化水素基を有する（メタ）アクリル単量体であるか、または
式：
ＣＨ_２＝Ｃ(－Ｒ^６２)－Ｃ(＝Ｏ)－Ｙ^６１－Ｒ^６１
［式中、Ｒ^６１は、ポリジメチルシロキサン基を有する基であり、
Ｒ^６２は、水素原子、一価の有機基、またはハロゲン原子であり、
Ｙ^６１は、２～４価の炭素数１の炭化水素基、－Ｃ_６Ｈ_４－、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ（＝Ｏ）_２－または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）から選ばれる少なくとも１つ以上で構成される２～４価の基である。］
で示される、ポリジメチルシロキサン基を有する（メタ）アクリル単量体である態様４～８のいずれかに記載の有機微粒子。
態様１０：
反応性単量体（III）において、反応性基が、エポキシ基、クロロメチル基、ブロモメチル基、ヨードメチル基、ブロックイソシアネート基であり、親水性基が、ヒドロキシル基、アミノ基（Ｎに結合するＨがメチル基、エチル基、プロピル基、またはブチル基に変換されたものを含む）、カルボン酸基、スルホン酸基、リン酸基、カルボン酸、スルホン酸、リン酸のアルカリ金属またはアルカリ土類金属塩基、塩素または臭素、ヨウ素イオンが対アニオンであるアンモニウム塩基、エチレングリコール基、ポリエチレングリコール基、アセトン骨格を有する基（－Ｃ（＝Ｏ）－ＣＨ_３）からなる群から選択された少なくとも１種の基である、または反応性・親水性単量体（III）が炭素数６以下の短鎖の炭化水素基を側鎖に有する（メタ）アクリルアミドである態様７～９のいずれかに記載の有機微粒子。
態様１１：
疎水性単量体（I）が、
ｔ－ブチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、２，６，８－トリメチルノナン－４－イル＝アクリレート、
イソボロニル（メタ）アクリレート、ボルニル（メタ）アクリレート、アダマンチル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、フェニル（メタ）アクリレート、ナフチルアクリレート、ベンジルアクリレート
ｔ－ブチルスチレン、メチルスチレン、スチレン、シクロヘキシル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロブチル（メタ）アクリレート、シクロへプチル（メタ）アクリレート、２，４－ジｔ－ブチルスチレン、２，４，６－トリメチルスチレン、からなる群から選択された少なくとも１種の単量体であり、
架橋性単量体（II）が、ジビニルベンゼン、１，４－ブタンジオールジ(メタ)アクリレート、１，６－ヘキサンジオールジ(メタ)アクリレート、１，９－ノナンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ポリエチレングルコールジ（メタ）アクリレート、トリエチエレングルコールジ（メタ）アクリレート、エチレングルコールジ（メタ）アクリレート、メチレングルコールジ（メタ）アクリレート、ポリテトラメチレングルコールジ（メタ）アクリレート、ジメチロールトリシクロデカンジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、アダマンチルジ（メタ）アクリレート、グリセリンジ（メタ）アクリレート、トリシクロデカンジメタノ-ルジ（メタ）アクリレ-ト、ジシクロペンタニルジ（メタ）アクリレート、５－ヒドロキシ－１，３－アダマンタンジ（メタ）アクリレートからなる群から選択された少なくとも１種の単量体であり、
反応性・親水性単量体（III）が、グリシジル(メタ)アクリレート、グリセロール(メタ)アクリレート、ヒドロキシメチル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２，３－ジヒドロキシプロピル(メタ)アクリレート、３－クロロ－２－ヒドロキシプロピル(メタ)アクリレート、３－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、２－アセトアセトキシエチル（メタ）アクリレート、４－ヒドロキシブチルアクリレートグリシジルエーテル、アクリル酸、メタクリル酸、トリメチルシリル（メタ）アクリレート、２－（トリメチルシリルオキシ）エチル（メタ）アクリレート、２－（ジメチルアミノ）エチル（メタ）アクリレート、２－（ｔｅｒｔ－ブチルアミノ）エチル（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート 四級化物、テトラヒドロフルフリル（メタ）アクリレート、ポリエチレングリコール（メタ）アクリレート、ジアセトン（メタ）アクリルアミド、イソプロピル（メタ）アクリルアミド、ｔ－ブチル（メタ）アクリルアミド、エチル（メタ）アクリルアミド、メチル（メタ）アクリルアミド；および
4-ヒドロキシメチルスチレン、４－ヒドロキシエチルスチレン、4-アミノメチルスチレン、４－アミノエチルスチレン、２－（４－ビニルフェニル）オキシラン、２－（４－ビニルベンゾイル）オキシランからなる群から選択された少なくとも１種の単量体であり、
短鎖炭化水素基含有単量体（III）が、メチルメタクリレート、エチルメタクリレート、α―クロロメチルアクリレート、α―クロロエチルアクリレートからなる群から選択された少なくとも１種の単量体であり、
（メタ）アクリル単量体（IV）が、
ステアリル（メタ）アクリレート、ステアリン酸アミドエチル（メタ）アクリレート、ＣＨ_２＝ＣＨＣ（＝Ｏ）ＯＣ_２Ｈ_４ＮＨＣ（＝Ｏ）Ｃ_１７Ｈ_３５、ＣＨ_２＝ＣＨＣ（＝Ｏ）ＯＣ_２Ｈ_４ＮＨＳＯ_２Ｃ_１８Ｈ_３７、ＣＨ_２＝ＣＨＣ（＝Ｏ）ＯＣ_２Ｈ_４ＮＨＣ（＝Ｏ）ＯＣ_１８Ｈ_３７、ＣＨ_２＝ＣＨＣ（＝Ｏ）ＯＣ_２Ｈ_４ＯＣ（＝Ｏ）ＮＨＣ_１８Ｈ_３７、ＣＨ_２＝ＣＨＣ（＝Ｏ）ＯＣ_２Ｈ_４ＮＨＣ（＝Ｏ）ＮＨＣ_１８Ｈ_３７、
式：

または

［式中、ｎは１～５００の数である。］
からなる群から選択された少なくとも１種の単量体である態様４～１０のいずれかに記載の有機微粒子。
態様１２：
（i）疎水性単量体（I）／反応性・親水性単量体および・又は短鎖炭化水素基含有単量体（III）のモル比が、１００／０～５０／５０、
（ii）架橋性単量体（II）が、疎水性単量体（I）、反応性・親水性単量体および・又は短鎖炭化水素基含有単量体（III）、及び（メタ）アクリル単量体（IV）の合計１００モル部に対して、０．１～３０モル部、
又は、（iii）（メタ）アクリル単量体（IV）が、疎水性単量体（I）及び反応性・親水性単量体および・又は短鎖炭化水素基含有単量体（III）の合計１００モル部に対して、０～３０モル部
の少なくとも一つを満たす、態様４～１１のいずれかに記載の有機微粒子。
態様１３：
態様１～１２のいずれかに記載の有機微粒子を含んでなる耐水圧向上剤。
態様１４：
態様１～１２のいずれかに記載の有機微粒子の、耐水圧向上剤としての使用。
態様１５：
（Ａ）態様１～１２のいずれかに記載の有機微粒子、および
（Ｂ）水性媒体
を含んでなる耐水圧向上剤組成物。
態様１６：
有機微粒子（Ａ）の量が耐水圧向上剤組成物に対して５０重量％以下である態様１５に記載の耐水圧向上剤組成物。
態様１７：
さらに、（Ｃ）バインダー樹脂、（Ｄ）界面活性剤、および（Ｅ）架橋剤のどれか一つ以上を含む態様１５または１６に記載の耐水圧向上剤組成物。
態様１８：
バインダー樹脂（Ｃ）が、側鎖に炭素数３～４０の炭化水素基を有する非フッ素重合体、および側鎖に炭素数１～２０のフルオロアルキル基を有する含フッ素重合体から選択された少なくとも１種の重合体である態様１７に記載の耐水圧向上剤組成物。
態様１９：
バインダー樹脂（Ｃ）が、アクリル重合体、ウレタン重合体、ポリオレフィン、ポリエステル、ポリエーテル、ポリアミド、ポリイミド、ポリスチレン、シリコーン重合体およびこれらの組み合わせである態様１７または１８のいずれかに記載の耐水圧向上剤組成物。
態様２０：
バインダー樹脂（Ｃ）／有機微粒子（Ａ）の重量比が１／９９～９０／１０もしくは２０／８０～９９／１または、バインダー樹脂（Ｃ）の量が、バインダー樹脂（Ｃ）と有機微粒子（Ａ）の重量を合計に対して、３０～９９重量％である態様１７～１９のいずれかに記載の耐水圧向上剤組成物。
態様２１：
水性媒体中で、単量体１００重量部に対して３０重量部以下である界面活性剤の存在下で、単量体を重合させて有機微粒子（Ａ）の水分散体を得る工程、
を有する態様１５～２０のいずれかに記載の耐水圧向上剤組成物の製造方法。
態様２２：
さらに、
有機微粒子（Ａ）の水分散体にバインダー樹脂（Ｃ）の水分散体を加えることによって、あるいは有機微粒子（Ａ）の水分散体の中においてバインダー樹脂用の単量体を重合してバインダー樹脂（Ｃ）を得ることによって、あるいはバインダー樹脂の水分散体の中において、有機微粒子用の単量体を重合することによって、有機微粒子（Ａ）およびバインダー樹脂（Ｃ）が分散した水分散体を得る工程
を有する態様２１に記載の製造方法。
態様２３：
態様１５～２０のいずれかに記載の耐水圧向上剤組成物を含む処理液を繊維製品に適用する繊維製品の処理方法。
態様２４：
態様１５～２０のいずれかに記載の耐水圧向上剤組成物を適用した、繊維製品。
態様２５：
(i)耐水圧比（＝有機微粒子が付着した繊維製品の耐水圧／ブランクの繊維製品の耐水圧）が１．０３以上、(ii)透気度比（＝有機微粒子が付着した繊維製品の透気度／ブランクの繊維製品の透気度）が０．９以下、の少なくともどれか一つを満たす態様２４に記載の繊維製品。
態様２６：
繊維製品がアウトドア用品用の布、スポーツ用品用の布、雨具用の布、医療用の布、または不織布である、態様２４または２５に記載の繊維製品。
態様２７：
繊維製品が医療用の手術着、防護服、オーニング、シェード、テントである、態様２６に記載の繊維製品。 Preferred embodiments of the present disclosure are as follows.
Aspect 1:
Organic fine particles that can exist on a base material in a state of having a particle shape and exhibit a water pressure resistant effect on the base material.
Aspect 2:
When attached to cloth, (i) water pressure resistance ratio (= water resistance of treated cloth with organic fine particles / water resistance of blank untreated cloth) is 1.03 or more, (ii) air permeability ratio (=) The organic fine particles according to embodiment 1, wherein the air permeability of the treated cloth to which the organic fine particles are attached / the air permeability of the blank untreated cloth) satisfies at least one of 0.9 or less.
Aspect 3:
The organic fine particles according to Aspect 1 or 2, wherein the fine particles observable on the cloth have a particle size of 50 to 700 nm.
Aspect 4:
(I) Aspects 1 to include a polymer having a repeating unit formed from a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms. The organic fine particles according to any one of 3.
Aspect 5:
(I) A hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms, and (II) at least two ethylenically unsaturated diaries. Crosslinkable monomer with double bond,
Organic fine particles containing a polymer having repeating units formed from.
Aspect 6:
(I) Contains a polymer having repeating units formed from a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3-40 carbon atoms. Organic fine particles
Among the hydrophobic monomers (I), organic fine particles containing 20 mol% or more of high glass transition point monomers having a glass transition point of homopolymer of 100 ° C. or higher.
Aspect 7:
The polymer is
(III) A reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or a hydrophilic group, or one ethylenically unsaturated double bond and at least one. A short-chain hydrocarbon-containing monomer having one or two hydrocarbon groups with one or two carbon atoms,
And / or (IV) (meth) acrylic monomers having a linear hydrocarbon group or polydimethylsiloxane group with 3-40 carbon atoms,
The organic fine particles according to aspects 4 to 6, which also have a repeating unit formed from at least one monomer selected from the above.
Aspect 8:
The organic according to any one of embodiments 4 to 7, wherein in the hydrophobic monomer (I), the branched hydrocarbon group has 3 to 11 carbon atoms and the cyclic hydrocarbon group has 4 to 15 carbon atoms. Fine particles.
Aspect 9:
Hydrophobic monomer (I) has the formula:
CH ₂ = C (-R ¹² ) -C (= O) -Y ¹¹ (R ¹¹ ) _k
Or CH ₂ = C (-R ¹⁴ ) -Y ¹² (H) _5-l (R ¹³ ) _l
[In the formula, R ¹¹ and R ¹³ are independently branched or cyclic hydrocarbon groups having 3 to 40 carbon atoms, respectively.
R ¹² and R ¹⁴ are hydrogen atoms, monovalent organic groups or halogen atoms.
Y ¹¹ is -O-,-or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms).
Y ¹² is a benzene ring and
H is a hydrogen atom
H and R ¹³ are directly bonded to Y ¹² , respectively.
k is 1 to 3 and l is 0 to 3. ]
It is a monomer indicated by
The crosslinkable monomer (II) has the formula:
formula:

