JP2018076434A

JP2018076434A - Composition, two-pack type composition, article and method for producing article

Info

Publication number: JP2018076434A
Application number: JP2016219069A
Authority: JP
Inventors: 信行音澤; Nobuyuki Otosawa
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2016-11-09
Filing date: 2016-11-09
Publication date: 2018-05-17

Abstract

PROBLEM TO BE SOLVED: To provide a composition capable of forming a film excellent in water sliding property.SOLUTION: A composition contains a first condensate that is a condensate of a hydrolyzate of alkoxysilane, has a branched siloxane bond and a monovalent organic group and has a polarity force component (γS) of surface free energy of a solid of less than 5 mN/m, and a second condensate that is a condensate of a hydrolyzate of alkoxysilane, has a branched siloxane bond and a monovalent organic group, and has a polarity force component (γS) of surface free energy of a solid of 5 mN/m or more.SELECTED DRAWING: None

Description

本発明は、組成物、該組成物を有する２液型組成物、前記組成物から形成された膜を有する物品、前記２液型組成物を用いた物品の製造方法に関する。 The present invention relates to a composition, a two-part composition having the composition, an article having a film formed from the composition, and a method for producing an article using the two-part composition.

従来より、固体表面に液滴が付着しても速やかに除去されるように、撥水処理を行う方法が提案されている。例えば、アルキル基やペルフルオロアルキル基等を有する有機シランを用いて、固体表面に膜を形成することによって固体表面の表面エネルギーを低下させ、撥水性を向上させる方法が知られている。
しかし、例えば微小水滴等、撥水性を付与した固体表面を水平面に対して９０°以上傾けても、水滴が固体表面に留まる場合がある。すなわち、単に表面エネルギーを低下させて接触角を大きくするだけでは滑水性が不充分な場合がある。滑水性が良いとは、固体表面上の水滴が転がりやすいことを意味する。 Conventionally, a method of performing a water repellent treatment has been proposed so that even if a droplet adheres to the solid surface, it is quickly removed. For example, a method for improving water repellency by reducing the surface energy of a solid surface by forming a film on the solid surface using an organic silane having an alkyl group, a perfluoroalkyl group, or the like is known.
However, even if a solid surface imparted with water repellency, such as a minute water droplet, is tilted by 90 ° or more with respect to the horizontal plane, the water droplet may remain on the solid surface. That is, there is a case where the sliding property is insufficient only by simply reducing the surface energy and increasing the contact angle. Good water slidability means that water droplets on the solid surface are easy to roll.

特許文献１、２では、固体表面上に、液滴の滑落性、耐指紋付着性、防曇性等を有する被膜を形成する組成物として、炭素数が８〜１２のアルキルトリメトキシシランまたは炭素数が８〜１２のアルキルトリエトキシシランと、テトラメトキシシランまたはテトラエトキシシランとを、有機溶媒、水、触媒を含む溶液中で加水分解および縮合させて得られる組成物が提案されている。 In Patent Documents 1 and 2, as a composition for forming a film having a sliding property of a droplet, anti-fingerprint adhesion, anti-fogging property, etc. on a solid surface, an alkyltrimethoxysilane having 8 to 12 carbon atoms or carbon A composition obtained by hydrolyzing and condensing an alkyltriethoxysilane having a number of 8 to 12 with tetramethoxysilane or tetraethoxysilane in a solution containing an organic solvent, water, and a catalyst has been proposed.

特許第５９５０３９９号公報Japanese Patent No. 5950399 国際公開第２０１４／１３６２７５号International Publication No. 2014/136275

しかしながら、近年は種々の設備や器具の表面において高い滑水性が要求され、従来の組成物で得られる膜の滑水性は必ずしも充分ではない。本発明者によれば、特許文献１、２に記載の組成物で得られる膜の滑水性が不充分であることを確認した。
本発明の目的は、滑水性に優れた膜を形成できる組成物、該組成物を有する２液型組成物、前記組成物から形成された膜を有する物品、前記２液型組成物を用いた物品の製造方法を提供することにある。 However, in recent years, high water slidability is required on the surfaces of various facilities and instruments, and the water slidability of membranes obtained with conventional compositions is not always sufficient. According to this inventor, it confirmed that the water-sliding property of the film | membrane obtained with the composition of patent document 1, 2 was inadequate.
An object of the present invention is to use a composition capable of forming a film excellent in lubricity, a two-part composition having the composition, an article having a film formed from the composition, and the two-part composition. The object is to provide a method for manufacturing an article.