or

[In the formula, R ³¹ and R ³³ are independently directly bonded to each other and have a hydrocarbon group having 1 to 20 carbon atoms (may include a hydrocarbon moiety having a −OH group), − (CH ₂ CH ₂ O). At least one selected from r- (r is an integer of 1 to 10), -C ₆ H _4- , -O-, or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms). It is a 2- to 4-valent group composed of two or more.
R ³² , R ³⁴ , R ³⁵ and R ³⁶ are independently hydrogen atoms, monovalent organic groups, or halogen atoms, respectively.
Y ³¹ is -O- or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms).
p is 2 to 4,
q is 1 to 5. ]
It is a monomer indicated by
Reactive / hydrophilic monomer (III) has the formula:
formula:
CH ₂ = C (-R ⁴² ) -C (= O) -Y ^41- (R ⁴³ ) _o (R ⁴¹ ) _t
Or CH ₂ = C (-R ⁴⁵ ) -Y ^42- (H) _5-n (R ⁴⁴ ) _u
[In the formula, R ⁴¹ and R ⁴⁴ are independently reactive or hydrophilic groups, respectively.
R ⁴² and R ⁴⁵ are hydrogen atoms, monovalent organic groups, or halogen atoms.
Y ⁴¹ is a direct bond, -O-, or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms).
R ⁴³ is a group having a direct bond, —O—, or a hydrocarbon group having 2 to 4 valences of 1 to 10 carbon atoms (which may include a hydrocarbon moiety having an −OH group).
Y ⁴² is a benzene ring and
H is a hydrogen atom
H and R ⁴⁴ are directly coupled to Y ⁴² , respectively.
t and u are 1 to 3,
o is 0 or 1. ]
The monomer indicated by, or
The short-chain hydrocarbon-containing monomer (III) has the formula:
CH ₂ = C (-R ⁴⁷ ) -C (= O) -Y ⁴³ -R ⁴⁶
[In the formula, ^R46 is a hydrocarbon group having 1 or 2 carbon atoms.
R ⁴⁷ is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁴³ is a direct bond, -O-, or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms). ]
It is a monomer indicated by
The (meth) acrylic monomer (IV) has the formula:
CH ₂ = C (-R ⁵² ) -C (= O) -Y ⁵¹ (R ⁵¹ ) _s
[In the formula, R ⁵¹ is a linear hydrocarbon group having 3 to 40 carbon atoms independently.
R ⁵² is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁵¹ is a hydrocarbon group having 2 to 4 valences of 1 carbon atom (particularly -CH _2- , -CH = and -C≡), -C ₆ H _4- , -O-, -C (= O). -, -S (= O) ₂ -or-NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms) and is composed of at least one 2- to 4-valent group (R'is a hydrocarbon group having 1 to 4 carbon atoms). However, this is not the case with only divalent hydrocarbon groups).
s is 1 to 3. ]
It is a (meth) acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms, which is represented by the formula:
CH ₂ = C (-R ⁶² ) -C (= O) -Y ⁶¹ -R ⁶¹
[In the formula, ^R61 is a group having a polydimethylsiloxane group.
R ⁶² is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁶¹ is a hydrocarbon group having 2 to 4 valences of 1 carbon atom, -C ₆ H _4- , -O-, -C (= O)-, -S (= O) _2- or -NR'-( R'is a 2- to 4-valent group composed of at least one selected from H or a hydrocarbon group having 1 to 4 carbon atoms. ]
The organic fine particles according to any one of aspects 4 to 8, which are (meth) acrylic monomers having a polydimethylsiloxane group, which are shown in.
Aspect 10:
In the reactive monomer (III), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group or a blocked isocyanate group, and the hydrophilic group is a hydroxyl group or an amino group (H bonded to N). Is converted to a methyl group, an ethyl group, a propyl group, or a butyl group), a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a carboxylic acid, a sulfonic acid, an alkali metal or alkaline earth metal of phosphoric acid. At least one selected from the group consisting of a base, chlorine or bromine, an ammonium base having an iodine ion as a counter anion, an ethylene glycol group, a polyethylene glycol group, and a group having an acetone skeleton (-C (= O) -CH ₃ ). The group according to any one of embodiments 7 to 9, wherein the reactive / hydrophilic monomer (III) is a (meth) acrylamide having a short-chain hydrocarbon group having 6 or less carbon atoms in the side chain. Organic fine particles.
Aspect 11:
Hydrophobic monomer (I)
t-Butyl (meth) acrylate, isopropyl (meth) acrylate, 2,6,8-trimethylnonane-4-yl = acrylate,
Isoboronyl (meth) acrylate, Bornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenyl (meth) acrylate, naphthyl acrylate, benzyl acrylate t-butylstyrene , Methylstyrene, styrene, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclobutyl (meth) acrylate, cycloheptyl (meth) acrylate, 2,4-dit-butylstyrene, 2,4,6-trimethylstyrene , At least one monomer selected from the group consisting of,
The crosslinkable monomer (II) is divinylbenzene, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neo. Pentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene glycol di (meth) acrylate, methylene glycol di (meth) acrylate, polytetramethylene glue. Coledi (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, trimethylolpropane tri (meth) acrylate, adamantyldi (meth) acrylate, glycerindi (meth) acrylate, tricyclodecanedimethanoldi (meth) ) At least one monomer selected from the group consisting of acrylate, dicyclopentanyldi (meth) acrylate, and 5-hydroxy-1,3-adamantandi (meth) acrylate.
Reactive / hydrophilic monomer (III) is glycidyl (meth) acrylate, glycerol (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth) acrylate, 2- (trimethylsilyloxy) ethyl (meth) acrylate, 2- (Dimethylamino) ethyl (meth) acrylate, 2- (tert-butylamino) ethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate quaternized product, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (meth) Acrylate, diacetone (meth) acrylamide, isopropyl (meth) acrylamide, t-butyl (meth) acrylamide, ethyl (meth) acrylamide, methyl (meth) acrylamide; and
Selected from the group consisting of 4-hydroxymethylstyrene, 4-hydroxyethylstyrene, 4-aminomethylstyrene, 4-aminoethylstyrene, 2- (4-vinylphenyl) oxylane, 2- (4-vinylbenzoyl) oxylane. At least one monomer,
The short-chain hydrocarbon group-containing monomer (III) is at least one monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, α-chloromethyl acrylate, and α-chloroethyl acrylate.
(Meta) Acrylic monomer (IV)
Stearyl (meth) acrylate, amide ethyl stearate (meth) acrylate, CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) C ₁₇ H _35, CH ₂ = CHC (= O) OC ₂ H ₄ NHSO ₂ C ₁₈ H ₃₇ , CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) OC ₁₈ H ₃₇ , CH ₂ = CHC (= O) OC ₂ H ₄ OC (= O) NHC ₁₈ H ₃₇ , CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) NHC ₁₈ H ₃₇ ,
formula:

or

[In the formula, n is a number from 1 to 500. ]
The organic fine particles according to any one of aspects 4 to 10, which are at least one monomer selected from the group consisting of.
Aspect 12:
(I) The molar ratio of the hydrophobic monomer (I) / reactive / hydrophilic monomer and / or the short-chain hydrocarbon group-containing monomer (III) is 100/0 to 50/50.
(Ii) The crosslinkable monomer (II) is a hydrophobic monomer (I), a reactive / hydrophilic monomer and / or a short-chain hydrocarbon group-containing monomer (III), and (meth). 0.1 to 30 mol parts for a total of 100 mol parts of the acrylic monomer (IV),
Alternatively, (iii) the (meth) acrylic monomer (IV) is a hydrophobic monomer (I) and a reactive / hydrophilic monomer and / or a short-chain hydrocarbon group-containing monomer (III). The organic fine particles according to any one of aspects 4 to 11, which satisfy at least one of 0 to 30 mol parts with respect to 100 mol parts in total.
Aspect 13:
A water pressure resistant improving agent containing the organic fine particles according to any one of aspects 1 to 12.
Aspect 14:
Use of the organic fine particles according to any one of aspects 1 to 12 as a water pressure resistance improving agent.
Aspect 15:
(A) A water pressure resistant improving agent composition comprising the organic fine particles according to any one of aspects 1 to 12 and (B) an aqueous medium.
Aspect 16:
The water pressure resistant improving agent composition according to aspect 15, wherein the amount of the organic fine particles (A) is 50% by weight or less with respect to the water pressure resistant improving agent composition.
Aspect 17:
The water pressure resistance improving agent composition according to aspect 15 or 16, further comprising (C) a binder resin, (D) a surfactant, and (E) one or more of a cross-linking agent.
Aspect 18:
The binder resin (C) is selected from at least a non-fluorinated polymer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain and a fluorine-containing polymer having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain. The water pressure resistant improving agent composition according to embodiment 17, which is a polymer of one type.
Aspect 19:
The water pressure resistance improvement according to any one of aspects 17 or 18, wherein the binder resin (C) is an acrylic polymer, a urethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, polystyrene, a silicone polymer, or a combination thereof. Agent composition.
Aspect 20:
The weight ratio of the binder resin (C) / organic fine particles (A) is 1/99 to 90/10 or 20/80 to 99/1, or the amount of the binder resin (C) is the binder resin (C) and the organic fine particles (C). The water pressure resistant improving agent composition according to any one of aspects 17 to 19, wherein the weight of A) is 30 to 99% by weight based on the total weight.
Aspect 21:
A step of polymerizing a monomer to obtain an aqueous dispersion of organic fine particles (A) in the presence of a surfactant having a weight of 30 parts by weight or less with respect to 100 parts by weight of the monomer in an aqueous medium.
The method for producing a water pressure resistant improving agent composition according to any one of embodiments 15 to 20.
Aspect 22:
moreover,
Binder resin by adding the aqueous dispersion of the binder resin (C) to the aqueous dispersion of the organic fine particles (A) or by polymerizing the monomer for the binder resin in the aqueous dispersion of the organic fine particles (A). By obtaining (C) or by polymerizing a monomer for organic fine particles in an aqueous dispersion of a binder resin, an aqueous dispersion in which the organic fine particles (A) and the binder resin (C) are dispersed can be obtained. 21. The production method according to aspect 21, which comprises a step of obtaining.
Aspect 23:
A method for treating a textile product by applying the treatment liquid containing the water pressure resistant improving agent composition according to any one of embodiments 15 to 20 to the textile product.
Aspect 24:
A textile product to which the water pressure resistance improving agent composition according to any one of embodiments 15 to 20 is applied.
Aspect 25:
(i) Water pressure resistance ratio (= water pressure resistance of textile products with organic fine particles / water pressure resistance of blank textile products) is 1.03 or more, (ii) air permeability ratio (= permeability of textile products with organic fine particles attached) The textile product according to aspect 24, wherein the air permeability / air permeability of the blank textile product) satisfies at least one of 0.9 or less.
Aspect 26:
The textile product according to aspect 24 or 25, wherein the textile product is a cloth for outdoor goods, a cloth for sports goods, a cloth for rain gear, a cloth for medical use, or a non-woven fabric.
Aspect 27:
26. The textile product according to aspect 26, wherein the textile product is a medical surgical gown, protective clothing, awning, shade, tent.

The organic fine particles and the water repellent composition of the present disclosure can impart excellent water pressure resistance and waterproof property to a base material such as a textile product.

The water pressure resistance improving agent contains organic fine particles. The water pressure resistance improving agent may be composed of only organic fine particles, or may contain other components in addition to the organic fine particles.
The water repellent composition functions as a water pressure resistance improving agent.
The water repellent composition (that is, the water pressure resistant improving agent) is
It contains (A) organic fine particles and (B) an aqueous medium.
The water repellent composition further
It may contain (C) a binder resin and / or (D) a surfactant. By including the binder resin (C), higher water pressure resistance can be obtained.

In a preferred embodiment, the water repellent composition contains the following components.
Organic fine particles (A),
Organic fine particles (A) + aqueous medium (B),
Organic fine particles (A) + aqueous medium (B) + binder resin (C),
Organic fine particles (A) + aqueous medium (B) + surfactant (D),
Organic fine particles (A) + aqueous medium (B) + binder resin (C) + surfactant (D)
Organic fine particles (A) + aqueous medium (B) + binder resin (C) + cross-linking agent (E) or organic fine particles (A) + aqueous medium (B) + binder resin (C) + surfactant (D) + Crosslinking agent (E)

(A) Organic fine particles Organic fine particles act as an active ingredient that exhibits water repellency and water pressure resistance. The organic fine particles are preferably formed of a non-fluorine polymer.
The average particle size of the organic fine particles may be 30 to 1000 nm, preferably 40 to 700 nm or 45 to 300 nm from the viewpoint of water pressure resistance and stability of the aqueous dispersion. The average particle size means the average particle size of particles measured by a dynamic light scattering method (DLS).

The organic fine particles retain their particle shape on the substrate and exhibit water pressure resistance.
The water pressure resistance that develops is
(i) When attached to cloth, the water pressure resistance ratio is 1.03 or more, and / or
(ii) It is preferable to mean that the air permeability ratio is 0.9 or less when attached to a cloth.
The water pressure resistance ratio is the ratio of (water pressure resistance of the treated cloth to which organic fine particles are attached) / (water pressure resistance of the blank untreated cloth), and the air permeability ratio is (air permeability of the treated cloth to which organic fine particles are attached). ) / (Air permeability of blank untreated cloth).

The water pressure resistance ratio may be 1.03 or more, 1.05 or more, 1.1 or more, 1.2 or more, or 1.3 to 3.0. The water pressure resistance is measured according to JIS L 1092: 2009 (waterproof test method for textile products). Specifically, the water pressure resistance of the treated cloth to which the organic fine particles are attached is determined by immersing the cloth, for example, PET cloth (grain: 88 g / m ² , 70 denier, gray) in the composition containing the organic fine particles and then passing it through a mangle. , A PET cloth to which organic fine particles are attached is prepared by passing it through a pin tenter at 170 ° C. for 1 minute, and is obtained. The water pressure resistance of the blank untreated cloth is determined for the untreated cloth, for example PET cloth (weight: 88 g / m ² , 70 denier, gray). The untreated means that the organic fine particles are not applied, and the untreated cloth may be a cloth to which the binder resin is applied. When an untreated cloth to which the binder resin is not applied is used as the blank, the water pressure resistance ratio may be 10 or more, further 12 or more, and 100 or less.
The water pressure resistance is preferably higher than that when the organic fine particles are not applied, and the water pressure resistance value is improved by 3%, for example, 5%, and further 10% as compared with the water pressure resistance of the cloth when the organic fine particles are not applied. Is preferable.

The air permeability ratio may be 0.9 or less, 0.8 or less, or 0.7 to 0.3. Air permeability is measured according to JIS P 8117: 2009. Specifically, the air permeability when the organic fine particles are attached is determined by immersing a PET cloth (grain: 88 g / m ² , 70 denier, gray) in a composition containing the organic fine particles, passing it through a mangle, and at 170 ° C. It is obtained by passing it through a pin tenter for 1 minute, preparing a PET cloth to which organic fine particles are attached, and using. The air permeability of the blank untreated fabric is determined for, for example, untreated PET fabric (weight: 88 g / m ² , 70 denier, gray). The untreated means that the organic fine particles are not applied, and the untreated cloth may be a cloth to which the binder resin is applied. Further, depending on the purpose of use of the cloth, it may not be required that the air permeability is the same as that of the untreated cloth, in which case the air permeability ratio may be outside the above range. For example, in furniture applications such as shades and sofas, air permeability may not be required.

The water repellency that develops is
(i) The contact angle of water is 120 degrees or more when attached to cloth, or
(ii) The falling speed when attached to cloth is 100 mm / s or more, or
(iii) It means that the water repellency test of the cloth is 80 points or more when it is attached to the cloth.

Water contact angle on a cloth to which a composition containing organic fine particles is attached (water contact angle on a cloth to which organic fine particles are attached or water on a cloth to which organic fine particles and a binder (and other components) are attached) The contact angle) is preferably 120 degrees or more, more preferably 130 degrees or more, still more preferably 140 degrees or more. Specifically, the contact angle of water on the cloth is such that the PET cloth (grain: 88 g / m ² , 70 denier, gray) is dipped in a composition containing organic fine particles, passed through a mangle, and passed at 170 ° C. for 1 minute. A PET cloth with organic fine particles attached is prepared by passing it through a pin tenter, 2 μL of water is dropped on this PET cloth, and the static contact angle 1 second after the drop is measured by a fully automatic contact angle meter (DropMaster701 manufactured by Kyowa Surface Science Co., Ltd.). ) Is used for measurement.

In the cloth (PET cloth), the falling speed of water is preferably 100 mm / s or more, for example, 130 mm / sec or more, and more preferably 150 mm / sec or more or 200 mm / sec or more. The falling speed is the average falling speed at a distance of about 40 mm in which 20 μL of water is dropped from a microsyringe onto a substrate having an inclination of 30 degrees. Specifically, after immersing a PET cloth (grain: 88 g / m ² , 70 denier, gray) in a composition containing organic fine particles, the mixture is passed through a mangle and a pin tenter at 170 ° C. for 1 minute to adhere the organic fine particles. Prepare the PET cloth, and use a fully automatic contact angle meter (DropMaster701 manufactured by Kyowa Interface Science) to drop 20 μL of water from a microsyringer onto the PET cloth with an inclination of 30 degrees, and watch the dropped water fall. Measured using a high-speed camera (VW-9000 manufactured by Keyence Co., Ltd.), the average falling speed at a distance of about 40 mm is defined as the falling speed.

The water repellency test is preferably 80 points or more or 90 points or more.
The water repellency test is performed according to the spray method of JIS-L-1092 (AATCC-22). Details of the water repellency test are described in the examples herein.

The unevenness of the fine particles on the substrate can be observed with a laser microscope or a scanning electron microscope. After applying the particles on the substrate, the average diameter (average particle size) of the particles after heating is preferably 50% or more, preferably 60%, before and after heating (for example, at 170 ° C. for 1 minute). The above is more preferable. Alternatively, the average particle size of the fine particles observable on the cloth is preferably 30 to 1000 nm, more preferably 40 to 700 nm or 50 to 500 nm. This average particle size is generally preferably the average particle size after coating the particles on the substrate and then heating (at 170 ° C. for 1 minute).

In some embodiments, the organic microparticles are
(I) A polymer having a repeating unit formed from a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms. ,
moreover,
(II) Containing a polymer having or not having a repeating unit formed from a crosslinkable monomer having at least two ethylenically unsaturated double bonds.

In some embodiments, the organic microparticles are further described.
(III) A reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or a hydrophilic group, or one ethylenically unsaturated double bond and at least one. A short-chain hydrocarbon-containing monomer having one or two hydrocarbon groups and / or (IV) a linear hydrocarbon or polydimethylsiloxane group having 3-40 carbon atoms (meth). Acrylic monomer,
It comprises a polymer having repeating units formed from.
Each of the monomers (I) to (IV) (and the other monomer (V)) may have two or more types of monomers.
The polymer constituting the organic fine particles is preferably a non-fluorine polymer.

を有することが好ましい。 (I) Hydrophobic Monomer The hydrophobic monomer (I) has at least one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms.
The hydrophobic monomer (I) is a branched hydrocarbon group (for example, a branched alkyl group), particularly a t-butyl group or an isopropyl group, a group having a multi-branched structure as shown in the following formula:

It is preferable to have.

The hydrophobic monomer (I) is preferably an acrylate compound, an acrylamide compound or a styrene compound containing a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms. That is, the hydrophobic monomer (I) is an acrylate compound containing a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms, and an acrylamide containing a branched or cyclic hydrocarbon group having 3 to 40 carbon atoms. The compound is preferably a styrene compound containing a branched or cyclic hydrocarbon group (excluding the benzene ring) having 3 to 40 carbon atoms. The hydrophobic monomer (I) is preferably a non-fluorine monomer.

Hydrophobic monomer (I) is expressed by the formula:
CH ₂ = C (-R ¹² ) -C (= O) -Y ¹¹ (R ¹¹ ) _k
Or CH ₂ = C (-R ¹⁴ ) -Y ¹² (H) _5-l (R ¹³ ) _l
[In the formula, R ¹¹ and R ¹³ are independently branched or cyclic hydrocarbon groups having 3 to 40 carbon atoms, respectively.
R ¹² and R ¹⁴ are hydrogen atoms, monovalent organic groups, or halogen atoms.
Y ¹¹ has at least one group selected from -O- or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms), or -O- or -NR'-2. It is a concatenated group of valence to tetravalent.
Y ¹² is a benzene ring and
H is a hydrogen atom
H and R ¹³ are directly bonded to Y ¹² , respectively.
k is 1 to 3 and l is 1 to 5. ]
It is preferably a monomer represented by.

R ¹¹ and R ¹³ are branched or cyclic hydrocarbon groups. Branched hydrocarbon groups (eg, 3 to 11 carbon atoms (particularly 3 to 8 or 4 to 6) or 12 to 30) are aliphatic hydrocarbon groups, particularly saturated aliphatic hydrocarbon groups, particularly alkyl groups. Is preferable. The cyclic hydrocarbon group may be an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an aromatic aliphatic hydrocarbon group. -CH ₃ groups have lower surface free energy than -CH _2- and tend to show water repellency. Therefore, a structure with many branches and many -CH ₃ groups is preferable. In the branched hydrocarbon group, the number of -CH ₃ groups may be 2 to 15, for example 3 to 10, 3 to 9, 4 to 8 or 4 to 6.

に示すような多分岐構造の基であってよい。 A branched hydrocarbon group (for example, a branched alkyl group) is an alkyl group having 3 or 4 carbon atoms, particularly a t-butyl group or an isopropyl group, or a hydrocarbon group having a multi-branched structure having 5 to 30 carbon atoms (for example, a hydrocarbon group having a multi-branched structure). Especially alkyl groups), for example:

It may be the basis of a multi-branched structure as shown in.

The cyclic hydrocarbon group may be a saturated or unsaturated monocyclic group, a polycyclic group, a bridging ring group, or the like. The cyclic hydrocarbon group is preferably saturated. The cyclic hydrocarbon group preferably has 4 to 20 carbon atoms (for example, 6 to 15 or 6 to 10). Examples of the cyclic hydrocarbon group include a cyclic aliphatic group having 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and an aromatic aliphatic group having 7 to 20 carbon atoms. The number of carbon atoms of the cyclic hydrocarbon group may be 15 or less, for example, 10 or less. The carbon atom in the ring of the cyclic hydrocarbon group may be directly bonded to the ester group in the (meth) acrylate group, or may be bonded via a spacer of the hydrocarbon. ^In R11, the cyclic hydrocarbon group is preferably a saturated cyclic aliphatic group.

Specific examples of the cyclic hydrocarbon group include a cyclohexyl group, a cyclopentyl group, a cyclobutyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, an isoboronyl group, a naphthalene group, a boronyl group, a tricyclodecanyl group and a phenyl group. , Biphenyl group, triphenyl group.

R ¹² and R ¹⁴ may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or -CF ₃ groups. Examples of R ¹² and R ¹⁴ may be a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom and a cyano group. R ¹² and R ¹⁴ are preferably hydrogen atoms, methyl groups or chlorine atoms. R ¹² is more preferably a methyl group. Since R ¹² is a methyl group, higher water pressure resistance can be obtained. R ¹⁴ is preferably a hydrogen atom, particularly from the viewpoint of reactivity.

Y ¹¹ is preferably a divalent group. Y ¹¹ is preferably —O— or —NH—.

Y ¹² is a benzene ring. The monomer having Y ¹² has a styryl group. In the monomer having Y ¹² , 1 to ³ R13 groups and 2 to 4 hydrogen atoms are bonded to the benzene ring.

k is preferably 1.
l may be 1 to 3, but is preferably 1 or 2.

The hydrophobic monomer is a combination of a monomer having a branched hydrocarbon group and a monomer having a cyclic hydrocarbon group, or a monomer having a monocyclic cyclic hydrocarbon group and a polycyclic ring. Alternatively, it may be a combination of monomers having a cyclic hydrocarbon group of a bridging ring. In the hydrophobic monomer, the weight ratio of the monomer having a branched hydrocarbon group and the monomer having a cyclic hydrocarbon group, and the monomer having a monocyclic cyclic hydrocarbon group and the polycyclic Alternatively, the weight ratio of the monomer having a cyclic hydrocarbon group of the crosslinked ring may be 10/90 to 90/10, 30/70 to 70/30 or 40/60 to 60 to 40.

Specific examples of the hydrophobic monomer (I) are as follows. The compound having the following chemical formula is an acrylic compound in which the α-position is a hydrogen atom, and specific examples may be a methacrylic compound in which the α-position is a methyl group and an α-chloroacrylic compound in which the α-position is a chlorine atom. A methacrylic compound having a methyl group at the α-position is preferable. Also in the styrene derivative, the compound having the following chemical formula is an acrylic compound in which the α-position is a hydrogen atom, but specific examples are an α-methylstyrene compound in which the α-position is a methyl group and α-chloro in which the α-position is a chlorine atom. It may be a styrene compound, and a styrene compound having a hydrogen atom at the α-position is preferable.

［式中、ｔＢｕは、ｔ－ブチルである。］

[In the formula, tBu is t-butyl. ]

Specific examples of the monomer having a cyclic hydrocarbon group include cyclobutyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, and cyclooctyl (meth). Meta) acrylate, t-butylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) ) Acrylate, tricyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate and the like.

Preferred specific examples of the hydrophobic monomer (I) are t-butyl (meth) acrylate, t-butylstyrene, methylstyrene, styrene, isopropyl (meth) acrylate, 2,6,8-trimethylnonan-4-yl. = Acrylate, 2,4-dit-butylstyrene, 2,4,6-trimethylstyrene, cyclobutyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cycloheptyl ( Meta) acrylate, cyclooctyl (meth) acrylate, isobolonyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, 2,3,4-methylphenyl (meth) acrylate.

More preferable specific examples of the hydrophobic monomer (I) are t-butyl (meth) acrylate, isobornyl methacrylate, cyclohexyl methacrylate, t-butyl styrene, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, and adamantyl. (Meta) acrylate, 2-ethyl-2-adamantyl (meth) acrylate.

The hydrophobic monomer (I) may be a high glass transition point monomer (high Tg monomer). When the organic fine particles do not contain the crosslinkable monomer (II), the hydrophobic monomer (I) is preferably a high Tg monomer. The high Tg monomer refers to a monomer having a Tg of 50 ° C. or higher in the homopolymer. Among the monomers (I), the high Tg monomer (Ia) has a glass transition point of 50 ° C. or higher, preferably 100 ° C. or higher. The glass transition point of the homopolymer may be, for example, 120 ° C. or higher, particularly 150 ° C. or higher, and may be 250 ° C. or lower.
The glass transition point (glass transition temperature) of the homopolymer was calculated by differential scanning calorimetry (DSC). A DSC curve is obtained by raising the temperature of 10 mg of the sample at 10 ° C./min, and the midpoint between the extension of each baseline before and after the secondary transition of the DSC curve and the intersection of the tangent at the inflection of the DSC curve. Can be obtained as the temperature indicated by. The organic fine particles may have only one kind of monomer or two or more kinds as hydrophobic monomers, and have high Tg hydrophobic monomers (IA) and /. Alternatively, each of them may independently have a hydrophobic monomer (I) that does not have a high Tg.

または

［式中、Ｒ^２１およびＲ^２３は、炭素数１～３０の炭化水素基、－Ｃ_６Ｈ_４－、－Ｏ－、または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）から選ばれる少なくとも１つ以上で構成される基であり、
Ｒ^２２およびＲ^２４は、水素原子、一価の有機基、またはハロゲン原子であり、
Ｙ^２１は、－Ｏ－、または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）である。］
で示される単量体であってよい。 The high glass transition point monomer is the formula:

or

[In the formula, R ²¹ and R ²³ are hydrocarbon groups having 1 to 30 carbon atoms, -C ₆ H _4- , -O-, or -NR'-(R'is H or 1 to 4 carbon atoms. A group composed of at least one selected from (hydrocarbon groups).
R ²² and R ²⁴ are hydrogen atoms, monovalent organic groups, or halogen atoms.
Y ²¹ is -O- or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms). ]
It may be a monomer represented by.

Examples of R ²¹ and R ²³ are a cyclohexyl group, a dicyclopentanyl group, a dicyclopentenyl group, an adamantyl group, an isobolonyl group, a naphthalene group, a bornyl group, a tricyclodecanyl group, and a phenyl group.

R ²² and R ²⁴ may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or -CF ₃ groups. Examples of R ²² and R ²⁴ are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, fluorine atom, -CF ₃ group and cyano group. R ²² and R ²⁴ are preferably hydrogen atoms, methyl groups, and chlorine atoms. It is more preferable that R ²² is a methyl group. Since R ²² is a methyl group, higher water repellency and higher water pressure resistance can be obtained. On the other hand, R ²⁴ is preferably a hydrogen atom from the viewpoint of reactivity, but a methyl group is preferable from the viewpoint of water repellency and water pressure resistance, and R ²⁴ is selected so as to have both reactivity and water repellency. It is preferable to do so.
Y ²¹ is preferably —O— or —NH—.

Specific examples of the high glass transition point monomer include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth). ) Acrylate, tricyclodecanyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, 2-t-butylphenyl (meth) acrylate, naphthyl (meth) acrylate and other acrylate esters. And styrene, α-methylstyrene, styrene derivative and the like.

(II) Crosslinkable Monomer The crosslinkable monomer (II) is a compound having at least two (particularly two, three or four) ethylenically unsaturated double bonds. The crosslinkable monomer (II) is preferably a non-fluorine monomer.

または

［式中、Ｒ^３１およびＲ^３３は、それぞれ独立的に直接結合、あるいは炭素数１～２０の炭化水素基（－OH基を有する炭化水素部位を含んでもよい）、－（ＣＨ_２ＣＨ_２Ｏ）_ｒ－（ｒは１～１０の整数）、－Ｃ_６Ｈ_４－、－Ｏ－、または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）から選ばれる少なくとも１つ以上で構成される２～４価の基であり、
Ｒ^３２、Ｒ^３４、Ｒ^３５およびＲ^３６は、それぞれ独立的に、水素原子、一価の有機基、またはハロゲン原子であり、
Ｙ^３１は、－Ｏ－、または－ＮＲ’－（Ｒ’は、Ｈまたは炭素数１～４の炭化水素基）であり、
ｐは、２～４であり、
ｑは１～５である。］
で示される単量体であることが好ましい。 The crosslinkable monomer (II) is of the formula:

or

[In the formula, R ³¹ and R ³³ are independently directly bonded, or have a hydrocarbon group having 1 to 20 carbon atoms (may include a hydrocarbon moiety having a −OH group), − (CH ₂ CH ₂ O). ) R- ( _r is an integer of 1 to 10), -C ₆ H _4- , -O-, or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms). It is a 2- to 4-valent group composed of one or more.
R ³² , R ³⁴ , R ³⁵ and R ³⁶ are independently hydrogen atoms, monovalent organic groups, or halogen atoms, respectively.
Y ³¹ is -O- or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms).
p is 2 to 4,
q is 1 to 5. ]
It is preferably a monomer represented by.