本発明は、以下の［１］〜［１３］の構成を有する、組成物、２液型組成物、物品、および物品の製造方法を提供する。
［１］アルコキシシランの加水分解物の縮合物であって、分岐状のシロキサン結合および１価の有機基を有し、下記の測定方法で求められる固体の表面自由エネルギーの極性力成分（γＳ^ｐ）が５ｍＮ／ｍ未満である第１の縮合物と、
アルコキシシランの加水分解物の縮合物であって、分岐状のシロキサン結合および１価の有機基を有し、下記の測定方法で求められる固体の表面自由エネルギーの極性力成分（γＳ^ｐ）が５ｍＮ／ｍ以上である第２の縮合物と、
を含むことを特徴とする組成物。
固体の表面自由エネルギーの極性力成分（γＳ^ｐ）の測定方法：測定対象の縮合物からなる膜を形成し、下記γＬ^１、γＬ^ｄ１およびγＬ^ｐ１が既知である第１の液体と前記膜との接触角（θ^１）を測定し、下記γＬ^２、γＬ^ｄ２およびγＬ^ｐ２が既知である第２の液体と前記膜との接触角（θ^２）を測定する。次いで、これらの値を下式（Ｉ−１）および下式（Ｉ−２）に代入する。次いで、下式（Ｉ−１）および下式（Ｉ−２）の連立方程式から、固体の表面自由エネルギーγＳの分散力成分（γＳ^ｄ）と極性力成分（γＳ^ｐ）を求める。
（γＳ^ｄ・γＬ^ｄ１）^１／２＋（γＳ^ｐ・γＬ^ｐ１）^１／２＝γＬ^１（１＋ｃｏｓθ^１）／２…（Ｉ−１）
（γＳ^ｄ・γＬ^ｄ２）^１／２＋（γＳ^ｐ・γＬ^ｐ２）^１／２＝γＬ^２（１＋ｃｏｓθ^２）／２…（Ｉ−２）
γＳ^ｄ：固体の表面自由エネルギーγＳの分散力成分。
γＳ^ｐ：固体の表面自由エネルギーγＳの極性力成分。
γＬ^１：第１の液体の表面張力。
γＬ^２：第２の液体の表面張力。
θ^１：第１の液体の接触角。
θ^２：第２の液体の接触角。
γＬ^ｄ１：第１の液体の表面張力の分散力成分。
γＬ^ｐ１：第１の液体の表面張力の極性力成分。
γＬ^ｄ２：第２の液体の表面張力の分散力成分。
γＬ^ｐ２：第２の液体の表面張力の極性力成分。
［２］第１のアルコキシシランの加水分解物の縮合物である第１の縮合物と、第２のアルコキシシランの加水分解物の縮合物である第２の縮合物と、を含む組成物であって、
前記第１のアルコキシシランが、アルコキシ基を３個以上有し下記Ｒ^３を有しないアルコキシシランと、下記Ｒ^３を有するアルコキシシランとを含む、またはアルコキシ基を３個以上有しかつ下記Ｒ^３を有するアルコキシシランを含み、下記Ｒ^４を有するアルコキシシランを含まなく、
前記第２のアルコキシシランが、アルコキシ基を３個以上有し下記Ｒ^４を有しないアルコキシシランと、下記Ｒ^４を有するアルコキシシランとを含む、またはアルコキシ基を３個以上有しかつ下記Ｒ^４を有するアルコキシシランを含み、下記Ｒ^３を有するアルコキシシランを含まない、
ことを特徴とする組成物。
Ｒ^３：炭素数８以上のアルキル基、炭素数８以上のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数８以上のフルオロアルキル基、または炭素数８以上のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。
Ｒ^４：炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基、炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のアルキル基、炭素数３〜６のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のフルオロアルキル基、または炭素数３〜６のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。
［３］第１のアルコキシシランの加水分解物の縮合物である第１の縮合物と、第２のアルコキシシランの加水分解物の縮合物である第２の縮合物と、を含む組成物であって、
前記第１のアルコキシシランが、下式（１）〜（５）で表される化合物からなる群から選ばれる１種以上からなり、かつ、少なくとも式（１）で表される化合物と式（４）で表される化合物、または式（５）で表される化合物を含み、
前記第２のアルコキシシランが、下式（１１）〜（１５）で表される化合物からなる群から選ばれる１種以上からなり、かつ、少なくとも式（１１）で表される化合物と式（１４）で表される化合物、または式（１５）で表される化合物を含む、
ことを特徴とする組成物。
Ｓｉ−（ＯＲ^１）_４ …（１）
Ｒ^２ _２−Ｓｉ−（ＯＲ^１）_２ …（２）
Ｒ^２ _３−Ｓｉ−（ＯＲ^１） …（３）
Ｒ^３−Ｓｉ−Ｒ^２（ＯＲ^１）_２ …（４）
Ｒ^３−Ｓｉ−（ＯＲ^１）_３ …（５）
（式中、Ｒ^１は炭素数１〜４のアルキル基であり、Ｒ^２はメチル基またはエチル基であり、Ｒ^３は炭素数８以上のアルキル基、炭素数８以上のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数８以上のフルオロアルキル基、または炭素数８以上のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。なお、ＯＲ^１およびＲ^２が複数個ある場合にはそれらは同じでも異なっていてもよい。）
Ｓｉ−（ＯＲ^１１）_４ …（１１）
Ｒ^２１ _２−Ｓｉ−（ＯＲ^１１）_２ …（１２）
Ｒ^２１ _３−Ｓｉ−（ＯＲ^１１） …（１３）
Ｒ^４−Ｓｉ−Ｒ^２１（ＯＲ^１１）_２ …（１４）
Ｒ^４−Ｓｉ−（ＯＲ^１１）_３ …（１５）
（式中、Ｒ^１１は炭素数１〜４のアルキル基であり、Ｒ^２１はメチル基またはエチル基であり、Ｒ^４は炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基、炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のアルキル基、炭素数３〜６のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のフルオロアルキル基、または炭素数３〜６のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。なお、ＯＲ^１１およびＲ^２１が複数個ある場合にはそれらは同じでも異なっていてもよい。） The present invention provides a composition, a two-component composition, an article, and a method for producing the article having the following configurations [1] to [13].
[1] Condensation product of alkoxysilane hydrolyzate having a branched siloxane bond and a monovalent organic group, and a polar force component (γS ^{p of} solid surface free energy obtained by the following measurement method ) Is less than 5 mN / m, and
This is a condensate of a hydrolyzate of alkoxysilane, which has a branched siloxane bond and a monovalent organic group, and the polar force component (γS ^p ) of the solid surface free energy determined by the following measurement method is 5 mN A second condensate that is at least / m;
The composition characterized by including.
Method for measuring polar force component (γS ^p ) of surface free energy of solid: forming a film made of a condensate to be measured, and the first liquid having the following γL ¹ , γL ^d1 and γL ^p1 and the film contact angle (theta ¹⁾ was measured in the following γL ^2, γL ^d2 and GanmaL ^p2 to measure the contact angle (theta ²⁾ of the second liquid and the film is known. Then, these values are substituted into the following formula (I-1) and the following formula (I-2). Next, the dispersion force component (γS ^d ) and the polar force component (γS ^p ) of the surface free energy γS of the solid are obtained from the simultaneous equations of the following formulas (I-1) and (I-2).
(ΓS ^d · γL ^d1 ) ^1/2 + (γS ^p · γL ^p1 ) ^1/2 = γL ¹ (1 + cos θ ¹ ) / 2 (I-1)
(ΓS ^d · γL ^d2 ) ^1/2 + (γS ^p · γL ^p2 ) ^1/2 = γL ² (1 + cos θ ² ) / 2 (I-2)
γS ^d : Dispersion force component of the surface free energy γS of the solid.
γS ^p : Polar force component of solid surface free energy γS.
γL ¹ : surface tension of the first liquid.
γL ² : surface tension of the second liquid.
θ ¹ : contact angle of the first liquid.
θ ² : contact angle of the second liquid.
γL ^d1 : Dispersive force component of the surface tension of the first liquid.
γL ^p1 : Polar force component of the surface tension of the first liquid.
γL ^d2 : Dispersion force component of the surface tension of the second liquid.
γL ^p2 : Polar force component of the surface tension of the second liquid.
[2] A composition comprising: a first condensate that is a condensate of a hydrolyzate of a first alkoxysilane; and a second condensate that is a condensate of a hydrolyzate of a second alkoxysilane. There,
Said first alkoxysilane, an alkoxysilane having no following R ³ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^3, having the following R ³ Which does not include an alkoxysilane having the following R ⁴ :
Said second alkoxysilane, an alkoxysilane having no following R ⁴ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^4, having the following R ⁴ include alkoxysilanes having not contain an alkoxysilane having the following R ^3,
The composition characterized by the above-mentioned.
R ³ : an alkyl group having 8 or more carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 8 or more carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a fluoroalkyl having 8 or more carbon atoms A group having an etheric oxygen atom between carbon-carbon atoms of the group.
R ⁴ : a group in which one or more hydrogen atoms of an alkyl group having 1 to 20 carbon atoms are substituted with a polar group, and a group in which one or more hydrogen atoms of an alkyl group having 1 to 20 carbon atoms are substituted with a polar group A group having an etheric oxygen atom between carbon-carbon atoms, an alkyl group having 3 to 6 carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, 3 carbon atoms Or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkyl group of -6 or a C3-C6 fluoroalkyl group.
[3] A composition comprising: a first condensate that is a condensate of a hydrolyzate of a first alkoxysilane; and a second condensate that is a condensate of a hydrolyzate of a second alkoxysilane. There,
The first alkoxysilane comprises one or more selected from the group consisting of compounds represented by the following formulas (1) to (5), and at least a compound represented by formula (1) and formula (4) ), Or a compound represented by formula (5),
The second alkoxysilane comprises at least one selected from the group consisting of compounds represented by the following formulas (11) to (15), and at least a compound represented by the formula (11) and the formula (14): ) Or a compound represented by formula (15),
The composition characterized by the above-mentioned.
Si- (OR ¹ ) ₄ (1)
R ² ₂ —Si— (OR ¹ ) ₂ (2)
R ² ₃ —Si— (OR ¹ ) (3)
R ³ —Si—R ² (OR ¹ ) ₂ (4)
R ³ —Si— (OR ¹ ) ₃ (5)
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is an alkyl group having 8 or more carbon atoms, or a carbon atom of an alkyl group having 8 or more carbon atoms) A group having an etheric oxygen atom between carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkyl group having 8 or more carbon atoms. ^When there are a plurality of ¹ and R ^2, they may be the same or different.)
Si- (OR ¹¹ ) ₄ (11)
R ²¹ ₂ —Si— (OR ¹¹ ) ₂ (12)
R ²¹ ₃ —Si— (OR ¹¹ ) (13)
R ⁴ —Si—R ²¹ (OR ¹¹ ) ₂ (14)
R ⁴ —Si— (OR ¹¹ ) ₃ (15)
Wherein R ¹¹ is an alkyl group having 1 to 4 carbon atoms, R ²¹ is a methyl group or an ethyl group, and R ⁴ is one or more hydrogen atoms of the alkyl group having 1 to 20 carbon atoms. A group having 1 to 20 carbon atoms, a group having at least one hydrogen atom of an alkyl group having 1 to 20 carbon atoms, and a group having an etheric oxygen atom between carbon-carbon atoms of a group having a polar group substituted, and having 3 to 6 carbon atoms Carbon-carbon of an alkyl group, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 6 carbon atoms, or a fluoroalkyl group having 3 to 6 carbon atoms (It is a group having an etheric oxygen atom between atoms, and when there are a plurality of OR ¹¹ and R ^21, they may be the same or different.)

［４］前記極性基が、−ＳＨ、−ＯＨ、−Ｃ（＝Ｏ）Ｈ、−Ｃｌ、−ＣＮ、−Ｆ、−ＣＦ_３、−ＣＦ_２Ｈ、−ＣＯＯＨ、−ＣＯＯＲ^５、−ＰＯ_３Ｈ、−ＳＯ_３Ｈ、−ＮＨ_２および−ＮＲ^６ _２（ただし、Ｒ^５、Ｒ^６は炭素数１〜６のアルキル基）からなる群から選ばれる１種以上である、［２］または［３］の組成物。
［５］前記組成物中に存在する、前記Ｒ^３と前記Ｒ^４とのモル比（Ｒ^３／Ｒ^４）が１／２〜１，０００／１である、［２］〜［４］のいずれかの組成物。
［６］前記第１の縮合物と前記第２の縮合物との質量比（第１の縮合物／第２の縮合物）が１／２〜１，０００／１である、［１］〜［５］のいずれかの組成物。
［７］さらに溶媒を含む、［１］〜［６］のいずれかの組成物。
［８］前記［１］〜［７］のいずれかの組成物から形成された膜を基材の表面に有することを特徴とする物品。
［９］前記膜上に滴下された体積１０μＬの水滴の水転落角が２５°以下である、［８］の物品。 [4] The polar group is —SH, —OH, —C (═O) H, —Cl, —CN, —F, —CF ₃ , —CF ₂ H, —COOH, —COOR ⁵ , —PO _3. [2] or [2], which is one or more selected from the group consisting of H, —SO ₃ H, —NH ₂ and —NR ⁶ ₂ (wherein R ⁵ and R ⁶ are each an alkyl group having 1 to ⁶ carbon atoms) 3].
[5] The molar ratio (R ³ / R ⁴ ) between R ³ and R ⁴ present in the composition is 1/2 to 1,000 / 1, [2] to [4] Any composition.
[6] The mass ratio of the first condensate to the second condensate (first condensate / second condensate) is 1/2 to 1,000 / 1, [1] to The composition according to any one of [5].
[7] The composition according to any one of [1] to [6], further comprising a solvent.
[8] An article having a film formed from the composition according to any one of [1] to [7] on the surface of a substrate.
[9] The article according to [8], wherein a water drop angle of a water droplet having a volume of 10 μL dropped on the film is 25 ° or less.