The examples of R ³¹ and R ³³ are directly bonded, may be interrupted by an oxygen atom and / or have a hydrogen atom substituted with an OH group and have a 2- to 4-valent (eg, 2- to 3-valent) carbon number. 1 to 20 (or 2 to 10) hydrocarbon groups, ethylene glycol groups, propylene glycol groups, glycerol groups, cyclohexyl groups, dicyclopentanyl groups, adamantyl groups, isoboronyl groups, naphthalene groups, bornyl groups, tricyclodecanyl A group and a phenyl group, or a group containing any of these groups. R ³¹ and R ³³ may be a polymer group, and the structural unit constituting the polymer group may be the above-exemplified group (for example, an ethylene glycol group). R ³¹ and R ³³ are preferably divalent groups.

Y ³¹ is preferably —O— or —NH—.
R ³² , R ³⁴ , R ³⁵ and R ³⁶ may each independently be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Alternatively, it may be -CF ₃ units. Examples of R ³² , R ³⁴ , R ³⁵ and R ³⁶ are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, fluorine atom, -CF ₃ group and cyano group. R ³² , R ³⁴ , R ³⁵ and R ³⁶ are preferably hydrogen atoms, methyl groups, or chlorine atoms. It is more preferable that R ³² is a methyl group. Since R ³² is a methyl group, higher water repellency and higher water pressure resistance can be obtained. R ³⁴ , R ³⁵ and R ³⁶ are preferably hydrogen atoms, especially from the viewpoint of reactivity.

p may be 2 or 3, especially 2.
q may be 1 to 3, especially 1.

Specific examples of the crosslinkable monomer (II) are divinylbenzene, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth). Acrylate, Neopentylglycoldi (meth) acrylate, Polyethyleneglucoldi (meth) acrylate, Triethylolpropane di (meth) acrylate, Ethyleneglucoldi (meth) acrylate, Methyleneglucoldi (meth) acrylate, Poly Tetramethyleneglucol di (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, trimethylolpropane tri (meth) acrylate, adamantyldi (meth) acrylate, glycerindi (meth) acrylate, tricyclodecanedimethano- Ludi (meth) acrylate, dicyclopentanyldi (meth) acrylate, 5-hydroxy-1,3-adamantandi (meth) acrylate.

The crosslinkable monomer (II) is preferably a di (meth) acrylate compound or divinylbenzene.

(III) Reactive / hydrophilic monomer or short-chain hydrocarbon group-containing monomer Reactive / hydrophilic monomer (III) has one ethylenically unsaturated double bond and at least one reactivity. It has a group and / or a hydrophilic group. The short chain hydrocarbon group-containing monomer (III) has one ethylenically unsaturated double bond and at least one hydrocarbon group having 1 or 2 carbon atoms.
Examples of reactive groups are epoxy groups (eg, glycidyl groups), chloromethyl groups, bromomethyl groups, iodomethyl groups, blocked isocyanate groups.
Examples of hydrophilic groups are hydroxyl groups, amino groups (including those in which H bonded to N is converted to a methyl group, an ethyl group, a propyl group, or a butyl group), a carboxylic acid group, a sulfonic acid group, and a phosphoric acid. Group, carboxylic acid, sulfonic acid, alkali metal or alkaline earth metal base of phosphoric acid, chlorine or bromine, ammonium base with iodine ion as counter anion, ethylene glycol group, polyethylene glycol group, group having acetone skeleton (-C) (= O) -CH ₃ ).

The reactive / hydrophilic monomer (III) includes not only the above-mentioned reactive group and hydrophilic group, but also a compound having a group having a higher hydrophilicity than the hydrophobic monomer (I). The reactive / hydrophilic monomer (III) has an octanol / water partition coefficient that distributes more to water than the hydrophobic monomer (I), and has a reactive group and hydrophilicity as described above. Includes those that do not contain groups. For example, (meth) acrylamide having a short-chain hydrocarbon group having 6 or less carbon atoms in the side chain can be mentioned. Specifically, it is methyl (meth) acrylamide, ethyl (meth) acrylamide, n-butyl (meth) acrylamide, t-butyl (meth) acrylamide, propyl (meth) acrylamide, and isopropyl (meth) acrylamide.
The reactive / hydrophilic monomer (III) is preferably a non-fluorine monomer.

The reactive / hydrophilic monomer (III) has the formula:
CH ₂ = C (-R ⁴² ) -C (= O) -Y ^41- (R ⁴³ ) _o (R ⁴¹ ) _t
Or CH ₂ = C (-R ⁴⁵ ) -Y ^42- (H) _5-u (R ⁴⁴ ) _u
[In the formula, R ⁴¹ and R ⁴⁴ are independently reactive or hydrophilic groups, respectively.
R ⁴² and R ⁴⁵ are hydrogen atoms, monovalent organic groups, or halogen atoms.
Y ⁴¹ is a direct bond, -O-, or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms).
R ⁴³ is a group having a direct bond, —O—, or a hydrocarbon group having 2 to 4 valences of 1 to 10 carbon atoms (which may include a hydrocarbon moiety having an −OH group).
Y ⁴² is a benzene ring and
H is a hydrogen atom
H and R ⁴⁴ are directly coupled to Y ⁴² , respectively.
t and u are 1 to 3,
o is 0 or 1. ]
It is preferably a monomer represented by.

The short-chain hydrocarbon group-containing monomer (III) has the formula:
CH ₂ = C (-R ⁴⁷ ) -C (= O) -Y ⁴³ -R ⁴⁶
[In the formula, ^R46 is a hydrocarbon group having 1 or 2 carbon atoms.
R ⁴⁷ is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁴³ is a direct bond, -O-, or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms). ]
It is preferably a monomer represented by.

R ⁴¹ and R ⁴⁴ are monovalent bases. In R ⁴¹ and R ⁴⁴ , examples of reactive or hydrophilic groups are as described above (such as epoxy groups or hydroxyl groups).
R ⁴⁶ is a hydrocarbon group having 1 or 2 carbon atoms, and examples thereof include a methyl group and an ethyl group. Methyl groups are preferred.

R ⁴² , R ⁴⁵ and R ⁴⁷ may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group. Alternatively, it may be -CF ₃ units. Examples of R ⁴² , R ⁴⁵ and R ⁴⁷ are hydrogen atom, methyl group, chlorine atom, bromine atom, iodine atom, fluorine atom, -CF ₃ group and cyano group. R ⁴² , R ⁴⁵ and R ⁴⁷ are preferably hydrogen atoms, methyl groups and chlorine atoms. It is more preferable that R ⁴² and R ⁴⁷ are methyl groups. Since R ⁴² and R ⁴⁷ are methyl groups, higher water repellency and higher water pressure resistance can be obtained. R ⁴⁵ is preferably a hydrogen atom, particularly from the viewpoint of reactivity.
Y ⁴¹ and Y ⁴³ are preferably —O— or —NH—.

R ⁴³ is preferably a hydrocarbon group having 2 to 4 valences and 1 to 10 carbon atoms (may include a hydrocarbon moiety having an −OH group). Examples of 2- to tetravalent 1-carbon hydrocarbon groups are -CH _2- , having a branched structure-CH =, and having a branched structure-C≡. R ⁴³ is a divalent alkylene group, eg- (CH ₂ ) _r- (r is a number from 1 to 5), or a divalent, trivalent or tetravalent alkyl group, eg-(CH). ₂ ) _r- (CH-) _s -H (r is a number from 1 to 5, s is 1, 2 or 3. The positions of the CH ₂ and CH- groups do not have to be in the order described. .) Is preferable. A divalent alkylene group (for example, 1 to 4 carbon atoms) is more preferable.

Y ⁴² is a benzene ring. The monomer having Y ⁴² has a styryl group. In the monomer having Y ⁴² , 1 to 3 R ⁴⁴ groups and 2 to 4 hydrogen atoms are bonded to the benzene ring.

o is preferably 1.
t is preferably 1.
u may be 1 to 3, but is preferably 1 or 2.

Specific examples of the reactive / hydrophilic monomer (III) include glycidyl (meth) acrylate, glycerol (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and 3-hydroxypropyl (meth) acrylate. , 2-Hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) Acrylate, 2-hydroxybutyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth) acrylate, 2- (trimethylsilyloxy) ethyl (meth) ) Acrylate, 2- (dimethylamino) ethyl (meth) acrylate, 2- (tert-butylamino) ethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate quaternized product, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (Meta) acrylate, diacetone (meth) acrylamide, isopropyl (meth) acrylamide, t-butyl (meth) acrylamide, ethyl (meth) acrylamide, methyl (meth) acrylamide; and
4-Hydroxymethylstyrene, 4-hydroxyethylstyrene, 4-aminomethylstyrene, 4-aminoethylstyrene, 2- (4-vinylphenyl) oxylane, 2- (4-vinylbenzoyl) oxylane.

Specific examples of the short-chain hydrocarbon group-containing monomer (III) are methyl (meth) acrylate, ethyl (meth) acrylate, α-chloromethyl acrylate, and α-chloroethyl acrylate.

(IV) (Meta) Acrylic Monomer The (meth) acrylic monomer (IV) has a linear hydrocarbon group or a polydimethylsiloxane group having 3 to 40 carbon atoms.
The (meth) acrylic monomer (IV) may be a (meth) acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms.

The (meth) acrylic monomer (IV) has the formula:
CH ₂ = C (-R ⁵² ) -C (= O) -Y ⁵¹ (R ⁵¹ ) _s
[In the formula, R ⁵¹ is a linear hydrocarbon group having 3 to 40 carbon atoms independently.
R ⁵² is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁵¹ is a hydrocarbon group having 2 to 4 valences of 1 carbon atom (particularly -CH _2- , -CH = and -C≡), -C ₆ H _4- , -O-, -C (= O). -, -S (= O) ₂ -or-NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms) and is composed of at least one 2- to 4-valent group (R'is a hydrocarbon group having 1 to 4 carbon atoms). However, this is not the case with only divalent hydrocarbon groups).
s is 1 to 3. ]
It is preferably a monomer represented by.

R ⁵¹ is a linear hydrocarbon group. The carbon number of R ⁵¹ is preferably 12 to 24 or 16 to 22. Specific examples of R ⁵¹ are n-lauryl, n-stearyl, and n-behenyl.

s is 1, 2 or 3. s is preferably 1 or 2.

s is 1, 2 or 3. However, when Y ⁵¹ has a tetravalent hydrocarbon group having 1 carbon atom (specifically, —C≡ having a branched structure), s = 3. When Y ⁵¹ has a trivalent hydrocarbon group having 1 carbon atom (for example, −CH = having a branched structure), s = 2. When Y ⁵¹ does not have trivalent and tetravalent 1 carbon hydrocarbon groups (eg, Y ⁵¹ has divalent 1 carbon 1 hydrocarbon groups (-CH _2- ) (eg 1-6). If you have), s = 1.

R ⁵² may be a hydrogen atom, a methyl group, a halogen atom, a substituted or unsubstituted benzyl group, a substituted or unsubstituted phenyl group, or an —CF ₃ group. Examples of R ⁵² may be a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom, or a cyano group. R ⁵² is preferably a hydrogen atom, a methyl group or a chlorine atom. R ⁵² is more preferably a methyl group. Since R ⁵² is a methyl group, higher water pressure resistance can be obtained.

Y ⁵¹ is preferably a divalent group or a trivalent group, particularly a divalent group.
Examples of 2- to tetravalent 1-carbon hydrocarbon groups are -CH _2- , having a branched structure-CH =, and having a branched structure-C≡.

を有することが特に好ましい。 When Y ⁵¹ is a divalent group, it may or may not have —CH _2- . When Y ⁵¹ is a trivalent group, it preferably has a branched structure -CH =.
-CH _2- (-H (C-)-)-CH _2- ,
That is,

Is particularly preferable to have.

（２価）、
－ＣＨ_２－（－Ｈ（Ｃ－）－）－ＣＨ_２－ （３価）、
すなわち、

である。 Y ⁵¹ is -Y'-, -Y'-Y'-, -Y'-C (= O)-, -C (= O) -Y'-, -Y'-C (= O) -Y '-, -Y'-X'-, -Y'-X'-Y'-, -Y'-X'-Y'-C (= O)-, -Y'-X'-C (= O) ) -Y'-, -Y'-X'-Y'-C (= O) -Y'-, or -Y'-X'-Y'-X'-
[In the formula, Y'is an independent direct bond, -O-, -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms) or -S (= O) _2- . can be,
X'is-(CH ₂ ) _m- (m is an integer of 1-5), a linear hydrocarbon group with unsaturated bonds of 1-5 carbons, 1-5 or 3-5 carbons. A hydrocarbon group having a branched structure of, or-(CH ₂ ) _l -C ₆ H _4- (CH ₂ ) _l- (l is an independently integer of 0 to 5, and -C ₆ H _4- It is a phenylene group). ]
May be.
The hydrocarbon group having a branched structure having 3 to 5 carbon atoms may be divalent, trivalent or tetravalent. Specific examples of the hydrocarbon group having a branched structure having 3 to 5 carbon atoms are as follows.
-CH (CH ₃ ) -CH _2- (divalent),

(Divalent),
-CH _2- (-H (C-)-)-CH _2- (trivalent),
That is,

Is.

Specific examples of Y ⁵¹ , which is a divalent group, are -O-, -NH-, -OC (= O)-, -NH-C (= O)-, and -OC (= O)-. NH-, -NH-C (= O) -O-, -NH-C (= O) -NH-, -O-C _{6 H 4-, -NH-C 6 H 4- ,} -O- (CH) ₂ ) _m -O-, -NH- (CH _{2) m-NH-, -O- (CH 2) m-NH-, -NH- (CH 2 ) m - O- , -O-} (CH ₂ ) _m -OC (= O)-, -O- (CH ₂ ) _m -C (= O) -O-, -NH- (CH ₂ ) _m -OC (= O)-, -NH- (CH ₂ ) _m -C (= O) -O-, -O- (CH ₂ ) _m -OC (= O) -NH-, -O- (CH ₂ ) _m -NH-C (= O) ) -O-, -O- (CH ₂ ) _m -C (= O) -NH-, -O- (CH ₂ ) _m -NH-C (= O)-, -O- (CH ₂ ) _m- NH-C (= O) -NH-, -O- (CH ₂ ) _m -OC ₆ H _4- , -O- (CH ₂ ) _m -NH-S (= O) _2- , -O- (CH ₂ ) _m -S (= O) ₂ -NH-, -NH- (CH ₂ ) _m -NH-S (= O) _2- , -NH- (CH ₂ ) _m -S (= O) ₂ -NH-, -NH- (CH ₂ ) _m -OC (= O) -NH-, -NH- (CH ₂ ) _m -NH-C (= O) -O-, -NH- (CH ₂ ) ) _M -C (= O) -NH-, -NH- (CH ₂ ) _m -NH-C (= O)-, -NH- (CH ₂ ) _m -NH-C (= O) -NH-, -NH- (CH ₂ ) _m -OC ₆ H ₄ -or-NH- (CH ₂ ) _m -NH-C ₆ H _4- [In the formula, m is an integer from 1 to 5, especially 2 Or 4. ].

Y ⁵¹ , which is a divalent group, is -O-, -NH-, -O- (CH _{2) m-OC (= O)-, -O- (CH 2 ) m - NH} -C (=). O)-, -O- (CH ₂ ) _m -OC (= O) -NH-, -O- (CH ₂ ) _m -NH-C (= O) -O-, -O- (CH ₂ ) ) _M -NH-C (= O) -NH-, -O- (CH ₂ ) _m -NH-S (= O) ₂ -or -O- (CH ₂ ) _m -S (= O) ₂ -NH -, -NH- (CH ₂ ) _m -OC (= O)-, -NH- (CH ₂ ) _m -NH-C (= O)-, -NH- (CH ₂ ) _m -OC (= O) -NH-, -NH- (CH ₂ ) _m -NH-C (= O) -O-, -NH- (CH ₂ ) _m -NH-C (= O) -NH-
[In the formula, m is an integer from 1 to 5, especially 2 or 4. ]
Is preferable.

Y ⁵¹ , which is the basis of divalent, is -O-, -O- (CH ₂ ) _m -OC (= O) -NH-, -O- (CH ₂ ) _m -NH-C (= O). -O- or -O- (CH ₂ ) _m -NH-C (= O)-, -O- (CH ₂ ) _m -NH-S (= O) ₂ -or-O- (CH ₂ ) _m -S (= O) ₂ -NH-, especially -O- (CH ₂ ) _m -NH-C (= O)-
[In the formula, m is an integer from 1 to 5, especially 2 or 4. ]
Is more preferable. It is particularly preferable that Y ⁵¹ is —O—.

であることが好ましい。 Y ⁵¹ , which is the basis of trivalent, is

Is preferable.

Specific examples of the (meth) acrylic monomer (IV) having a linear hydrocarbon group having 3 to 40 carbon atoms are as follows.

［上記式中、ｎは３～４０の数であり、ｍは１～５の数である。］

[In the above formula, n is a number of 3 to 40 and m is a number of 1 to 5. ]

Preferred specific examples of the (meth) acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms are n-lauryl (meth) acrylate, n-stearyl (meth) acrylate, and n-behenyl (meth). Acrylate, amide ethyl stearate (meth) acrylate, n-lauryl (meth) acrylamide, n-stearyl (meth) acrylamide, n-behenyl (meth) acrylamide, CH ₂ = CHC (= O) OC ₂ H ₄ NHSO ₂ C ₁₈ H _37, CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) C ₁₇ H _35, CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) OC ₁₈ H ₃₇ , CH ₂ = CHC (= O) OC ₂ H ₄ OC (= O) NHC ₁₈ H ₃₇ , CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) NHC ₁₈ H ₃₇ . In the above structural formula, the α-position shows hydrogen acrylic and acrylamide, but the α-position also includes methyl methacrylic and methacrylamide.

The (meth) acrylic monomer (IV) may be a (meth) acrylic monomer having a polydimethylsiloxane group.
The (meth) acrylic monomer (IV) may have a polydimethylsiloxane group in the side chain.

The (meth) acrylic monomer (IV) has the formula:
CH ₂ = C (-R ⁶² ) -C (= O) -Y ⁶¹ -R ⁶¹
[In the formula, ^R61 is a group having a polydimethylsiloxane group.
R ⁶² is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁶¹ is a hydrocarbon group having 2 to 4 valences of 1 carbon atom, -C ₆ H _4- , -O-, -C (= O)-, -S (= O) _2- or -NR'-( R'is a 2- to 4-valent group composed of at least one selected from H or a hydrocarbon group having 1 to 4 carbon atoms). ]
It is preferably a monomer represented by.

R ⁶¹ is a group having a polydimethylsiloxane group, and has an average formula:
-(SiR ₂ O) _a SiR ₃
[In the formula, a is 2 to 4000, for example, 3 to 400.
Each R is independently a monovalent alkyl group having 1 to 12 carbon atoms, and at least two Rs are methyl groups. ]
It is preferably a group represented by.
R ⁶² is preferably a hydrogen atom, a methyl group or a chlorine atom.
Y ⁶¹ is a hydrocarbon group having 1 to 8 carbon atoms (for example, an alkylene group having 1 to 8 carbon atoms or 2 to 4 carbon atoms, particularly -C _{3H 6-} ), -O- (CH ₂ ) _p- , -O. -(CH ₂ ) _p -NHC (= O)-(CH ₂ ) _q- or -NH- (CH ₂ ) _q- (p is a number from 1 to 5, q is a number from 1 to 5). .) Is preferable.

［式中、ｎは１～５００の数である。］
である。 Specific examples of the (meth) acrylic monomer (IV) having a polydimethylsiloxane group include

[In the formula, n is a number from 1 to 500. ]
Is.

(V) Other Monomer A monomer (V) other than the monomer (I) to (IV) may be used.
Examples of other monomers (V) include, for example, ethylene, vinyl acetate, acrylonitrile, vinyl chloride, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and vinyl. Contains alkyl ether. Other monomers are not limited to these examples. The other monomer (V) is preferably a non-fluorine monomer.

As used herein, "(meth) acrylate" means acrylate or methacrylate, and "(meth) acrylamide" means acrylamide or methacrylamide.

Each of the monomers (I) to (V) may be a single type or a mixture of two or more types.

In the present disclosure, the preferred combinations of monomers in the polymer are as follows.
Monomer (I) + Monomer (II)
Monomer (I) + Monomer (III)
Monomer (I) + Monomer (II) + Monomer (III)
Monomer (I) + Monomer (II) + Monomer (IV)
Monomer (I) + Monomer (III) + Monomer (IV)
Monomer (I) + Monomer (II) + Monomer (III) + Monomer (IV)

Particularly preferred combinations are as follows. Monomer (I) + Monomer (II)
Monomer (I) + Monomer (III)
Monomer (I) + Monomer (II) + Monomer (III)
Monomer (I) + Monomer (II) + Monomer (IV)
Monomer (I) + Monomer (II) + Monomer (III) + Monomer (IV)
Each of the above-mentioned monomers may be of only one type or may be two or more types. For example, a combination of two types of monomer (I), one type of monomer (II), and one type of monomer (III) may be used.

In the polymer, the amount of the hydrophobic monomer (I) may be 40 to 100% by weight, 50 to 99% by weight, 55 to 98% by weight or 58 to 97% by weight with respect to the polymer.
In the polymer, the molar ratio of the hydrophobic monomer (I) / reactive / hydrophilic monomer and / or the short-chain hydrocarbon group-containing monomer (III) is 50/50 to 100/0, 80. / 20-99.5 / 0.5, 85/15-98 / 2 or 90/10-99 / 1, or 40/60-90 / 10, 55/45-85/15, 58/42-80 / It may be 20 or 60/40 to 78/22.
The amount of the crosslinkable monomer (II) is 100 mol in total of the hydrophobic monomer (I), the reactive / hydrophilic monomer and / or the short-chain hydrocarbon group-containing monomer (II). It may be 0 to 30 mol, 0.5 to 25 mol or 1 to 20 mol, or 0 to 15 mol, 0.2 to 10 mol or 0.5 to 5 mol.
The amount of the (meth) acrylic monomer (IV) is 100 mol in total of the hydrophobic monomer (I), the reactive / hydrophilic monomer and / or the short-chain hydrocarbon group-containing monomer (II). It may be 0 to 60 mol, 0.5 to 40 mol, 1 to 30 mol, or 1 to 20 mol.
The amount of the other monomer (V) may be 0-30 mol, 0.5-25 mol, 1-20 mol or 1-10 mol with respect to 100 mol in total.

Alternatively, for 100 mol of polymer
Hydrophobic monomer (I) is 40-99.5 mol, 50-99 mol or 60-99 mol,
Crosslinkable monomer (II) is 0-30 mol, 0.5-25 mol or 1-20 mol, or 0-10 mol, 0.2-6 mol or 0.5-4 mol,
Reactive / hydrophilic monomers and / or short-chain hydrocarbon group-containing monomers (III) are 0-50 mol, 0.5-40 mol or 1-20 mol, or 0-15 mol, 0. 2-10 mol or 0.5-5 mol,
The (meth) acrylic monomer (IV) is 0 to 50 mol, 1 to 40 mol or 1 to 30 mol, or 0 to 15 mol, 0.2 to 10 mol or 0.5 to 5 mol,
May be.
In the absence of the monomer (II), the high Tg monomer (Ia) of the monomer (I) may be 1-80 mol, 2-70 mol, or 5-60 mol.

The water-repellent polymer may be a random polymer or a block copolymer, but is preferably a random polymer.

The amount of the organic fine particles (A) is 50% by weight or less, for example, 0.01 to 40% by weight, particularly 0.05 to 30% by weight or 0.1 to 20% by weight, based on the water pressure resistance improving agent composition. It's okay.

(B) Aqueous medium The water pressure resistant improving agent composition (or water repellent composition) contains an aqueous medium. The aqueous medium is water, or a mixture of water and an organic solvent.
The water repellent composition is generally an aqueous dispersion in which the polymer is dispersed in an aqueous medium (water or a mixture of water and an organic solvent).
The aqueous medium may be water alone or a mixture of water and a (miscible) organic solvent. The amount of the organic solvent may be 30% by weight or less, for example, 10% by weight or less with respect to the liquid medium. The aqueous medium is preferably water alone.
The amount of the aqueous medium may be 50 to 99.5 parts by weight, particularly 70 to 99.5 parts by weight, when the total amount of the water-repellent polymer and the aqueous medium is 100 parts by weight.

(C) Binder resin The binder resin acts as a binder for binding organic fine particles to a base material. A water-repellent resin is preferable as the binder resin. The water-repellent resin also acts as an active ingredient that exhibits water repellency. Examples of binder resins are acrylic polymers, urethane polymers, polyolefins, polyesters, polyethers, polyamides, polyimides, polystyrenes and silicone polymers.
The water-repellent resin is a non-fluorine polymer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain, or a fluorine-containing polymer having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain. The water-repellent resin is preferably a non-fluorine polymer.
In a non-fluorine polymer having a hydrocarbon group having 3 to 40 carbon atoms, the hydrocarbon group is preferably a branched hydrocarbon group or a long-chain (or long-chain linear) hydrocarbon group.
Examples of water-repellent resins are urethane polymers, silicone polymers, acrylic polymers, and polystyrene.
An example of a non-fluorinated polymer is an amidoamine dendrimer having a long chain hydrocarbon group, which is described in US Pat. No. 8,703,894. The disclosure of this document is incorporated herein by reference.

Urethane polymers having a hydrocarbon group having 3 to 40 carbon atoms in the side chain include, for example, an isocyanate group-containing compound (for example, monoisocyanate or polyisocyanate, specifically diisocyanate or triisocyanate) and 3 to 40 carbon atoms. It can be produced by reacting a hydroxyl group-containing compound having a hydrocarbon group of.
Polyurethanes having a branched structure such as a t-butyl group, an isopropyl group, a 2,6,8-trimethylnonan-4-yl group on the side chain may be, for example, an isocyanate group-containing compound (for example, monoisocyanate or polyisocyanate, specifically. Can be produced by reacting diisocyanate or triisocyanate) with a hydroxyl group-containing compound having a branched structure such as a t-butyl group, an isopropyl group, and a 2,6,8-trimethylnonan-4-yl group.
Examples of urethane polymers include sorbitan tristearate, sorbitan monostearate, and urethane compounds having long-chain hydrocarbon groups comprising polyfunctional isocyanurates, which are described in US Patent Publication 2014/0295724. The disclosure of this document is incorporated herein by reference. An example of a urethane polymer is polyurethane having a long-chain hydrocarbon group, which is described in Japan Special Table 2019-519653 (International Publication 2018/007549). The disclosure of this document is incorporated herein by reference.

A silicone polymer having a hydrocarbon group having 3 to 40 carbon atoms in a side chain can be produced, for example, by reacting with a dichlorosilane compound containing dichlorosilane having a hydrocarbon group having 3 to 40 carbon atoms.
Polysilicone having a branched structure such as t-butyl group, isopropyl group, 2,6,8-trimethylnonan-4-yl group in the side chain is, for example, t-butyl group, isopropyl group, 2,6,8-. It can be produced by reacting a dichlorosilane compound containing a dichlorosilane having a branched structure such as a trimethylnonan-4-yl group.
Examples of silicone polymers include long-chain alkyl-modified polydimethylsiloxane.

（特に、ステアリン酸アミドエチル（メタ）アクリレート）
［上記式中、ｎは７～４０の数であり、ｍは１～５の数である。］
である。 An acrylic polymer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain can be produced by polymerizing a monomer containing an acrylic monomer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain. Examples of acrylic monomers are similar to those described for Hydrophobic Monomers (IV) above. Specific examples of the acrylic monomer include, for example,
Stearyl (meth) acrylate, behenyl (meth) acrylate,

(In particular, amide ethyl stearate (meth) acrylate)
[In the above formula, n is a number of 7 to 40 and m is a number of 1 to 5. ]
Is.

Acrylic polymers having a branched structure such as a t-butyl group, an isopropyl group, a 2,6,8-trimethylnonan-4-yl group on the side chain have a t-butyl group, an isopropyl group, 2,6 on the side chain. It can be produced by polymerizing a monomer containing an acrylic monomer having a branched structure such as 8-trimethylnonan-4-yl group. Examples of the acrylic monomer are the same as those described for the hydrophobic monomer (I) above. Specific examples of the acrylic monomer are, for example, t-butyl (meth) acrylate, isopropyl (meth) acrylate, and 2,6,8-trimethylnonane-4-yl-acrylate.

Examples of acrylic polymers include repeating units derived from acrylic monomers having long-chain hydrocarbon groups such as behenyl (meth) acrylates and stearyl (meth) acrylates, and vinylidene chloride and / or vinyl chloride. There are polymers containing repeating units.
Examples of acrylic polymers include repeating units derived from acrylic monomers having long-chain hydrocarbon groups such as behenyl (meth) acrylate and stearyl (meth) acrylate, and derived from vinylidene chloride and / or vinyl chloride. There is a polymer containing a repeating unit and a repeating unit derived from styrene or α-methylstyrene, and this acrylic polymer may be mixed with paraffin wax and used. An example of this is described in Japan Special Table 2012-52062 (International Publication 2010/115496). The disclosure of this document is incorporated herein by reference.
Examples of acrylic polymers include repeating units derived from acrylic monomers having long-chain hydrocarbon groups such as stearyl (meth) acrylate, repeating units derived from vinylidene chloride and / or vinyl chloride, and poly. There are polymers containing repeating units derived from reactive emulsifiers such as oxyalkylene alkenyl ethers, which are described in Japanese Patent Application Laid-Open No. 2017-25440 (International Publication 2017/014131). The disclosure of this document is incorporated herein by reference.

In the fluorine-containing polymer having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain, the fluoroalkyl group is preferably a perfluoroalkyl group.
Examples of the fluorine-containing water-repellent resin include (meth) acrylate having a perfluoroalkyl group having 4 to 8 carbon atoms in the side chain and long-chain alkyl (meth) acrylate such as behenyl (meth) acrylate and stearyl (meth) acrylate. There are fluoroacrylic polymers containing repeating units formed from.
Other monomers may be used for the urethane polymer, the silicone polymer, the acrylic polymer, and the polystyrene of the non-fluorine polymer and the fluorine-containing polymer.
Examples of other monomers include, for example, ethylene, vinyl acetate, acrylonitrile, vinyl chloride, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth). Includes acrylates, (meth) acrylates with polydimethylsiloxanes on the side chains, and vinyl alkyl ethers. Other monomers are not limited to these examples.