［１０］下記第１の組成物と、下記第２の組成物からなることを特徴とする２液型組成物。
第１の組成物：アルコキシシランの加水分解物の縮合物であって、分岐状のシロキサン結合および１価の有機基を有し、下記の測定方法で求められる固体の表面自由エネルギーの極性力成分（γＳ^ｐ）が５ｍＮ／ｍ未満である第１の縮合物と溶媒とを含む組成物。
第２の組成物：アルコキシシランの加水分解物の縮合物であって、分岐状のシロキサン結合および１価の有機基を有し、下記の測定方法で求められる固体の表面自由エネルギーの極性力成分（γＳ^ｐ）が５ｍＮ／ｍ以上である第２の縮合物と溶媒とを含む組成物。
固体の表面自由エネルギーの極性力成分（γＳ^ｐ）の測定方法：測定対象の縮合物からなる膜を形成し、下記γＬ^１、γＬ^ｄ１およびγＬ^ｐ１が既知である第１の液体と前記膜との接触角（θ^１）を測定し、下記γＬ^２、γＬ^ｄ２およびγＬ^ｐ２が既知である第２の液体と前記膜との接触角（θ^２）を測定する。次いで、これらの値を下式（Ｉ−１）および下式（Ｉ−２）に代入する。次いで、下式（Ｉ−１）および下式（Ｉ−２）の連立方程式から、固体の表面自由エネルギーγＳの分散力成分（γＳ^ｄ）と極性力成分（γＳ^ｐ）を求める。
（γＳ^ｄ・γＬ^ｄ１）^１／２＋（γＳ^ｐ・γＬ^ｐ１）^１／２＝γＬ^１（１＋ｃｏｓθ^１）／２…（Ｉ−１）
（γＳ^ｄ・γＬ^ｄ２）^１／２＋（γＳ^ｐ・γＬ^ｐ２）^１／２＝γＬ^２（１＋ｃｏｓθ^２）／２…（Ｉ−２）
γＳ^ｄ：固体の表面自由エネルギーγＳの分散力成分。
γＳ^ｐ：固体の表面自由エネルギーγＳの極性力成分。
γＬ^１：第１の液体の表面張力。
γＬ^２：第２の液体の表面張力。
θ^１：第１の液体の接触角。
θ^２：第２の液体の接触角。
γＬ^ｄ１：第１の液体の表面張力の分散力成分。
γＬ^ｐ１：第１の液体の表面張力の極性力成分。
γＬ^ｄ２：第２の液体の表面張力の分散力成分。
γＬ^ｐ２：第２の液体の表面張力の極性力成分。
［１１］第１のアルコキシシランの加水分解物の縮合物と溶媒とを含む第１の組成物と、第２のアルコキシシランの加水分解物の縮合物と溶媒とを含む第２の組成物からなる２液型組成物であって、
前記第１のアルコキシシランが、アルコキシ基を３個以上有し下記Ｒ^３を有しないアルコキシシランと、下記Ｒ^３を有するアルコキシシランとを含む、またはアルコキシ基を３個以上有しかつ下記Ｒ^３を有するアルコキシシランを含み、下記Ｒ^４を有するアルコキシシランを含まなく、
前記第２のアルコキシシランが、アルコキシ基を３個以上有し下記Ｒ^４を有しないアルコキシシランと、下記Ｒ^４を有するアルコキシシランとを含む、またはアルコキシ基を３個以上有しかつ下記Ｒ^４を有するアルコキシシランを含み、下記Ｒ^３を有するアルコキシシランを含まない、
ことを特徴とする２液型組成物。
Ｒ^３：炭素数８以上のアルキル基、炭素数８以上のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数８以上のフルオロアルキル基、または炭素数８以上のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。
Ｒ^４：炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基、炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のアルキル基、炭素数３〜６のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のフルオロアルキル基、または炭素数３〜６のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。
［１２］第１のアルコキシシランの加水分解物の縮合物と溶媒とを含む第１の組成物と、第２のアルコキシシランの加水分解物の縮合物と溶媒とを含む第２の組成物からなる２液型組成物であって、
前記第１のアルコキシシランが、下式（１）〜（５）で表される化合物からなる群から選ばれる１種以上からなり、かつ、少なくとも式（１）で表される化合物と式（４）で表される化合物、または式（５）で表される化合物を含み、
前記第２のアルコキシシランが、下式（１１）〜（１５）で表される化合物からなる群から選ばれる１種以上からなり、かつ、少なくとも式（１１）で表される化合物と式（１４）で表される化合物、または式（１５）で表される化合物を含む、
ことを特徴とする２液型組成物。
Ｓｉ−（ＯＲ^１）_４ …（１）
Ｒ^２ _２−Ｓｉ−（ＯＲ^１）_２ …（２）
Ｒ^２ _３−Ｓｉ−（ＯＲ^１） …（３）
Ｒ^３−Ｓｉ−Ｒ^２（ＯＲ^１）_２ …（４）
Ｒ^３−Ｓｉ−（ＯＲ^１）_３ …（５）
（式中、Ｒ^１は炭素数１〜４のアルキル基であり、Ｒ^２はメチル基またはエチル基であり、Ｒ^３は炭素数８以上のアルキル基、炭素数８以上のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数８以上のフルオロアルキル基、または炭素数８以上のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。なお、ＯＲ^１およびＲ^２が複数個ある場合にはそれらは同じでも異なっていてもよい。）
Ｓｉ−（ＯＲ^１１）_４ …（１１）
Ｒ^２１ _２−Ｓｉ−（ＯＲ^１１）_２ …（１２）
Ｒ^２１ _３−Ｓｉ−（ＯＲ^１１） …（１３）
Ｒ^４−Ｓｉ−Ｒ^２１（ＯＲ^１１）_２ …（１４）
Ｒ^４−Ｓｉ−（ＯＲ^１１）_３ …（１５）
（式中、Ｒ^１１は炭素数１〜４のアルキル基であり、Ｒ^２１はメチル基またはエチル基であり、Ｒ^４は炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基、炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のアルキル基、炭素数３〜６のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のフルオロアルキル基、または炭素数３〜６のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。なお、ＯＲ^１１およびＲ^２１が複数個ある場合にはそれらは同じでも異なっていてもよい。）
［１３］前記［１０］〜［１２］のいずれかの２液型組成物において、前記第１の組成物と前記第２の組成物とを混合し、次いで、基材の表面に塗布して、基材の表面に膜を形成することを特徴とする物品の製造方法。 [10] A two-component composition comprising the following first composition and the following second composition.
First composition: Condensate of hydrolyzate of alkoxysilane, having a branched siloxane bond and a monovalent organic group, and a polar force component of solid surface free energy obtained by the following measurement method A composition comprising a first condensate having a (γS ^p ) of less than 5 mN / m and a solvent.
Second composition: Condensate of hydrolyzate of alkoxysilane, having a branched siloxane bond and a monovalent organic group, and a polar force component of solid surface free energy obtained by the following measurement method A composition comprising a second condensate having a (γS ^p ) of 5 mN / m or more and a solvent.
Method for measuring polar force component (γS ^p ) of surface free energy of solid: forming a film made of a condensate to be measured, and the first liquid having the following γL ¹ , γL ^d1 and γL ^p1 and the film contact angle (theta ¹⁾ was measured in the following γL ^2, γL ^d2 and GanmaL ^p2 to measure the contact angle (theta ²⁾ of the second liquid and the film is known. Then, these values are substituted into the following formula (I-1) and the following formula (I-2). Next, the dispersion force component (γS ^d ) and the polar force component (γS ^p ) of the surface free energy γS of the solid are obtained from the simultaneous equations of the following formulas (I-1) and (I-2).
(ΓS ^d · γL ^d1 ) ^1/2 + (γS ^p · γL ^p1 ) ^1/2 = γL ¹ (1 + cos θ ¹ ) / 2 (I-1)
(ΓS ^d · γL ^d2 ) ^1/2 + (γS ^p · γL ^p2 ) ^1/2 = γL ² (1 + cos θ ² ) / 2 (I-2)
γS ^d : Dispersion force component of the surface free energy γS of the solid.
γS ^p : Polar force component of solid surface free energy γS.
γL ¹ : surface tension of the first liquid.
γL ² : surface tension of the second liquid.
θ ¹ : contact angle of the first liquid.
θ ² : contact angle of the second liquid.
γL ^d1 : Dispersive force component of the surface tension of the first liquid.
γL ^p1 : Polar force component of the surface tension of the first liquid.
γL ^d2 : Dispersion force component of the surface tension of the second liquid.
γL ^p2 : Polar force component of the surface tension of the second liquid.
[11] From a first composition containing a first alkoxysilane hydrolyzate condensate and a solvent, and a second alkoxysilane hydrolyzate condensate and a solvent. A two-part composition comprising:
Said first alkoxysilane, an alkoxysilane having no following R ³ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^3, having the following R ³ Which does not include an alkoxysilane having the following R ⁴ :
Said second alkoxysilane, an alkoxysilane having no following R ⁴ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^4, having the following R ⁴ include alkoxysilanes having not contain an alkoxysilane having the following R ^3,
A two-part composition characterized by that.
R ³ : an alkyl group having 8 or more carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 8 or more carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a fluoroalkyl having 8 or more carbon atoms A group having an etheric oxygen atom between carbon-carbon atoms of the group.
R ⁴ : a group in which one or more hydrogen atoms of an alkyl group having 1 to 20 carbon atoms are substituted with a polar group, and a group in which one or more hydrogen atoms of an alkyl group having 1 to 20 carbon atoms are substituted with a polar group A group having an etheric oxygen atom between carbon-carbon atoms, an alkyl group having 3 to 6 carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, 3 carbon atoms Or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkyl group of -6 or a C3-C6 fluoroalkyl group.
[12] From the first composition containing the condensate of the hydrolyzate of the first alkoxysilane and the solvent, and the second composition containing the condensate of the hydrolyzate of the second alkoxysilane and the solvent. A two-part composition comprising:
The first alkoxysilane comprises one or more selected from the group consisting of compounds represented by the following formulas (1) to (5), and at least a compound represented by formula (1) and formula (4) ), Or a compound represented by formula (5),
The second alkoxysilane comprises at least one selected from the group consisting of compounds represented by the following formulas (11) to (15), and at least a compound represented by the formula (11) and the formula (14): ) Or a compound represented by formula (15),
A two-part composition characterized by that.
Si- (OR ¹ ) ₄ (1)
R ² ₂ —Si— (OR ¹ ) ₂ (2)
R ² ₃ —Si— (OR ¹ ) (3)
R ³ —Si—R ² (OR ¹ ) ₂ (4)
R ³ —Si— (OR ¹ ) ₃ (5)
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is an alkyl group having 8 or more carbon atoms, or a carbon atom of an alkyl group having 8 or more carbon atoms) A group having an etheric oxygen atom between carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkyl group having 8 or more carbon atoms. ^When there are a plurality of ¹ and R ^2, they may be the same or different.)
Si- (OR ¹¹ ) ₄ (11)
R ²¹ ₂ —Si— (OR ¹¹ ) ₂ (12)
R ²¹ ₃ —Si— (OR ¹¹ ) (13)
R ⁴ —Si—R ²¹ (OR ¹¹ ) ₂ (14)
R ⁴ —Si— (OR ¹¹ ) ₃ (15)
Wherein R ¹¹ is an alkyl group having 1 to 4 carbon atoms, R ²¹ is a methyl group or an ethyl group, and R ⁴ is one or more hydrogen atoms of the alkyl group having 1 to 20 carbon atoms. A group having 1 to 20 carbon atoms, a group having at least one hydrogen atom of an alkyl group having 1 to 20 carbon atoms, and a group having an etheric oxygen atom between carbon-carbon atoms of a group having a polar group substituted, and having 3 to 6 carbon atoms Carbon-carbon of an alkyl group, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 6 carbon atoms, or a fluoroalkyl group having 3 to 6 carbon atoms (It is a group having an etheric oxygen atom between atoms, and when there are a plurality of OR ¹¹ and R ^21, they may be the same or different.)
[13] In the two-component composition according to any one of [10] to [12], the first composition and the second composition are mixed and then applied to the surface of the substrate. A method for producing an article, comprising forming a film on a surface of a substrate.