The weight ratio of the binder resin (C) / organic fine particles (A) is 1/99 to 99/1, 20/80 to 99/1 or 30/70 to 95/5, for example, 55/45 to 90/10. It's okay. The amount of the binder resin (C) is preferably 30 to 99% by weight, preferably 50 to 98% by weight, more preferably 60 to 97% by weight, based on the total weight of the binder resin (C) and the organic fine particles (A). preferable.

(D) Surfactant The water repellent composition may or may not contain a surfactant (emulsifier). Generally, in order to stabilize the particles during polymerization and the aqueous dispersion after polymerization, a small amount of surfactant is added at the time of polymerization (for example, 0.01 to 30 parts by weight with respect to 100 parts by weight of the monomer). May be added in, or a surfactant may be added after the polymerization.
Especially when the object to be treated is a textile product, it is preferable that the surfactant contains a nonionic surfactant in the water-repellent composition. Further, the surfactant preferably contains one or more surfactants selected from a cationic surfactant, an anionic surfactant, and an amphoteric surfactant. It is preferable to use a combination of a nonionic surfactant and a cationic surfactant.

Each of the nonionic surfactant, the cationic surfactant, and the amphoteric surfactant may be one kind or a combination of two or more.
The amount of the surfactant is 30 parts by weight or less (for example, 0 to 15 parts by weight or 0.01 to 15 parts by weight), preferably 15 parts by weight or less (for example, 0) with respect to 100 parts by weight of the organic fine particles (A). .1 to 10 parts by weight). Generally, when a surfactant is added, the stability of the aqueous dispersion and the permeability to the cloth are improved, but the water repellency is lowered. It is preferable to select the type and amount of the surfactant so as to achieve both of these effects.

(E) Cross-linking agent The cross-linking agent (E) is preferably one that cross-links when the aqueous dispersion of organic fine particles is treated on a cloth and then heated. Further, it is preferable that the cross-linking agent itself is also dispersed in water.

A preferred example of the cross-linking agent (E) is a blocked isocyanate compound. The blocked isocyanate compound is
[A (NCO) _m (in the formula, A is a group remaining after the isocyanate group is removed from the polyisocyanate, and m is an integer of 2 to 8)] Isocyanate is [RH (formula). Among them, R may be a hydrocarbon group which may be substituted with a hetero atom such as a nitrogen atom or an oxygen atom, and H may be a hydrogen atom)] produced by reacting with a blocking agent. can do.

A (NCO) _m is, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), or the like.
Examples of blocking agents that form R groups are oximes, phenols, alcohols, mercaptans, amides, imides, imidazoles, ureas, amines, imines, pyrazoles and active methylene compounds.

As the cross-linking agent (E), blocked isocyanates such as oxime blocked toluene diisocyanate, blocked hexamethylene diisocyanate, and blocked diphenylmethane diisocyanate are preferable.
The amount of the cross-linking agent (E) is 0 to 30 parts by weight or 0.01 to 20 parts by weight, for example 0.1 to 18 parts by weight, based on 100 parts by weight of the total of the organic fine particles (A) and the binder resin (C). It may be a department.

(F) The additive water repellent composition is added to the organic fine particles (A) and the aqueous medium (B), and optionally the binder resin (C), the surfactant (D) and / or the cross-linking agent (E). , Additive (F) may be contained.
Examples of additives are other water repellents, oil repellents, drying rate regulators, film forming aids, compatibilizers, antifreeze agents, viscosity regulators, UV absorbers, antioxidants, pH regulators, extinguishing agents. Foaming agents, texture regulators, slip property regulators, antistatic agents, hydrophilic agents, antibacterial agents, preservatives, insect repellents, fragrances, flame retardants, etc.
The amount of the additive is 0 to 20 parts by weight or 0.05 to 20 parts by weight, for example 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the organic fine particles (A) and the binder resin (C). It's okay.

The polymer (polymer constituting organic fine particles and polymer constituting the binder resin) can be produced by any of ordinary polymerization methods, and the conditions of the polymerization reaction can be arbitrarily selected. Examples of such a polymerization method include solution polymerization, suspension polymerization, and emulsion polymerization. Emulsion polymerization is preferred.
The organic fine particles are preferably produced by emulsion polymerization from the viewpoint of ease of synthesis and stability of the fine particles.

As long as a water repellent composition in the form of an aqueous dispersion is obtained, the method for producing the polymer is not limited. For example, a polymer (organic fine particles) may be produced by polymerizing a monomer for organic fine particles in an aqueous medium in the presence or absence of a surfactant. Alternatively, after the polymer is produced by solution polymerization, an aqueous dispersion can be obtained by adding a surfactant and water and removing the solvent.

When the water repellent composition contains organic fine particles and a binder resin, the production of the aqueous dispersion of the organic fine particles and the production of the aqueous dispersion of the binder resin are performed separately, and the water dispersion of the organic fine particles and the binder resin are produced separately. By mixing with an aqueous dispersion, a water repellent composition containing organic fine particles and a binder resin can be produced. Alternatively, a water repellent composition containing the organic fine particles and the binder resin can be produced by polymerizing the monomer for the binder resin in the aqueous dispersion of the organic fine particles. Further, by polymerizing a monomer for organic fine particles in an aqueous dispersion of a binder resin, a water repellent composition containing the organic fine particles and the binder resin can be produced.

In emulsion polymerization without a surfactant, it is preferable to polymerize the monomer at a low concentration (for example, monomer concentration 1 to 30% by weight, particularly 1 to 15% by weight) in an aqueous medium.

In emulsion polymerization using a surfactant or a reactive emulsifier, a small amount (single) of a monomer (IV) having a static contact angle of 90 degrees or more for water of a homopolymer among the monomers (I) is used. It is preferable to add 30 mol parts or less, for example, 0.1 to 20 mol parts) to 100 mol parts of the whole polymer. As a result, polymerization can be carried out at a high concentration, and the water repellency of the polymer becomes high.
Examples of monomers to be added are t-butylstyrene, stearyl (meth) acrylate, behenyl (meth) acrylate, stearyl (meth) acrylamide, 2,6,8-trimethylnonan-4-yl-acrylate, 2, 4-di t-butyl styrene, 2,4,6-trimethylstyrene, amide ethyl stearate (meth) acrylate, CH ₂ = CHC (= O) OC ₂ H ₄ NHSO ₂ C ₁₈ H _37, 4-t-butyl phenyl A (meth) acrylic monomer having (meth) acrylate, 2,3,4-methylphenyl (meth) acrylate, cyclohexyl (meth) acrylate, isoboronyl (meth) acrylate, and polydimethylsiloxane group.
CH ₂ = C (-R ⁶² ) -C (= O) -Y ⁶¹ -R ⁶¹
[In the formula, ^R61 is a group having a polydimethylsiloxane group.
R ⁶² is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁶¹ is a hydrocarbon group having 2 to 4 valences of 1 carbon atom, -C ₆ H _4- , -O-, -C (= O)-, -S (= O) _2- or -NR'-( R'is a 2- to 4-valent group composed of at least one selected from H or a hydrocarbon group having 1 to 4 carbon atoms). ]
It is a monomer represented by.

In solution polymerization, a method of dissolving a monomer in an organic solvent in the presence of a polymerization initiator, substituting with nitrogen, and then heating and stirring in the range of 30 to 120 ° C. for 1 to 10 hours is adopted. Examples of the polymerization initiator include azobisisobutyronitrile, benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, cumene hydroperoxide, t-butylperoxypivalate, diisopropylperoxydicarbonate and the like. Can be mentioned. The polymerization initiator is used in the range of 0.01 to 20 mol parts, for example, 0.01 to 10 mol parts with respect to 100 mol parts of the monomer.

The organic solvent is inert to the monomer and dissolves or uniformly disperses them. For example, an ester (for example, an ester having 2 to 30 carbon atoms, specifically, ethyl acetate or butyl acetate) or a ketone. (For example, a ketone having 2 to 30 carbon atoms, specifically, a methyl ethyl ketone or a diisobutyl ketone), an alcohol (for example, an alcohol having 1 to 30 carbon atoms, specifically, isopropyl alcohol, ethanol, methanol) may be used. .. Specific examples of the organic solvent include acetone, chloroform, HCHC225, isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, and the like. Examples thereof include diisobutylketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichlorethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane. Assuming that the total of the monomer and the organic solvent is 100 parts by weight, the organic solvent is used in the range of 50 to 99.5 parts by weight, for example, 60 to 99 parts by weight.

In emulsion polymerization, a method is adopted in which a monomer is emulsified in water in the presence of a polymerization initiator and an emulsifier, substituted with nitrogen, and then stirred and polymerized in the range of 30 to 80 ° C. for 1 to 10 hours. The polymerization initiators are benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, 1-hydroxycyclohexylhydro peroxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutyamidine-dihydrochloride, 2 , 2'-azobis (2-methylpropion amidine) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propion Amid], 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], peroxide Water-soluble substances such as sodium, potassium persulfate, and ammonium persulfate, azobisisobutyronitrile, benzoyl peroxide, dit-butyl peroxide, lauryl peroxide, cumene hydroperoxide, and t-butyl peroxypivalate. , Diisopropyl peroxydicarbonate and other oil-soluble substances are used. The polymerization initiator is used in the range of 0.01 to 10 mol parts with respect to 100 mol parts of the monomer. If necessary, a reducing agent such as longalit, ascorbic acid, tartaric acid, sodium sulfite, isoascorbic acid, and ferrous sulfate may be used in combination.

As the emulsifier, various anionic, cationic or nonionic emulsifiers can be used, and they are used in the range of 0.5 to 30 parts by weight with respect to 100 parts by weight of the monomer. It is preferred to use anionic and / or nonionic and / or cationic emulsifiers. When the monomers are not completely compatible, it is also preferable to add a compatibilizer, for example, a water-soluble organic solvent, which is sufficiently compatible with these monomers. It is possible to improve emulsifying property and copolymerizability by adding a compatibilizer.

Examples of the water-soluble organic solvent include acetone, methyl ethyl ketone, ethyl acetate, propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, isopropanol, ethanol, methanol and the like. . It may be used in the range of 1 to 50 parts by weight, for example, 1 to 40 parts by weight.

A chain transfer agent may be used in the polymerization. The molecular weight of the polymer can be changed according to the amount of the chain transfer agent used. Examples of chain transfer agents are mercaptan group-containing compounds such as lauryl mercaptan, thioglycol, thioglycerol (particularly alkyl mercaptan (eg, 1-30 carbon atoms)), inorganic salts such as sodium hypophosphite, sodium bisulfite. And so on. The amount of the chain transfer agent used may be in the range of 0.01 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total amount of the monomers.

The water repellent composition is generally preferably an aqueous dispersion. The water repellent composition comprises a polymer (active ingredient of the water repellent composition) and an aqueous medium. The amount of the aqueous medium may be, for example, 50-99.9% by weight, particularly 70-99.5% by weight, based on the water repellent composition.
In the water repellent composition, the concentration of the polymer may be 0.1 to 50% by weight, for example 0.5 to 40% by weight.

The water repellent composition (and the aqueous dispersion of organic fine particles) can be used as an external treatment agent (surface treatment agent) or an internal treatment agent. The water repellent composition (and the aqueous dispersion of organic fine particles) can be used as an oil repellent, an antifouling agent, a stain remover, a release agent or a mold release agent.

When the water repellent composition is an external treatment agent, it can be applied to the object to be treated by a conventionally known method. Usually, the water repellent composition is dispersed in an organic solvent or water, diluted, and adhered to the surface of the object to be treated by a known method such as dip coating, spray coating, foam coating and the like, and dried. Is taken. If necessary, it may be applied together with a suitable cross-linking agent (for example, blocked isocyanate) for curing. Further, it is also possible to add an insect repellent, a softener, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent and the like to the water repellent composition and use them in combination. The concentration of the polymer in the treatment liquid to be brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example, 0.05 to 10% by weight.

The object to be treated with the water repellent composition (and the aqueous dispersion of organic fine particles) is preferably one that is required to have water pressure resistance. Examples of objects to be treated include textiles, paper, wood, leather, fur and the like. Various examples can be given as textile products. For example, animal and vegetable natural fibers such as cotton, hemp, wool and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride and polypropylene, semi-synthetic fibers such as rayon and acetate, glass fibers and carbon fibers. , Inorganic fibers such as asbestos fibers, or mixed fibers thereof.

The textile product may be in any form such as fiber or cloth.
The water repellent composition can also be used as an antifouling agent, a release agent, and a mold release agent (for example, an internal mold release agent or an external mold release agent). For example, the surface of the substrate can be easily stripped from another surface (another surface on the substrate or a surface on another substrate).

The organic microparticles can be applied to fibrous substrates (eg, textile products) by any of the methods known for treating textile products with liquids. When the textile product is a cloth, the cloth may be dipped in the solution, or the solution may be attached or sprayed on the cloth. The treated textile product is dried and preferably heated at, for example, 100 ° C. to 200 ° C. in order to develop water repellency.

Alternatively, the organic fine particles may be applied to the textile product by a cleaning method, and may be applied to the textile product by, for example, a washing application or a dry cleaning method.

The textile products to be processed are typically fabrics, which include textiles, knitted fabrics and non-woven fabrics, fabrics and carpets in the form of clothing, but textiles or yarns or intermediate textile products (eg, sliver or Coarse yarn, etc.) may be used. The textile material may be a natural fiber (eg, cotton or wool), a synthetic fiber (eg, biscorayon or leocell), or a synthetic fiber (eg, polyester, polyamide or acrylic fiber), or , A mixture of fibers (eg, a mixture of natural and synthetic fibers, etc.).

Alternatively, the fibrous substrate may be leather. Aqueous or aqueous emulsions of organic particulates to make the leather hydrophobic and oleophobic at various stages of leather processing, for example during the wet processing of the leather or during the finishing of the leather. May be applied to leather.
Alternatively, the fibrous substrate may be paper. The organic particles may be applied to preformed paper or at various stages of papermaking, for example during the drying period of the paper.

Organic fine particles can be used in applications where water pressure resistance is required. Particularly preferred applications are fabrics for outdoor equipment, cloths for sports equipment, cloths for raincoats and other rain gear, medical cloths, especially non-woven fabrics, such as medical surgical gowns, protective clothing, awnings, especially shades and tents. And so on.

"Treatment" means applying the treatment agent to the object to be treated by dipping, spraying, coating or the like. By the treatment, the organic fine particles which are the active ingredients of the treatment agent adhere to the object to be treated. By the treatment, the organic fine particles permeate the inside of the object to be treated and / or adhere to the surface of the object to be treated.