本発明の組成物によれば、滑水性に優れた膜を形成できる。
本発明の２液型組成物によれば、滑水性に優れた膜を形成できる。
本発明の物品は、滑水性に優れた膜を有する。
本発明の物品の製造方法によれば、滑水性に優れた膜を有する物品を製造できる。 According to the composition of the present invention, a film having excellent water slidability can be formed.
According to the two-component composition of the present invention, a film excellent in lubricity can be formed.
The article of the present invention has a film excellent in water slidability.
According to the method for producing an article of the present invention, an article having a film excellent in lubricity can be produced.

本明細書において、式（１）で表される化合物を「化合物（１）」とも記す。他の式で表される化合物についても同様に記す。
本明細書における以下の用語の意味は、以下の通りである。
「フルオロアルキル基」とは、アルキル基の水素原子の全てあるいは一部がフッ素原子に置換されたアルキル基である。
「エーテル性酸素原子」とは、炭素−炭素原子間に１個存在する酸素原子（−Ｃ−Ｏ−Ｃ−）である。 In the present specification, the compound represented by the formula (1) is also referred to as “compound (1)”. The same applies to compounds represented by other formulas.
The meanings of the following terms in this specification are as follows.
The “fluoroalkyl group” is an alkyl group in which all or part of the hydrogen atoms of the alkyl group are substituted with fluorine atoms.
The “etheric oxygen atom” is an oxygen atom (—C—O—C—) that exists between carbon-carbon atoms.

本発明で用いられる縮合物の、固体の表面自由エネルギーの極性力成分（γＳ^ｐ）は、以下の測定方法で求められる値である。
まず、測定対象の縮合物からなる膜を形成し、下記γＬ^１、γＬ^ｄ１およびγＬ^ｐ１が既知である第１の液体と前記膜との接触角（θ^１）を測定し、下記γＬ^２、γＬ^ｄ２およびγＬ^ｐ２が既知である第２の液体と前記膜との接触角（θ^２）を測定する。次いで、これらの値を下式（Ｉ−１）および下式（Ｉ−２）に代入する。次いで、下式（Ｉ−１）および下式（Ｉ−２）の連立方程式から、固体の表面自由エネルギーγＳの分散力成分（γＳ^ｄ）と極性力成分（γＳ^ｐ）（いずれも単位はｍＮ／ｍ）を求める。
（γＳ^ｄ・γＬ^ｄ１）^１／２＋（γＳ^ｐ・γＬ^ｐ１）^１／２＝γＬ^１（１＋ｃｏｓθ^１）／２…（Ｉ−１）
（γＳ^ｄ・γＬ^ｄ２）^１／２＋（γＳ^ｐ・γＬ^ｐ２）^１／２＝γＬ^２（１＋ｃｏｓθ^２）／２…（Ｉ−２）
γＳ^ｄ：固体の表面自由エネルギーγＳの分散力成分。
γＳ^ｐ：固体の表面自由エネルギーγＳの極性力成分。
γＬ^１：第１の液体の表面張力。
γＬ^２：第２の液体の表面張力。
θ^１：第１の液体の接触角。
θ^２：第２の液体の接触角。
γＬ^ｄ１：第１の液体の表面張力の分散力成分。
γＬ^ｐ１：第１の液体の表面張力の極性力成分。
γＬ^ｄ２：第２の液体の表面張力の分散力成分。
γＬ^ｐ２：第２の液体の表面張力の極性力成分。
上式（Ｉ−１）および（Ｉ−２）は、下記拡張Ｆｏｗｋｅｓ式と下記Ｙｏｕｎｇの式から導かれる式である。
拡張Ｆｏｗｋｅｓ式：
γＳＬ＝γＳ＋γＬ−２（γｓｄ・γＬｄ）^１／２−２（γｓｐ・γＬｐ）^１／２
Ｙｏｕｎｇの式：
γＳ＝γＳＬ＋γＬ・ｃｏｓθ
（式中、γＳは固体の表面自由エネルギー、γＳＬ：固体と液体の界面の張力である。）
第１の液体として、水、ホルムアミド、エチレングリコール等の極性溶媒を用い、第２の液体としてアルカン、ジヨードメタン等の非極性溶媒を用いることが好ましい。例えば、第１の液体として水を用い、第２の液体としてノルマルヘキサデカンを用いることが好ましい。水のγＬ^ｄ１は２９．１ｍＮ／ｍ、γＬ^ｐ１は４３．７ｍＮ／ｍ、γＬ^１は７２．８ｍＮ／ｍであり、ノルマルヘキサデカンのγＬ^ｄ２は７．６ｍＮ／ｍ、γＬ^ｐ２は０ｍＮ／ｍ、γＬ^２は２７．６ｍＮ／ｍである。
接触角は、２５℃、４０％ＲＨの環境下、測定対象の縮合物からなる膜の表面に液体の約２μＬを滴下して測定する。
〔縮合物からなる膜〕
測定対象の縮合物からなる膜は、該縮合物を溶媒で希釈した塗布液を基材上に塗布し、加熱乾燥して固形分以外の溶媒を除去したものである。基材の材質はガラス、溶媒はエタノール、塗布液の固形分濃度は３質量％、塗布液の塗布量は、例えば５ｃｍ角の基材の場合は２ｍＬ、塗布方法はスピンコート、加熱乾燥時の加熱温度は１２０℃、加熱時間は１０分間とする。 The polar force component (γS ^p ) of the solid surface free energy of the condensate used in the present invention is a value determined by the following measurement method.
First, a film made of a condensate to be measured is formed, and a contact angle (θ ¹ ) between the first liquid with known γL ¹ , γL ^d1 and γL ^p1 and the film is measured, and the following γL ² , The contact angle (θ ² ) between the second liquid with known γL ^d2 and γL ^p2 and the film is measured. Then, these values are substituted into the following formula (I-1) and the following formula (I-2). Next, from the simultaneous equations of the following formulas (I-1) and (I-2), the dispersion force component (γS ^d ) and the polar force component (γS ^p ) of the surface free energy γS of the solid (both units are mN / M).
(ΓS ^d · γL ^d1 ) ^1/2 + (γS ^p · γL ^p1 ) ^1/2 = γL ¹ (1 + cos θ ¹ ) / 2 (I-1)
(ΓS ^d · γL ^d2 ) ^1/2 + (γS ^p · γL ^p2 ) ^1/2 = γL ² (1 + cos θ ² ) / 2 (I-2)
γS ^d : Dispersion force component of surface free energy γS of solid.
γS ^p : Polar force component of solid surface free energy γS.
γL ¹ : surface tension of the first liquid.
γL ² : surface tension of the second liquid.
θ ¹ : contact angle of the first liquid.
θ ² : contact angle of the second liquid.
γL ^d1 : Dispersive force component of the surface tension of the first liquid.
γL ^p1 : Polar force component of the surface tension of the first liquid.
γL ^d2 : Dispersion force component of the surface tension of the second liquid.
γL ^p2 : Polar force component of the surface tension of the second liquid.
The above formulas (I-1) and (I-2) are derived from the following extended Fowkes formula and the following Young formula.
Extended Fowkes formula:
γSL = γS + γL-2 ( γsd · γLd) 1/2 -2 (γsp · γLp) 1/2
Young's formula:
γS = γSL + γL · cos θ
(In the formula, γS is the surface free energy of the solid, and γSL is the tension at the interface between the solid and the liquid.)
It is preferable to use a polar solvent such as water, formamide, or ethylene glycol as the first liquid, and a nonpolar solvent such as alkane or diiodomethane as the second liquid. For example, it is preferable to use water as the first liquid and normal hexadecane as the second liquid. ΓL ^d1 of water is 29.1 mN / m, γL ^p1 is 43.7 mN / m, γL ¹ is 72.8 mN / m, γL ^d2 of normal hexadecane is 7.6 mN / m, γL ^p2 is 0 mN / m, γL ² is 27.6 mN / m.
The contact angle is measured by dropping about 2 μL of liquid onto the surface of the film made of the condensate to be measured in an environment of 25 ° C. and 40% RH.
[Membrane made of condensate]
The film made of the condensate to be measured is obtained by applying a coating solution obtained by diluting the condensate with a solvent on a substrate and drying by heating to remove a solvent other than the solid content. The material of the base material is glass, the solvent is ethanol, the solid content concentration of the coating solution is 3% by mass, the coating amount of the coating solution is, for example, 2 mL for a 5 cm square base material, the coating method is spin coating, The heating temperature is 120 ° C. and the heating time is 10 minutes.

本発明における膜の水転落角は、２５℃、４０％ＲＨの環境下で、膜の表面にイオン交換水の１０μＬを滴下し、水平面に対する膜の表面の角度（傾斜角度）を０°から９０°まで１．６°／秒の速度で傾けたときの、水滴が転がり始めた時点での傾斜角度である。この値が小さいほど、滑水性に優れることを意味する。 In the present invention, the water falling angle of the membrane is such that 10 μL of ion-exchanged water is dropped on the surface of the membrane in an environment of 25 ° C. and 40% RH, and the angle (tilt angle) of the membrane surface with respect to the horizontal plane is 0 ° to 90 °. The tilt angle at the time when the water droplet starts to roll when tilted at a speed of 1.6 ° / sec. It means that it is excellent in lubricity, so that this value is small.

〔組成物〕
本発明の組成物（以下、「本組成物」ともいう。）は、第１の縮合物と第２の縮合物とを含む。第１の縮合物および第２の縮合物はいずれも、アルコキシシランの加水分解物の縮合物である。
本発明で用いられるアルコキシシランは、ケイ素原子にｎ^０個（ｎ^０は１〜４の整数）のアルコキシ基が結合している化合物である。該アルコキシシランはケイ素原子にｎ^０個（ｎ^０は１〜４の整数）のアルコキシ基と、（４−ｎ^０）個の１価の有機基が結合している化合物が好ましい。
アルコキシシランの加水分解物とは、アルコキシシリル基（Ｓｉ−ＯＲ）の少なくとも一部が加水分解されてシラノール基（Ｓｉ−ＯＨ）になった状態を意味し、加水分解物の縮合物とは、少なくとも一部のシラノール基同士が縮合してシロキサン結合（Ｓｉ−Ｏ−Ｓｉ）が形成された状態を意味する。
第１の縮合物および第２の縮合物はいずれも、分岐状のシロキサン結合を有する。縮合物の原料として、アルコキシ基を３個以上有するアルコキシシランを１種以上用いることにより、分岐状のシロキサン結合が形成される。
第１の縮合物および第２の縮合物はいずれも１価の有機基を有する。該有機基の種類を変えることによって、固体の表面自由エネルギーの極性力成分（γＳ^ｐ）を調整できる。第１の縮合物中の有機基と第２の縮合物中の有機基とは、少なくとも一部が異なっている。〔Composition〕
The composition of the present invention (hereinafter also referred to as “the present composition”) includes a first condensate and a second condensate. Each of the first condensate and the second condensate is a condensate of a hydrolyzate of alkoxysilane.
The alkoxysilane used in the present invention is a compound in which n ⁰ (n ⁰ is an integer of 1 to 4) alkoxy groups are bonded to a silicon atom. The alkoxysilane is preferably a compound in which n ⁰ (n ⁰ is an integer of 1 to 4) alkoxy group and (4-n ⁰ ) monovalent organic groups are bonded to a silicon atom.
The hydrolyzate of alkoxysilane means a state in which at least part of the alkoxysilyl group (Si-OR) is hydrolyzed to form a silanol group (Si-OH). It means a state in which at least some silanol groups are condensed to form a siloxane bond (Si—O—Si).
Both the first condensate and the second condensate have a branched siloxane bond. By using one or more alkoxysilanes having three or more alkoxy groups as the condensate raw material, a branched siloxane bond is formed.
Both the first condensate and the second condensate have a monovalent organic group. By changing the type of the organic group, the polar force component (γS ^p ) of the surface free energy of the solid can be adjusted. The organic group in the first condensate and the organic group in the second condensate are at least partially different.

第１の縮合物と第２の縮合物とは、固体の表面自由エネルギーの極性力成分（γＳ^ｐ）が異なる。第１の縮合物の該極性力成分（γＳ^ｐ）は５ｍＮ／ｍ未満であり、第２の縮合物の該極性力成分（γＳ^ｐ）は５ｍＮ／ｍ以上である。該極性力成分（γＳ^ｐ）が互いに異なる縮合物を混合することにより、混合しない場合に比べて膜の滑水性が向上する。
第１の縮合物の該極性力成分（γＳ^ｐ）は、４ｍＮ／ｍ以下が好ましく、３ｍＮ／ｍ以下が特に好ましい。
第２の縮合物の該極性力成分（γＳ^ｐ）は、５ｍＮ／ｍ以上が好ましく、１０ｍＮ／ｍ以上が特に好ましい。上限は水転落角が小さくなりやすい点から５０ｍＮ／ｍ以下が好ましく、２５ｍＮ／ｍ以下が特に好ましい。
両者の該極性力成分（γＳ^ｐ）の差の絶対値は２〜４０ｍＮ／ｍが好ましく、５〜２０ｍＮ／ｍが特に好ましい。 The first condensate and the second condensate have different polar force components (γS ^p ) of the solid surface free energy. Polar force component of the first condensate (gammaS ^p) is less than 5 mN / m, polar force component in the second condensate (gammaS ^p) is 5 mN / m or more. By mixing condensates having different polar force components (γS ^p ), the water slidability of the membrane is improved as compared with the case where the polar force components (γS ^p ) are not mixed.
The polar force component (γS ^p ) of the first condensate is preferably 4 mN / m or less, particularly preferably 3 mN / m or less.
The polar force component (γS ^p ) of the second condensate is preferably 5 mN / m or more, particularly preferably 10 mN / m or more. The upper limit is preferably 50 mN / m or less, particularly preferably 25 mN / m or less, from the viewpoint that the water falling angle tends to be small.
The absolute value of the difference between the two polar force components (γS ^p ) is preferably 2 to 40 mN / m, particularly preferably 5 to 20 mN / m.

（第１の縮合物）
第１の縮合物の態様は、第１のアルコキシシランの加水分解物の縮合物である。前記第１のアルコキシシランは、アルコキシ基を３個以上有し下記Ｒ^３を有しないアルコキシシランと、下記Ｒ^３を有するアルコキシシランとを含む、またはアルコキシ基を３個以上有しかつ下記Ｒ^３を有するアルコキシシランを含み、後述のＲ^４を有するアルコキシシランを含まない。
Ｒ^３は炭素数８以上のアルキル基、炭素数８以上のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数８以上のフルオロアルキル基、または炭素数８以上のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。 (First condensate)
The aspect of the first condensate is a condensate of the hydrolyzate of the first alkoxysilane. Said first alkoxysilane, an alkoxysilane having no following R ³ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^3, having the following R ³ And alkoxysilane having R ⁴ described later is not included.
R ³ represents an alkyl group having 8 or more carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 8 or more carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a fluoroalkyl having 8 or more carbon atoms A group having an etheric oxygen atom between carbon-carbon atoms of the group.

第１の縮合物は、第１のアルコキシシランの加水分解物の縮合物であって、第１のアルコキシシランが、化合物（１）〜（５）からなる群から選ばれる１種以上からなり、かつ、少なくとも化合物（１）と化合物（４）、または化合物（５）を含むことが好ましい。
Ｓｉ−（ＯＲ^１）_４ …（１）
Ｒ^２ _２−Ｓｉ−（ＯＲ^１）_２ …（２）
Ｒ^２ _３−Ｓｉ−（ＯＲ^１） …（３）
Ｒ^３−Ｓｉ−Ｒ^２（ＯＲ^１）_２ …（４）
Ｒ^３−Ｓｉ−（ＯＲ^１）_３ …（５）
（式中、Ｒ^１は炭素数１〜４のアルキル基であり、Ｒ^２はメチル基またはエチル基であり、Ｒ^３は炭素数８以上のアルキル基、炭素数８以上のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数８以上のフルオロアルキル基、または炭素数８以上のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。なお、ＯＲ^１およびＲ^２が複数個ある場合にはそれらは同じでも異なっていてもよい。） The first condensate is a condensate of a hydrolyzate of the first alkoxysilane, and the first alkoxysilane comprises one or more selected from the group consisting of the compounds (1) to (5), And it is preferable that a compound (1) and a compound (4) or a compound (5) are included at least.
Si- (OR ¹ ) ₄ (1)
R ² ₂ —Si— (OR ¹ ) ₂ (2)
R ² ₃ —Si— (OR ¹ ) (3)
R ³ —Si—R ² (OR ¹ ) ₂ (4)
R ³ —Si— (OR ¹ ) ₃ (5)
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is an alkyl group having 8 or more carbon atoms, or a carbon atom of an alkyl group having 8 or more carbon atoms) A group having an etheric oxygen atom between carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkyl group having 8 or more carbon atoms. ^When there are a plurality of ¹ and R ^2, they may be the same or different.)

第１のアルコキシシランが、アルコキシ基を３個以上有するアルコキシシランを含むことで、第１の縮合物中に分岐状のシロキサン結合が形成される。
Ｒ^３は、固体の表面自由エネルギーの極性力成分（γＳ^ｐ）の低下に寄与する。 When the first alkoxysilane contains an alkoxysilane having three or more alkoxy groups, a branched siloxane bond is formed in the first condensate.
R ³ contributes to a decrease in the polar force component (γS ^p ) of the solid surface free energy.

Ｒ^３は直鎖状が好ましい。Ｒ^３の具体例としては、
Ｃ_ｎＨ_２ｎ＋１−（ｎは８〜３０の整数）、
Ｃ_ｔＦ_２ｔ＋１（ＣＨ_２）_ｍ−（ｔは４〜１２の整数、ｍは１〜４の整数、ｔ＋ｍは８〜１６）、
Ｈ（ＣＦ_２）_ａ（ＣＨ_２）_ｂ−（ａは４〜１２の整数、ｂは１〜４の整数、ａ＋ｂは８〜１６）、
Ｃ_ｃＦ_２ｃ＋１Ｏ（Ｃ_ｄＦ_２ｄＯ）_ｅ−（ＣＨ_２）_ｆ−Ｑ−（ＣＨ_２）_ｇ−（ｃは１〜１２の整数、ｄは１〜１０の整数、ｅは１〜２００の整数、ｆは０または１〜４の整数、ｇは１〜４の整数、ｃ＋（ｄ×ｅ）＋ｆ＋ｇは８以上の整数、Ｑは単結合または２価の有機基を示す。）が挙げられる。
前記（Ｃ_ｄＦ_２ｄＯ）_ｅにおいて、ｅ個の（Ｃ_ｄＦ_２ｄＯ）の炭素数（ｄ）は同じであっても異なってもよい。またｅ個の（Ｃ_ｄＦ_２ｄＯ）の結合順序は限定されない。例えば、これらの基がランダム状、交互またはブロック状に配置されてもよい。
前記Ｑの有機基の例としては、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−Ｃ（Ｏ）Ｏ−、−Ｃ（Ｏ）Ｓ−、−Ｎ（Ｒ^７）−、−ＳＯ_２−、−ＰＯ_２−、−Ｎ（Ｒ^７）−Ｃ（Ｏ）Ｏ−、−Ｎ（Ｒ^７）−Ｃ（Ｏ）−、−Ｎ（Ｒ^７）−ＳＯ_２−、または−Ｎ（Ｒ^７）−ＰＯ_２−（Ｒ^７は水素原子または炭素数１〜３のアルキル基を示す。）が挙げられる。 R ³ is preferably linear. Specific examples of R ³ include
C _n H _{2n + 1} − (n is an integer of 8 to 30),
_{_{_{C t F 2t + 1 (CH}}} 2) m - (t 4-12 integer, m is an integer from 1 to 4, t + m is 8 to 16),
_{_{_{H (CF 2) a (CH}}} 2) b - (a 4 to 12 integer, b is an integer from 1 to 4, a + b is 8 to 16),
_{_{_{_{C c F 2c + 1 O (}}}} C d F 2d O) e - (CH 2) f -Q- (CH 2) g - (c is an integer of 1 to 12, d is an integer of from 1 to 10, e is 1 to 200 F is 0 or an integer of 1 to 4, g is an integer of 1 to 4, c + (d × e) + f + g is an integer of 8 or more, and Q is a single bond or a divalent organic group. It is done.
In the (C _d F _2d O) _e , the number of carbon atoms (d) of e (C _d F _2d O) may be the same or different. Further, the bonding order of e (C _d F _2d O) is not limited. For example, these groups may be arranged randomly, alternately or in blocks.
Examples of the organic group of Q include —O—, —S—, —C (O) —, —C (O) O—, —C (O) S—, —N (R ⁷ ) —, — _{_{^{SO 2 -, - PO 2 -}}} , - N (R 7) -C (O) O -, - N (R 7) -C (O) -, - N (R 7) -SO 2 -, or -N (R ⁷ ) —PO ₂ — (R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).