Although the embodiments have been described above, it will be understood that various modifications of the embodiments and details are possible without departing from the spirit and scope of the claims.

Hereinafter, the present disclosure will be described in detail with reference to examples, but the present disclosure is not limited to these examples.
In the following, parts or% or ratios represent parts by weight or% by weight or ratios by weight unless otherwise specified.
The test procedure is as follows.

[Falling speed test]
In the falling speed test, a PET cloth (grain: 88 g / m ² , 70 denier, gray) is dipped in an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin, passed through a mangle, and passed at 170 ° C. 1 Pass it through a pin tenter for a minute, prepare a PET cloth with organic fine particles attached, and drop 20 μL of water from a microsyringer onto the PET cloth with an inclination of 30 ° using a fully automatic contact angle meter (DropMaster701 manufactured by Kyowa Surface Science). The state of the dropped water falling was measured using a high-speed camera (VW-9000 manufactured by Keyence Co., Ltd.), and the average falling speed at a distance of about 40 mm was taken as the falling speed.

[Contact angle measurement]
The static contact angle of water of a cloth (PET cloth) treated with an aqueous dispersion of organic fine particles or a composition containing organic fine particles and a binder resin is organic for PET cloth (grain: 88 g / m ² , 70 denier, gray). After immersing in an aqueous dispersion of fine particles or a composition containing organic fine particles and a binder resin, the PET cloth is passed through a mangle and a pin tenter at 170 ° C. for 1 minute to prepare a PET cloth to which the organic fine particles are attached, and 2 μL is placed on the PET cloth. The static contact angle 1 second after the drip was dropped, and the static contact angle was measured using a fully automatic contact angle meter (DropMaster701 manufactured by Kyowa Surface Science Co., Ltd.). The contact angle of the organic fine particles on the cloth (PET cloth) is preferably 120 ° or more, more preferably 130 ° or more, still more preferably 140 ° or more.
For the contact angle of the aqueous dispersion of the binder resin, the aqueous dispersion of the binder resin was drop cast onto a glass substrate (made of slide glass soda lime glass) and heated at 150 ° C. for 3 minutes to prepare a coating film. 2 μL of water was dropped onto the coating film, and the static contact angle 1 second after the drip was measured using a fully automatic contact angle meter (DropMaster701 manufactured by Kyowa Interface Science Co., Ltd.).

[Measurement of solid content]
1 g of the obtained aqueous dispersion of organic fine particles was placed in an aluminum cup and dried at 150 ° C. for 1 hour. The solid content was calculated from the weight before and after drying.

Solid content% = (weight before drying-weight after drying) / weight before drying x 100

[Water repellency test]
An aqueous dispersion of organic fine particles was prepared to a predetermined concentration, the cloth was dipped in this test solution, passed through a mangle, and the water repellency was evaluated with the heat-treated test cloth. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). As shown in the table below, the water repellent No. Represented by. The higher the score, the better the water repellency. A "+" attached to a number means that it is better than that number, and a "-" means that it is worse than that number. Evaluation was performed using a polyester cloth (PET) (weight: 88 g / m ² , 70 denier, gray).
The water repellency test is preferably 80 points or more or 90 points or more.

[Strong water repellency test]
When tested by the spray method of JIS-L-1092 (AATCC-22), the easiness of repelling water in contact with the cloth and the speed of running off the cloth were visually evaluated. The higher the score, the better the strong water repellency.

[Water pressure resistance test]
The test was carried out according to AATCC 127, and the water pressure resistance was measured.
The water pressure resistance test device used was a water resistance measuring instrument PHL-5000 (DAIEI KAGAKU SEIKI), and the part of the test piece that came into contact with water was 100 cm ² in size. Ion-exchanged water or equivalent water was used, and the temperature at the time of the test was 21 ° C ± 2 ° C. Attach the test piece to the water resistance test device so that the front side of the test piece hits the water, raise the water level at a speed of 600 mm / mm ± 30 mm / mm with a level device filled with water, and water comes from three places on the back side of the test piece. The water level at the time of exit was measured in mm.
The water pressure resistance is preferably higher than that when the organic fine particles are not applied, and the water pressure resistance value is improved by 3%, for example, 5%, and further 10% as compared with the water pressure resistance of the cloth when the organic fine particles are not applied. Is preferable.

[Measurement of particle size of dispersion]
For dynamic light scattering (DLS) measurement, NANOSAQLA manufactured by Otsuka Electronics Co., Ltd. was used to determine the average diameter of particles in the dispersion. The aqueous dispersion of organic fine particles was diluted with pure water to a solid content concentration of 0.1% and measured at 25 ° C. The particle size distribution was analyzed based on the scattering intensity.

[Water repellency and strong water repellency washing durability (water repellency (after washing) and strong water repellency (after washing))]
Washing according to the JIS L-0217-103 method is repeated 20 times, and the subsequent water repellency and strong water repellency are evaluated. After washing, it is preferable that the water repellency is 80 points or more and the strong water repellency is 2 points or more.

In the examples and comparative examples, the meanings of the abbreviations are as follows.
tBuMA: t-butyl methacrylate iBMA: isobornyl methacrylate CHMA: cyclohexyl methacrylate StA: stearyl acrylate DVB: divinylbenzene GMA: glycidyl methacrylate MMA: methyl methacrylate MAA: methacrylic acid DAAM: diacetone acrylamide NIPAM: isopropylacrylamide tBuAam: t-butyl Acrylamide DM4: Diaceaminoethyl methacrylate quaternized product (methyl chloride)
DM: 2-Dimethylaminoethyl methacrylate HBA: 4-Hydroxybutyl acrylate tBuAEMA: t-butylaminoethyl methacrylate EGDMA: Ethylene glycol dimethacrylate NPDMA: Neopentylglucol dimethacrylate GDMA: Glycerin dimethacrylate TMPTMA: Trimethylol propanetrimethacrylate NGDA : Nonanediol diacryllate emulsifier 1: Polyethylene glycol monooleyl ether (liquid)
Emulsifier 2: Stearyltrimonium chloride emulsifier 3: Setrimonium chloride emulsifier 4: Pooxyalkylene alkenyl ether (HLB13)
Crosslinker 1: Oxime blocked toluene diisocyanate Crosslinker 2: Blocked diphenylmethane diisocyanate

<Synthesis example B1>
Tripropylene glycol 30 g, CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) C ₁₇ H ₃₅ (C17AEA) 45 g, StA 34 g, N-alkyrole acrylamide 1 g, trialkylammonium chloride 2 g in a 500 ml plastic container. , Sorbitane monoalchelate 2 g, polyoxyethylene trialkyl ether 2.5 g, polyoxyethylene alkyl ether 3.5 g, pure water 180 g, stirred at 80 ° C. with a homomixer at 2000 rpm for 1 minute, and ultrasonically for 15 minutes. Dispersed. The emulsion dispersion was transferred to an autoclave, and after nitrogen substitution, 0.2 g of alkyl mercaptan and 20 g of vinyl chloride were added, 1 g of an azo-based initiator was added, and the mixture was heated and stirred at 60 ° C. for 20 hours to obtain an aqueous dispersion of a polymer. .. The contact angle of water in the film obtained by applying the emulsified dispersion to the glass substrate was 109 °.

<Synthesis example B2>
Put 28.9 g of sorbitan tristearate, 0.31 g of sorbitan monostearate, 7.5 g of hexamethylene triisocyanate (biuret), 37.5 g of methyl isobutyl ketone, and 0.03 g of dibutyltin laurate in a nitrogen-substituted reaction vessel. It was heated and stirred at ° C. 9 g of tripropylene glycol, 1.8 g of sorbitan tristearate, 0.75 g of polyethylene glycol monooleyl ether, 0.6 g of trimethyloctadecylammonium chloride, and 40 g of pure water were added to this solution and stirred. Methyl isobutyl ketone was removed by an evaporator to obtain an aqueous dispersion of a reaction product of sorbitan stearate and isocyanate. Further, an aqueous dispersion of a long-chain alkyl-modified polydimethylsiloxane wax was added to obtain an aqueous dispersion of the mixture. The contact angle of water in the film in which the dispersion was applied to the glass substrate was 105 °.

<Synthesis example B3>
CF ₃ CF _2- (CF ₂ CF ₂ ) _n -CH ₂ CH ₂ OCOC (Cl) = CH ₂ (n = 2.0) 39.53g, CF ₃ CF _2- (CF ₂ CF ₂ ) _n -CH ₂ in 1000mL autoclave CH ₂ OCOCH = CH ₂ (n = 2.0) 79.29 g, stearyl acrylate 46.01 g, pure water 415 g, water-soluble glycol solvent 60 g, polyoxyethylene oleyl ether 15.8 g, polyoxyethylene alkyl ether 4.75 g, and stir. It was emulsified and dispersed under ultrasonic waves at 60 ° C. for 15 minutes. After replacing the inside of the container with nitrogen, 50 g of vinyl chloride (VCM) was press-filled, 0.4 g of an azo group-containing water-soluble initiator was added, and the mixture was reacted at 60 ° C. for 20 hours to obtain an aqueous dispersion of the polymer. The composition of the polymer was almost the same as the composition of the charged monomer.

<Synthesis example 1>
0.39 g of t-butyl methacrylate (tBuMA), 0.16 g of glycidyl methacrylate (GMA), 0.37 g of isoboronyl methacrylate (iBMA), 0.072 g of divinylbenzene (DVB), polyethylene glycol mono in a reaction vessel substituted with nitrogen. 43 mg of oleyl ether (liquid), 1.5% by weight of stearyltrimonium chloride with respect to all the monomers, and 19 ml of pure water were added and dispersed. After nitrogen substitution, 15.1 mg of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65 ° C. for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content was 4.71%. The particle size (average particle size) of the aqueous dispersion was 71.1 nm.
<Example 1>
The aqueous dispersion of the organic fine particles of Synthesis Example 1 and the aqueous dispersion of Synthesis Example B1 are prepared so that the organic fine particles of Synthesis Example 1 have a solid content of 0.2% and the organic fine particles of Synthesis Example B1 have a solid content of 0.8% as a binder. The mixture was mixed to prepare an aqueous dispersion of organic fine particles and Synthesis Example B1. Further, 17% of the solid content of the cross-linking agent 1 with respect to the solid content of Synthesis Example B1 was added to this aqueous dispersion. The PET (cloth) treated with this aqueous dispersion (weight: 88 g / m ² , 70 denier, gray) has a falling speed of 117 mm / s, a water pressure resistance of 395 mm, a water repellency test of 95 points, and a strong water repellency test of 3. It was a point.

<Synthesis Examples 2-62>
The same procedure as in Synthesis Example 1 was repeated except that the monomers shown in Table 1 were used. The results are shown in Table 1. The monomer molar ratio in Table 1 indicates the molar equivalent to 1 mol of 2,2'-azobis (2-methylpropionamidine) dihydrochloride.

<Examples 2-62>
The same procedure as in Example 1 was repeated except that the aqueous dispersion of the fine particles of Synthesis Examples 2 to 62 was used instead of the aqueous dispersion of the fine particles of Synthesis Example 1. The results are shown in Table 1.

<Comparative Example 1>
An aqueous dispersion of Synthesis Example B1 was prepared so that the solid content of Synthesis Example B1 was 1.0%. The water pressure resistance of PET (cloth) treated with this aqueous dispersion (weight: 88 g / m ² , 70 denier, gray) was 357 mm.

<Comparative Example 2>
An aqueous dispersion of Synthesis Example B2 was prepared so that the solid content of Synthesis Example B2 was 1.0%. The water pressure resistance of PET (cloth) (weight: 88 g / m ² , 70 denier, gray) treated with this aqueous dispersion was 329 mm.

<Synthesis Example 63>
In a nitrogen-substituted reaction vessel, 0.66 g of t-butylstyrene (tBuSty), 0.39 g of glycidyl methacrylate (GMA), 0.018 g of divinylbenzene (DVB) and 33 ml of pure water were added and dispersed. After nitrogen substitution, 18.6 mg of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65 ° C. for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content was 2.23%. The static contact angle of water of PET (cloth) (grain: 88 g / m ² , 70 denier, gray) treated with only an aqueous dispersion of organic fine particles was 143.1 °, and the rolling speed was 265 mm / s.

<Synthesis Example 64>
0.50 g of t-butyl methacrylate (tBuMA), 0.20 g of glycidyl methacrylate (GMA), 0.47 g of isoboronyl methacrylate (iBMA), 0.091 g of divinylbenzene (DVB), and pure water are placed in a nitrogen-substituted reaction vessel. 39 ml was added and dispersed. After nitrogen substitution, 19.0 mg of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65 ° C. for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content was 2.32%. The static contact angle of water of PET (cloth) (grain: 88 g / m ² , 70 denier, gray) treated with only an aqueous dispersion of organic fine particles was 156.2 °, and the rolling speed was 227 mm / s.

<Synthesis Example 65>
9.61 g of t-butylstyrene (tBuSty), 11.37 g of glycidyl methacrylate (GMA), 0.52 g of divinylbenzene (DVB), 0.24 g of emulsifier 2 and 570 ml of pure water were added and dispersed in the reaction vessel. .. After nitrogen substitution, 54.2 mg of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65 ° C. After 30 minutes, 9.61 g of t-butylstyrene (tBuSty), 11.37 g of glycidyl methacrylate (GMA) and 0.52 g of divinylbenzene (DVB) were added, and the mixture was heated and stirred at 65 ° C. for 8 hours to disperse the organic fine particles in water. I got a body. The solid content was 5.4%. The particle size (average particle size) of the aqueous dispersion was 76 nm.

<Synthesis Example 66>
1.00 g of t-butylstyrene (tBuSty), 0.049 g of divinylbenzene (DVB), 52 mg of emulsifier 1 and 19 ml of pure water were added and dispersed in the reaction vessel. After nitrogen substitution, 16.9 mg of 2,2'-azobis (2-methylpropionamidine) dihydrochloride was added, and the mixture was heated and stirred at 65 ° C. for 8 hours to obtain an aqueous dispersion of organic fine particles. The solid content was 4.54%. The particle size (average particle size) of the aqueous dispersion was 234 nm.

<Examples 63 to 115>
The procedure is the same as that of Example 1 except that the aqueous dispersion of the fine particles, the dispersion of the binder, the concentration of the fine particles and the binder, the predetermined cloth, and the cross-linking agent 2 are used instead of the cross-linking agent 1 shown in Tables 2 to 4. Was repeated. The results are shown in Tables 2-4.

<Comparative Examples 3 to 11>
The same procedure as in Example 1 was repeated except that the aqueous dispersion of the fine particles was omitted, the type and concentration of the binder dispersion shown in the table, and the predetermined cloth shown in the table were used. The results are shown in Tables 2 and 4.

The water pressure resistance of the untreated PET cloth (gray basis weight: 88 g / m ² , 70 denier) was 25 mm.