第１のアルコキシシランは、化合物（５）からなるか、または化合物（１）と化合物（５）とを含むことがより好ましい。
第１のアルコキシシランが化合物（１）と化合物（５）とを含む場合、第１のアルコキシシランに対して、化合物（１）と化合物（５）との合計が１０〜１００モル％であることが好ましく、２０〜１００モル％がより好ましく、５０〜１００モル％が特に好ましい。１００モル％でもよい。
第１のアルコキシシラン中の化合物（１）と化合物（５）との含有比率（化合物（１）／化合物（５））は、０／１０〜９／１（モル比）が好ましく、１／１〜９／１（モル比）がより好ましく、３／１〜６／１（モル比）が特に好ましい。
化合物（５）の含有比率が前記範囲の下限値未満であると撥水性が発現しない。 More preferably, the first alkoxysilane consists of the compound (5) or contains the compound (1) and the compound (5).
When the first alkoxysilane includes the compound (1) and the compound (5), the total of the compound (1) and the compound (5) is 10 to 100 mol% with respect to the first alkoxysilane. Is preferable, 20-100 mol% is more preferable, and 50-100 mol% is especially preferable. 100 mol% may be sufficient.
The content ratio (compound (1) / compound (5)) of the compound (1) and the compound (5) in the first alkoxysilane is preferably 0/10 to 9/1 (molar ratio), and 1/1. ~ 9/1 (molar ratio) is more preferable, and 3/1 to 6/1 (molar ratio) is particularly preferable.
When the content ratio of the compound (5) is less than the lower limit of the above range, water repellency is not exhibited.

第１のアルコキシシランが、化合物（１）〜（５）からなる群から選ばれる２種以上を含む場合、該２種以上の化合物のＲ^１は互いに同じであってもよく、異なっていてもよい。
第１のアルコキシシランが、化合物（２）、（３）および（４）からなる群から選ばれる２種以上を含む場合、該２種以上の化合物のＲ^２は互いに同じであってもよく、異なっていてもよい。
第１のアルコキシシランが、化合物（４）および（５）からなる群から選ばれる２種以上を含む場合、該２種以上の化合物のＲ^３は互いに同じであってもよく、異なっていてもよい。 When the first alkoxysilane includes two or more selected from the group consisting of the compounds (1) to (5), R ¹ of the two or more compounds may be the same as or different from each other. Good.
When the first alkoxysilane includes two or more selected from the group consisting of the compounds (2), (3) and (4), R ² of the two or more compounds may be the same as each other, May be different.
When the first alkoxysilane includes two or more selected from the group consisting of the compounds (4) and (5), R ³ of the two or more compounds may be the same or different from each other. Good.

（第２の縮合物）
第２の縮合物の好ましい態様は、第２のアルコキシシランの加水分解物の縮合物である。前記第２のアルコキシシランは、アルコキシ基を３個以上有し下記Ｒ^４を有しないアルコキシシランと、下記Ｒ^４を有するアルコキシシランとを含む、またはアルコキシ基を３個以上有しかつ下記Ｒ^４を有するアルコキシシランを含み、前記Ｒ^３を有するアルコキシシランを含まない。
Ｒ^４は、炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基、炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のアルキル基、炭素数３〜６のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のフルオロアルキル基、または炭素数３〜６のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。 (Second condensate)
A preferred embodiment of the second condensate is a condensate of the hydrolyzate of the second alkoxysilane. Said second alkoxysilane, an alkoxysilane having no following R ⁴ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^4, having the following R ⁴ And the alkoxysilane having R ³ is not included.
R ⁴ is a group in which one or more hydrogen atoms of an alkyl group having 1 to 20 carbon atoms are substituted with a polar group, and one or more hydrogen atoms in an alkyl group having 1 to 20 carbon atoms are substituted with a polar group. A group having an etheric oxygen atom between carbon-carbon atoms of the group, an alkyl group having 3 to 6 carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, carbon number It is a group having an etheric oxygen atom between carbon-carbon atoms of a 3-6 fluoroalkyl group or a C3-C6 fluoroalkyl group.

第２の縮合物は、第２のアルコキシシランの加水分解物の縮合物であって、第２のアルコキシシランが、化合物（１１）〜（１５）からなる群から選ばれる１種以上からなり、かつ、少なくとも化合物（１１）と化合物（１４）、または化合物（１５）を含むことが好ましい。
Ｓｉ−（ＯＲ^１１）_４ …（１１）
Ｒ^２１ _２−Ｓｉ−（ＯＲ^１１）_２ …（１２）
Ｒ^２１ _３−Ｓｉ−（ＯＲ^１１） …（１３）
Ｒ^４−Ｓｉ−Ｒ^２１（ＯＲ^１１）_２ …（１４）
Ｒ^４−Ｓｉ−（ＯＲ^１１）_３ …（１５）
（式中、Ｒ^１１は炭素数１〜４のアルキル基であり、Ｒ^２１はメチル基またはエチル基であり、Ｒ^４は炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基、炭素数１〜２０のアルキル基の水素原子の１個以上が極性基で置換された基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のアルキル基、炭素数３〜６のアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基、炭素数３〜６のフルオロアルキル基、または炭素数３〜６のフルオロアルキル基の炭素−炭素原子間にエーテル性酸素原子を有する基である。なお、ＯＲ^１１およびＲ^２１が複数個ある場合にはそれらは同じでも異なっていてもよい。）
極性基としては、−ＳＨ、−ＯＨ、−Ｃ（＝Ｏ）Ｈ、−Ｃｌ、−ＣＮ、−Ｆ、−ＣＦ_３、−ＣＦ_２Ｈ、−ＣＯＯＨ、−ＣＯＯＲ^５、−ＰＯ_３Ｈ、−ＳＯ_３Ｈ、−ＮＨ_２および−ＮＲ^６ _２（ただし、Ｒ^５、Ｒ^６は炭素数１〜６のアルキル基）からなる群から選ばれる１種以上が挙げられる。 The second condensate is a condensate of the hydrolyzate of the second alkoxysilane, and the second alkoxysilane comprises one or more selected from the group consisting of the compounds (11) to (15), And it is preferable that a compound (11) and a compound (14) or a compound (15) are included at least.
Si- (OR ¹¹ ) ₄ (11)
R ²¹ ₂ —Si— (OR ¹¹ ) ₂ (12)
R ²¹ ₃ —Si— (OR ¹¹ ) (13)
R ⁴ —Si—R ²¹ (OR ¹¹ ) ₂ (14)
R ⁴ —Si— (OR ¹¹ ) ₃ (15)
Wherein R ¹¹ is an alkyl group having 1 to 4 carbon atoms, R ²¹ is a methyl group or an ethyl group, and R ⁴ is one or more hydrogen atoms of the alkyl group having 1 to 20 carbon atoms. A group having 1 to 20 carbon atoms, a group having at least one hydrogen atom of an alkyl group having 1 to 20 carbon atoms, and a group having an etheric oxygen atom between carbon-carbon atoms of a group having a polar group substituted, and having 3 to 6 carbon atoms Carbon-carbon of an alkyl group, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 6 carbon atoms, or a fluoroalkyl group having 3 to 6 carbon atoms (It is a group having an etheric oxygen atom between atoms, and when there are a plurality of OR ¹¹ and R ^21, they may be the same or different.)
Examples of the polar _{group, -SH, -OH, -C (=} O) H, -Cl, -CN, -F, -CF 3, -CF 2 H, -COOH, -COOR 5, -PO 3 H, - SO ₃ H, -NH ₂ and ^-NR _{6 2} (provided ^that, R 5, ^{R 6} is an alkyl group having 1 to 6 carbon atoms) include one or more selected from the group consisting of.

第２のアルコキシシランが、アルコキシ基を３個以上有するアルコキシシランを含むことで、第２の縮合物中に分岐状のシロキサン結合が形成される。
Ｒ^４は、固体の表面自由エネルギーの極性力成分（γＳ^ｐ）の増大に寄与する。 When the second alkoxysilane contains an alkoxysilane having 3 or more alkoxy groups, a branched siloxane bond is formed in the second condensate.
R ⁴ contributes to an increase in the polar force component (γS ^p ) of the solid surface free energy.

Ｒ^４のうち前記極性基を有する基は、直鎖状でも分岐状でもよい。炭素数は１〜２０であり、１〜１２が好ましく、１〜８がより好ましく、１〜４が特に好ましい。極性基の数は１〜５個が好ましく、１〜３個がより好ましく、１個が特に好ましい。極性基は少なくとも末端に存在することが好ましい。
具体例としては、
ＨＳ（ＣＨ_２）_ｈ−（ｈは１〜２０の整数）、
ＨＯ（ＣＨ_２）_ｉ−（ｉは１〜２０の整数）、
ＨＣ（＝Ｏ）（ＣＨ_２）_ｊ−（ｊは１〜２０の整数）、
Ｃｌ（ＣＨ_２）_ｋ−（ｋは１〜２０の整数）、
ＮＣ（ＣＨ_２）_ｌ−（ｌは１〜２０の整数）、
ＨＯ（Ｃ_２Ｈ_４Ｏ）_ｐ−（ｐは１〜１０の整数）が挙げられる。 The group having the polar group in R ⁴ may be linear or branched. Carbon number is 1-20, 1-12 are preferable, 1-8 are more preferable, and 1-4 are especially preferable. The number of polar groups is preferably 1 to 5, more preferably 1 to 3, and particularly preferably 1. The polar group is preferably present at least at the terminal.
As a specific example,
_{_{HS (CH 2) h - (}} h is an integer of 1 to 20),
_{_{HO (CH 2) i - (}} i is an integer of 1 to 20),
_{_{HC (= O) (CH 2}} ) j - (j is an integer of 1 to 20),
_{_{Cl (CH 2) k - (}} k is an integer of 1 to 20),
_{_{NC (CH 2) l - (}} l is an integer of 1 to 20),
_{_{_{HO (C 2 H 4 O)}}} p - (p is an integer of from 1 to 10) are exemplified.

Ｒ^４のうち前記極性基を有しない基は、直鎖状でもよく、分岐状でもよい。炭素数は３〜６である。
具体例としては、
Ｃ_ｑＨ_２ｑ＋１−（ｑは３〜６の整数）、
ＣＦ_３（ＣＨ_２）_ｒ−（ｒは２〜５の整数）
ＣＨ_３Ｏ（Ｃ_２Ｈ_４Ｏ）_ｓ−（ｓは１または２）が挙げられる。 The group having no polar group in R ⁴ may be linear or branched. Carbon number is 3-6.
As a specific example,
_{_{C q H 2q + 1 - (}} q is an integer of 3 to 6),
_{_{_{CF 3 (CH 2) r -}}} (r is 2-5 integer)
CH ₃ O (C ₂ H ₄ O) _s — (s is 1 or 2).

第２のアルコキシシランは、化合物（１５）からなるか、または化合物（１１）と化合物（１５）とを含むことがより好ましい。
第２のアルコキシシランが化合物（１１）と化合物（１５）とを含む場合、第２のアルコキシシランに対して、化合物（１１）と化合物（１５）との合計が１０〜１００モル％であることが好ましく、２０〜１００モル％がより好ましく、５０〜１００モル％が特に好ましい。１００モル％でもよい。
第２のアルコキシシラン中の化合物（１１）と化合物（１５）との含有比率（化合物（１１）／化合物（１５））は、０／１０〜９／１（モル比）が好ましく、１／１〜９／１（モル比）がより好ましく、３／１〜６／１（モル比）が特に好ましい。
化合物（１５）の含有比率が前記範囲の下限値未満であると撥水性が発現しない。 More preferably, the second alkoxysilane consists of the compound (15) or contains the compound (11) and the compound (15).
When the second alkoxysilane includes the compound (11) and the compound (15), the total of the compound (11) and the compound (15) is 10 to 100 mol% with respect to the second alkoxysilane. Is preferable, 20-100 mol% is more preferable, and 50-100 mol% is especially preferable. 100 mol% may be sufficient.
The content ratio of the compound (11) and the compound (15) in the second alkoxysilane (compound (11) / compound (15)) is preferably 0/10 to 9/1 (molar ratio), and 1/1 ~ 9/1 (molar ratio) is more preferable, and 3/1 to 6/1 (molar ratio) is particularly preferable.
When the content ratio of the compound (15) is less than the lower limit of the above range, water repellency is not exhibited.

第２のアルコキシシランが、化合物（１１）〜（１５）からなる群から選ばれる２種以上を含む場合、該２種以上の化合物のＲ^１１は互いに同じであってもよく、異なっていてもよい。
第２のアルコキシシランが、化合物（１２）、（１３）および（１４）からなる群から選ばれる２種以上を含む場合、該２種以上の化合物のＲ^２１は互いに同じであってもよく、異なっていてもよい。
第２のアルコキシシランが、化合物（１４）および（１５）からなる群から選ばれる２種以上を含む場合、該２種以上の化合物のＲ^４は互いに同じであってもよく、異なっていてもよい。 When the second alkoxysilane includes two or more selected from the group consisting of the compounds (11) to (15), R ¹¹ of the two or more compounds may be the same as or different from each other. Good.
When the second alkoxysilane includes two or more selected from the group consisting of the compounds (12), (13) and (14), R ²¹ of the two or more compounds may be the same as each other, May be different.
When the second alkoxysilane contains two or more selected from the group consisting of the compounds (14) and (15), R ⁴ of the two or more compounds may be the same or different from each other. Good.

（縮合物の製造方法）
第１の縮合物または第２の縮合物は、第１のアルコキシシランまたは第２のアルコキシシランを、水、触媒および有機溶媒を含む溶液中で加水分解および縮合させることでそれぞれ得られる。該加水分解および縮合は部分的でもよく、第１の縮合物または第２の縮合物に、未反応のアルコキシ基または未反応のシラノール基が残存してもよい。残存する未反応基は、本組成物を硬化させる際に加水分解および縮合させることができる。
触媒は、アルコキシ基の加水分解反応を促進させる触媒として公知の化合物を用いることができる。例えば塩酸、硫酸、硝酸、酢酸、無水酢酸、マレイン酸、無水マレイン酸、リンゴ酸等が挙げられる。
水の添加量は、第１のアルコキシシランまたは第２のアルコキシシランに含まれる全てのアルコキシ基が加水分解してシラノール基を生成するのに必要な量であることが好ましい。
有機溶媒は、前記水との混和性を有し、蒸気圧が水より高いものが好ましい。例えば、メタノール、エタノール、イソプロパノール等のアルコール類、テトラヒドロフラン等の環状エーテル類が挙げられる。有機溶媒の使用量は第１のアルコキシシランまたは第２のアルコキシシランの１質量部に対して１〜１０質量部が好ましく、１〜５質量部がより好ましく、２〜４質量部が特に好ましい。反応は室温で行うことができる。 (Condensate production method)
The first condensate or the second condensate can be obtained by hydrolyzing and condensing the first alkoxysilane or the second alkoxysilane in a solution containing water, a catalyst, and an organic solvent, respectively. The hydrolysis and condensation may be partial, and an unreacted alkoxy group or an unreacted silanol group may remain in the first condensate or the second condensate. The remaining unreacted groups can be hydrolyzed and condensed when the composition is cured.
As the catalyst, a known compound can be used as a catalyst for promoting the hydrolysis reaction of the alkoxy group. Examples thereof include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, acetic anhydride, maleic acid, maleic anhydride, malic acid and the like.
The amount of water added is preferably an amount necessary for hydrolyzing all alkoxy groups contained in the first alkoxysilane or the second alkoxysilane to produce silanol groups.
The organic solvent is preferably miscible with water and has a higher vapor pressure than water. Examples thereof include alcohols such as methanol, ethanol and isopropanol, and cyclic ethers such as tetrahydrofuran. The amount of the organic solvent used is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass, and particularly preferably 2 to 4 parts by mass with respect to 1 part by mass of the first alkoxysilane or the second alkoxysilane. The reaction can be carried out at room temperature.

（他の成分）
本組成物は、第１の縮合物または第２の縮合物の製造上不可避の成分を含んでもよい。具体的には、第１の縮合物または第２の縮合物の製造に用いた水、触媒、有機溶媒、副生物等を含んでもよい。
本組成物をコーティング液として使用する際は、基材表面への塗布性に優れる点から、本組成物は溶媒を含むことが好ましい。該溶媒は、第１の縮合物または第２の縮合物の製造に用いた溶媒でもよく、さらに溶媒を添加して希釈してもよい。第１の縮合物または第２の縮合物の製造に用いた溶媒を除去してから、溶媒を添加してもよい。溶媒としては、第１の縮合物または第２の縮合物の製造に用いられる有機溶媒と同様のものが挙げられる。
本組成物は、さらに必要に応じて、本組成物の安定性、膜の滑水性、外観等を損なわない範囲で、前記以外の他の成分を含んでいてもよい。
他の成分としては、例えば界面活性剤等が挙げられる。界面活性剤は１種を単独で用いても２種以上を併用してもよい。 (Other ingredients)
The present composition may contain components unavoidable for the production of the first condensate or the second condensate. Specifically, water, a catalyst, an organic solvent, a by-product and the like used for the production of the first condensate or the second condensate may be included.
When using this composition as a coating liquid, it is preferable that this composition contains a solvent from the point which is excellent in the applicability | paintability to the base-material surface. The solvent may be the solvent used in the production of the first condensate or the second condensate, and may be further diluted by adding a solvent. The solvent may be added after removing the solvent used in the production of the first condensate or the second condensate. Examples of the solvent include the same organic solvents used for the production of the first condensate or the second condensate.
The composition may further contain other components other than those described above as required, as long as the stability of the composition, the water slidability, the appearance, and the like of the composition are not impaired.
Examples of other components include a surfactant. Surfactant may be used individually by 1 type, or may use 2 or more types together.