The following cloths were used as the cloths shown in Tables 2 to 4.
Cloth 1: PET gray Cloth: 88g / m ² , 70 denier Cloth 2: High-density PET black cloth 3: Non-woven fabric (PP) 44g / m2
Cloth 4: Acrylic blue Cloth 5: T / C twill (65/35) Beige

The organic fine particles of the present disclosure can be used as an oil repellent, an antifouling agent, a stain remover, a release agent or a mold release agent having an effect of improving water pressure resistance. The organic fine particles of the present disclosure can be used as a water pressure resistance improving agent.
Organic fine particles can be used in applications where water pressure resistance is required. Particularly preferred applications are cloth for outdoor equipment, cloth for sports equipment, cloth for raincoats and other rain gear, cloth for medical use, especially non-woven fabrics, such as surgical gowns for medical use, protective clothing, awnings, especially shades and tents. And so on.

Claims (27)

Organic fine particles that can exist on a base material in a state of having a particle shape and exhibit a water pressure resistant effect on the base material. When attached to cloth, (i) water pressure resistance ratio (= water resistance of treated cloth with organic fine particles / water resistance of blank untreated cloth) is 1.03 or more, (ii) air permeability ratio (=) The organic fine particles according to claim 1, wherein the air permeability of the treated cloth to which the organic fine particles are attached / the air permeability of the blank untreated cloth) satisfies at least one of 0.9 or less. The organic fine particles according to claim 1 or 2, wherein the fine particles observable on the cloth have a particle size of 50 to 700 nm. (I) Claim 1 comprising a polymer having a repeating unit formed from a hydrophobic monomer having one ethylenically unsaturated double bond and at least one hydrocarbon group having 3 to 40 carbon atoms. The organic fine particles according to any one of 3 to 3. (I) A hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3 to 40 carbon atoms, and (II) at least two ethylenically unsaturated diaries. Crosslinkable monomer with double bond,
Organic fine particles containing a polymer having repeating units formed from. (I) Contains a polymer having repeating units formed from a hydrophobic monomer having one ethylenically unsaturated double bond and at least one branched or cyclic hydrocarbon group having 3-40 carbon atoms. Organic fine particles
Among the hydrophobic monomers (I), organic fine particles containing 20 mol% or more of high glass transition point monomers having a glass transition point of homopolymer of 100 ° C. or higher. The polymer is
(III) A reactive / hydrophilic monomer having one ethylenically unsaturated double bond and at least one reactive group and / or a hydrophilic group, or one ethylenically unsaturated double bond and at least one. A short-chain hydrocarbon-containing monomer having one or two hydrocarbon groups with one or two carbon atoms,
And / or (IV) (meth) acrylic monomers having a linear hydrocarbon group or polydimethylsiloxane group with 3-40 carbon atoms,
The organic fine particles according to any one of claims 4 to 6, which also have a repeating unit formed from at least one monomer selected from the above. The invention according to any one of claims 4 to 7, wherein in the hydrophobic monomer (I), the branched hydrocarbon group has 3 to 11 carbon atoms and the cyclic hydrocarbon group has 4 to 15 carbon atoms. Organic fine particles. Hydrophobic monomer (I) has the formula:
CH ₂ = C (-R ¹² ) -C (= O) -Y ¹¹ (R ¹¹ ) _k
Or CH ₂ = C (-R ¹⁴ ) -Y ¹² (H) _5-l (R ¹³ ) _l
[In the formula, R ¹¹ and R ¹³ are independently branched or cyclic hydrocarbon groups having 3 to 40 carbon atoms, respectively.
R ¹² and R ¹⁴ are hydrogen atoms, monovalent organic groups or halogen atoms.
Y ¹¹ is -O-,-or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms).
Y ¹² is a benzene ring and
H is a hydrogen atom
H and R ¹³ are directly bonded to Y ¹² , respectively.
k is 1 to 3 and l is 0 to 3. ]
It is a monomer indicated by
The crosslinkable monomer (II) has the formula:
formula:

or

[In the formula, R ³¹ and R ³³ are independently directly bonded to each other and have a hydrocarbon group having 1 to 20 carbon atoms (may include a hydrocarbon moiety having a −OH group), − (CH ₂ CH ₂ O). At least one selected from r- (r is an integer of 1 to 10), -C ₆ H _4- , -O-, or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms). It is a 2- to 4-valent group composed of two or more.
R ³² , R ³⁴ , R ³⁵ and R ³⁶ are independently hydrogen atoms, monovalent organic groups, or halogen atoms, respectively.
Y ³¹ is -O- or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms).
p is 2 to 4,
q is 1 to 5. ]
It is a monomer indicated by
Reactive / hydrophilic monomer (III) has the formula:
formula:
CH ₂ = C (-R ⁴² ) -C (= O) -Y ^41- (R ⁴³ ) _o (R ⁴¹ ) _t
Or CH ₂ = C (-R ⁴⁵ ) -Y ^42- (H) _5-n (R ⁴⁴ ) _u
[In the formula, R ⁴¹ and R ⁴⁴ are independently reactive or hydrophilic groups, respectively.
R ⁴² and R ⁴⁵ are hydrogen atoms, monovalent organic groups, or halogen atoms.
Y ⁴¹ is a direct bond, -O-, or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms).
R ⁴³ is a group having a direct bond, —O—, or a hydrocarbon group having 2 to 4 valences of 1 to 10 carbon atoms (which may include a hydrocarbon moiety having an −OH group).
Y ⁴² is a benzene ring and
H is a hydrogen atom
H and R ⁴⁴ are directly coupled to Y ⁴² , respectively.
t and u are 1 to 3,
o is 0 or 1. ]
The monomer indicated by, or
The short-chain hydrocarbon-containing monomer (III) has the formula:
CH ₂ = C (-R ⁴⁷ ) -C (= O) -Y ⁴³ -R ⁴⁶
[In the formula, ^R46 is a hydrocarbon group having 1 or 2 carbon atoms.
R ⁴⁷ is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁴³ is a direct bond, -O-, or -NR'-(R'is H or a hydrocarbon group having 1 to 4 carbon atoms). ]
It is a monomer indicated by
The (meth) acrylic monomer (IV) has the formula:
CH ₂ = C (-R ⁵² ) -C (= O) -Y ⁵¹ (R ⁵¹ ) _s
[In the formula, R ⁵¹ is a linear hydrocarbon group having 3 to 40 carbon atoms independently.
R ⁵² is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁵¹ is a hydrocarbon group having 2 to 4 valences of 1 carbon atom, -C ₆ H _4- , -O-, -C (= O)-, -S (= O) _2- or -NR'-( R'is a divalent to tetravalent group composed of at least one selected from H or a hydrocarbon group having 1 to 4 carbon atoms (except when only a divalent hydrocarbon group is used). ,
s is 1 to 3. ]
It is a (meth) acrylic monomer having a linear hydrocarbon group having 3 to 40 carbon atoms, which is represented by the formula:
CH ₂ = C (-R ⁶² ) -C (= O) -Y ⁶¹ -R ⁶¹
[In the formula, ^R61 is a group having a polydimethylsiloxane group.
R ⁶² is a hydrogen atom, a monovalent organic group, or a halogen atom.
Y ⁶¹ is a hydrocarbon group having 2 to 4 valences of 1 carbon atom, -C ₆ H _4- , -O-, -C (= O)-, -S (= O) _2- or -NR'-( R'is a 2- to 4-valent group composed of at least one selected from H or a hydrocarbon group having 1 to 4 carbon atoms. ]
The organic fine particles according to any one of claims 4 to 8, which are (meth) acrylic monomers having a polydimethylsiloxane group, which is indicated by. In the reactive monomer (III), the reactive group is an epoxy group, a chloromethyl group, a bromomethyl group, an iodomethyl group or a blocked isocyanate group, and the hydrophilic group is a hydroxyl group or an amino group (H bonded to N). Is converted to a methyl group, an ethyl group, a propyl group, or a butyl group), a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a carboxylic acid, a sulfonic acid, an alkali metal or alkaline earth metal of phosphoric acid. At least one selected from the group consisting of a base, chlorine or bromine, an ammonium base having an iodine ion as a counter anion, an ethylene glycol group, a polyethylene glycol group, and a group having an acetone skeleton (-C (= O) -CH ₃ ). The group according to any one of claims 7 to 9, wherein the reactive / hydrophilic monomer (III) is a (meth) acrylamide having a short-chain hydrocarbon group having 6 or less carbon atoms in the side chain. Organic fine particles. Hydrophobic monomer (I)
t-Butyl (meth) acrylate, isopropyl (meth) acrylate, 2,6,8-trimethylnonane-4-yl = acrylate,
Isoboronyl (meth) acrylate, Bornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenyl (meth) acrylate, naphthyl acrylate, benzyl acrylate t-butylstyrene , Methylstyrene, styrene, cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclobutyl (meth) acrylate, cycloheptyl (meth) acrylate, 2,4-dit-butylstyrene, 2,4,6-trimethylstyrene , At least one monomer selected from the group consisting of,
The crosslinkable monomer (II) is divinylbenzene, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neo. Pentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, ethylene glycol di (meth) acrylate, methylene glycol di (meth) acrylate, polytetramethylene glue. Coledi (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, trimethylolpropane tri (meth) acrylate, adamantyldi (meth) acrylate, glycerindi (meth) acrylate, tricyclodecanedimethanoldi (meth) ) At least one monomer selected from the group consisting of acrylate, dicyclopentanyldi (meth) acrylate, and 5-hydroxy-1,3-adamantandi (meth) acrylate.
Reactive / hydrophilic monomer (III) is glycidyl (meth) acrylate, glycerol (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2 -Hydroxybutyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, acrylic acid, methacrylic acid, trimethylsilyl (meth) acrylate, 2- (trimethylsilyloxy) ethyl (meth) acrylate, 2- (Dimethylamino) ethyl (meth) acrylate, 2- (tert-butylamino) ethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate quaternized product, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (meth) Acrylate, diacetone (meth) acrylamide, isopropyl (meth) acrylamide, t-butyl (meth) acrylamide, ethyl (meth) acrylamide, methyl (meth) acrylamide; and
Selected from the group consisting of 4-hydroxymethylstyrene, 4-hydroxyethylstyrene, 4-aminomethylstyrene, 4-aminoethylstyrene, 2- (4-vinylphenyl) oxylane, 2- (4-vinylbenzoyl) oxylane. At least one monomer,
The short-chain hydrocarbon group-containing monomer (III) is at least one monomer selected from the group consisting of methyl methacrylate, ethyl methacrylate, α-chloromethyl acrylate, and α-chloroethyl acrylate.
(Meta) Acrylic monomer (IV)
Stearyl (meth) acrylate, amide ethyl stearate (meth) acrylate, CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) C ₁₇ H _35, CH ₂ = CHC (= O) OC ₂ H ₄ NHSO ₂ C ₁₈ H ₃₇ , CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) OC ₁₈ H ₃₇ , CH ₂ = CHC (= O) OC ₂ H ₄ OC (= O) NHC ₁₈ H ₃₇ , CH ₂ = CHC (= O) OC ₂ H ₄ NHC (= O) NHC ₁₈ H ₃₇ ,
formula:

or

[In the formula, n is a number from 1 to 500. ]
The organic fine particles according to any one of claims 4 to 10, which are at least one monomer selected from the group consisting of. (I) The molar ratio of the hydrophobic monomer (I) / reactive / hydrophilic monomer and / or the short-chain hydrocarbon group-containing monomer (III) is 100/0 to 50/50.
(Ii) The crosslinkable monomer (II) is a hydrophobic monomer (I), a reactive / hydrophilic monomer and / or a short-chain hydrocarbon group-containing monomer (III), and (meth). 0.1 to 30 mol parts for a total of 100 mol parts of the acrylic monomer (IV),
Alternatively, (iii) the (meth) acrylic monomer (IV) is a hydrophobic monomer (I) and a reactive / hydrophilic monomer and / or a short-chain hydrocarbon group-containing monomer (III). The organic fine particles according to any one of claims 4 to 11, which satisfy at least one of 0 to 30 mol parts with respect to 100 mol parts in total. A water pressure resistant improving agent containing the organic fine particles according to any one of claims 1 to 12. Use of the organic fine particles according to any one of claims 1 to 12 as a water pressure resistance improving agent. A water pressure resistant improving agent composition comprising (A) the organic fine particles according to any one of claims 1 to 12 and (B) an aqueous medium. The water pressure resistant improving agent composition according to claim 15, wherein the amount of the organic fine particles (A) is 50% by weight or less with respect to the water pressure resistant improving agent composition. The water pressure resistance improving agent composition according to claim 15 or 16, further comprising any one or more of (C) a binder resin, (D) a surfactant, and (E) a cross-linking agent. The binder resin (C) is selected from at least a non-fluorinated polymer having a hydrocarbon group having 3 to 40 carbon atoms in the side chain and a fluorine-containing polymer having a fluoroalkyl group having 1 to 20 carbon atoms in the side chain. The water pressure resistant improving agent composition according to claim 17, which is one kind of polymer. The water pressure resistant according to any one of claims 17 or 18, wherein the binder resin (C) is an acrylic polymer, a urethane polymer, a polyolefin, a polyester, a polyether, a polyamide, a polyimide, polystyrene, a silicone polymer, or a combination thereof. Improver composition. The weight ratio of the binder resin (C) / organic fine particles (A) is 20/80 to 99/1, or the amount of the binder resin (C) is the total weight of the binder resin (C) and the organic fine particles (A). The water pressure resistant improving agent composition according to any one of claims 17 to 19, which is 30 to 99% by weight. A step of polymerizing a monomer to obtain an aqueous dispersion of organic fine particles (A) in the presence of a surfactant having a weight of 30 parts by weight or less with respect to 100 parts by weight of the monomer in an aqueous medium.
The method for producing a water pressure resistant improving agent composition according to any one of claims 15 to 20. moreover,
Binder resin by adding the aqueous dispersion of the binder resin (C) to the aqueous dispersion of the organic fine particles (A) or by polymerizing the monomer for the binder resin in the aqueous dispersion of the organic fine particles (A). By obtaining (C) or by polymerizing a monomer for organic fine particles in an aqueous dispersion of a binder resin, an aqueous dispersion in which the organic fine particles (A) and the binder resin (C) are dispersed can be obtained. The manufacturing method according to claim 21, which comprises a step of obtaining. A method for treating a textile product, wherein the treatment liquid containing the water pressure resistance improving agent composition according to any one of claims 15 to 20 is applied to the textile product. A textile product to which the water pressure resistance improving agent composition according to any one of claims 15 to 20 is applied. (i) Water pressure resistance ratio (= water pressure resistance of textile products with organic fine particles / water pressure resistance of blank textile products) is 1.03 or more, (ii) air permeability ratio (= permeability of textile products with organic fine particles attached) The textile product according to claim 24, which satisfies at least one of (air permeability / air permeability of blank textile product) of 0.9 or less. The textile product according to claim 24 or 25, wherein the textile product is a cloth for outdoor goods, a cloth for sports goods, a cloth for rain gear, a cloth for medical use, or a non-woven fabric. 26. The textile product of claim 26, wherein the textile product is a medical surgical gown, protective clothing, awning, shade, tent.