（各成分の含有割合）
本組成物に含まれる、第１の縮合物と第２の縮合物との質量比（第１の縮合物／第２の縮合物）は１／２〜１，０００／１が好ましく、１／１〜１００／１がより好ましく、３／１〜２０／１が特に好ましい。該質量比が前記範囲内であると、第１の縮合物と第２の縮合物を混合して用いることによる滑水性向上効果が充分に得られやすい。
第１の縮合物が前記第１のアルコキシシランの加水分解物の縮合物であり、第２の縮合物が前記第２のアルコキシシランの加水分解物の縮合物である場合、本組成物中に存在する、Ｒ^３とＲ^４のモル比（Ｒ^３／Ｒ^４）は１／２〜１，０００／１が好ましく、１／１〜１００／１がより好ましく、３／１〜２０／１が特に好ましい。該モル数の比が前記範囲内であると、第１の縮合物と第２の縮合物を混合して用いることによる滑水性向上効果が充分に得られやすい。
本組成物中の他の成分の含有量は、本組成物中の固形分（１００質量％）に対し、１０質量％以下が好ましく、３質量％以下が特に好ましい。下限は特に限定されず、０質量％であってもよい。
本組成物をコーティング液として用いる場合、コーティング液の固形分濃度は、０．１〜２０質量％が好ましく、１〜１０質量％がより好ましく、２〜５質量％が特に好ましい。該固形分濃度が前記範囲内であると、コーティング液を用いて形成される膜の膜厚が、滑水性、撥水性等の各種性能が充分に発揮される好適な範囲内となりやすい。
本組成物をコーティング液として用いる場合、コーティング液中の溶媒の含有量は、８０〜９９．９質量％が好ましく、９０〜９９質量％がより好ましく、９５〜９８質量％が特に好ましい。 (Content ratio of each component)
The mass ratio of the first condensate and the second condensate contained in the composition (first condensate / second condensate) is preferably 1/2 to 1,000 / 1, 1-100 / 1 is more preferable, and 3 / 1-20 / 1 is particularly preferable. When the mass ratio is within the above range, the effect of improving the water slidability by mixing the first condensate and the second condensate is easily obtained.
In the case where the first condensate is a condensate of the hydrolyzate of the first alkoxysilane and the second condensate is a condensate of the hydrolyzate of the second alkoxysilane, The molar ratio of R ³ to R ⁴ (R ³ / R ⁴ ) present is preferably 1/2 to 1,000 / 1, more preferably 1/1 to 100/1, and 3/1 to 20/1. Particularly preferred. When the ratio of the number of moles is within the above range, the effect of improving the water slidability by mixing and using the first condensate and the second condensate is easily obtained.
10 mass% or less is preferable with respect to solid content (100 mass%) in this composition, and, as for content of the other component in this composition, 3 mass% or less is especially preferable. The lower limit is not particularly limited, and may be 0% by mass.
When using this composition as a coating liquid, 0.1-20 mass% is preferable, as for the solid content concentration of a coating liquid, 1-10 mass% is more preferable, and 2-5 mass% is especially preferable. When the solid content concentration is within the above range, the thickness of the film formed using the coating liquid tends to be within a suitable range in which various performances such as water slidability and water repellency are sufficiently exhibited.
When using this composition as a coating liquid, 80-99.9 mass% is preferable, as for content of the solvent in a coating liquid, 90-99 mass% is more preferable, and 95-98 mass% is especially preferable.

（本組成物の製造方法）
本組成物は、前記製造方法で得た第１の縮合物、第２の縮合物、および必要に応じた他の成分および溶媒を混合して得られる。 (Method for producing the present composition)
The present composition is obtained by mixing the first condensate, the second condensate obtained by the above production method, and other components and a solvent as required.

（２液型組成物）
前記製造方法で得た第１の縮合物と溶媒を含む第１の組成物と、前記製造方法で得た第２の縮合物と溶媒を含む第２の組成物を別個に保管し、使用直前にこれらを混合して本組成物を調製してもよい。
本発明の２液型組成物は、第１の組成物と、第２の組成物からなる。
第１の組成物と第２の組成物は溶媒を含んでいてもよい。
第１の組成物と第２の組成物を混合する際に、さらに溶媒を加えて希釈してもよい。
２液型組成物において前記他の成分を含有させる場合、第１の組成物および第２の組成物の一方または両方に他の成分を含有させてもよく、第１の組成物と第２の組成物を混合する際に他の成分を添加してもよい。 (Two-component composition)
The first composition containing the first condensate and the solvent obtained by the production method and the second composition containing the second condensate and the solvent obtained by the production method are stored separately and immediately before use. These compositions may be mixed to prepare this composition.
The two-component composition of the present invention comprises a first composition and a second composition.
The first composition and the second composition may contain a solvent.
When mixing the first composition and the second composition, a solvent may be further added for dilution.
When the other component is contained in the two-component composition, one or both of the first composition and the second composition may contain the other component, and the first composition and the second composition Other ingredients may be added when mixing the composition.

（作用効果）
本組成物を用いて基材上に膜を形成すると、第１の縮合物のみを含む組成物で形成された膜の水転落角、および第２の縮合物のみを含む組成物で形成された膜の水転落のいずれよりも、水転落角が小さく滑水性に優れる膜を得ることができる。
その理由は明かではないが、膜表面に第１の縮合物に由来する領域と第２の縮合物に由来する領域とが混在して、膜表面の濡れ性や付着性が不均一になることによって、滑水性が向上すると推測される。 (Function and effect)
When a film was formed on a substrate using this composition, it was formed with a water drop angle of the film formed with the composition containing only the first condensate and a composition containing only the second condensate. A film having a small water tumbling angle and excellent water slidability can be obtained as compared with any of water tumbling of the film.
The reason is not clear, but the region derived from the first condensate and the region derived from the second condensate are mixed on the film surface, resulting in non-uniform wettability and adhesion on the film surface. Therefore, it is estimated that the water slidability is improved.

〔物品〕
本発明の物品は、本組成物から形成された膜を基材の表面に有する。
前記膜の厚さは、５〜５００ｎｍが好ましく、１０〜１００ｎｍが特に好ましい。膜の厚さが前記範囲の下限値以上であれば、充分な滑水性が発現しやすい。膜の厚さが前記範囲の上限値以下であれば、膜強度に優れる。
膜の厚さは、Ｊ．Ａ・ウーラム社に代表されるエリプソメータを用いた測定により求められる。 [Articles]
The article of the present invention has a film formed from the composition on the surface of the substrate.
The thickness of the film is preferably 5 to 500 nm, particularly preferably 10 to 100 nm. If the thickness of the film is equal to or greater than the lower limit of the above range, sufficient lubricity is likely to be manifested. When the thickness of the film is not more than the upper limit of the above range, the film strength is excellent.
The thickness of the membrane is It is determined by measurement using an ellipsometer represented by A. Woollam.

（基材）
本発明における基材は、滑水性の付与が求められている基材であれば特に限定されない。基材の材料としては、金属、樹脂、ガラス、サファイア、セラミック、石、木材、繊維、これらの２種以上の複合材料等が挙げられる。 (Base material)
The base material in the present invention is not particularly limited as long as it is a base material that is required to impart lubricity. Examples of the base material include metals, resins, glass, sapphire, ceramics, stones, wood, fibers, and composite materials of two or more of these.

（物品の製造方法）
本発明の物品は、例えば、溶媒を含む本組成物を基材の表面に塗布し、溶媒を除去して膜を形成する方法により製造できる。
本組成物の塗布方法としては、公知のウェットコーティング法を利用でき、例えばディップコート法、スピンコート法、ワイプコート法、スプレーコート法、スキージーコート法、ダイコート法、インクジェット法、フローコート法、ロールコート法、キャスト法、ラングミュア・ブロジェット法、グラビアコート法等が挙げられる。
溶媒の除去方法としては、溶媒の沸点以上の温度で加熱する方法が好ましい。ただし、基材の材質等によって加熱乾燥が困難な場合には、加熱を回避して乾燥すべきである。加熱条件は膜の組成や塗布面積等に応じて選択すればよい。 (Product manufacturing method)
The article of the present invention can be produced, for example, by a method of forming a film by applying the present composition containing a solvent to the surface of a substrate and removing the solvent.
As a coating method of the present composition, a known wet coating method can be used, for example, a dip coating method, a spin coating method, a wipe coating method, a spray coating method, a squeegee coating method, a die coating method, an ink jet method, a flow coating method, a roll. Examples thereof include a coating method, a casting method, a Langmuir / Blodgett method, and a gravure coating method.
As a method for removing the solvent, a method of heating at a temperature equal to or higher than the boiling point of the solvent is preferable. However, when heat drying is difficult due to the material of the substrate, etc., heating should be avoided to dry. The heating conditions may be selected according to the composition of the film, the application area, and the like.

本発明の２液型組成物を用いる場合は、第１の組成物と第２の組成物とを混合し、次いで、前記と同様にして基材の表面に塗布し、前記と同様にして溶媒を除去し、基材の表面に膜を形成する方法により物品を製造できる。 When using the two-component composition of the present invention, the first composition and the second composition are mixed, then applied to the surface of the substrate in the same manner as described above, and the solvent is determined in the same manner as described above. The article can be produced by a method of removing the film and forming a film on the surface of the substrate.

（作用効果）
本発明の物品が、基材の表面に有する膜は、本組成物から形成された膜であるため滑水性に優れる。 (Function and effect)
Since the film | membrane which the article | item of this invention has on the surface of a base material is a film | membrane formed from this composition, it is excellent in lubricity.

（物品の用途）
本発明の物品としては、滑水性が望まれているまたは必要とされている設備、装置、器具、部品等が好ましい。
物品の具体例としては、自動車の窓ガラス、自動車、バイク、自転車の塗装表面、台所設備、台所用品、台所設備に付設される排気装置、エア・コンディショナー等の空調設備のフィンやフィルター、入浴設備、洗面設備、医療用施設、医療用機械器具、鏡、眼鏡、インクジェットプリンター部品、便器、革靴、カーペット等が挙げられる。
冷蔵庫、冷凍庫、空調設備のフィンおよびフィルター等の水洗浄が実施される設備、装置、器具、部品等は、水洗浄後の水切り性を向上させるために、水滴が付着しにくくする機能が求められる。また、冷凍庫や空調設備のフィンおよびフィルター等の着氷防止膜としても使用可能である。滑水性に優れた膜は水滴が付着しにくいため、本発明の物品としては、水洗浄が実施される設備、装置、器具、部品等が好適である。 (Use of goods)
As the article of the present invention, facilities, devices, instruments, parts and the like in which water sliding is desired or required are preferable.
Specific examples of articles include automobile window glass, automobiles, motorcycles, bicycle paint surfaces, kitchen equipment, kitchenware, exhaust equipment attached to kitchen equipment, fins and filters for air conditioners such as air conditioners, bathing equipment, etc. , Toiletries, medical facilities, medical equipment, mirrors, glasses, inkjet printer parts, toilets, leather shoes, carpets, and the like.
Equipment, equipment, appliances, parts, etc. that are subjected to water washing such as refrigerators, freezers, fins and filters of air conditioning equipment are required to have a function to make water droplets difficult to adhere in order to improve drainage after water washing. . It can also be used as an anti-icing film for fins and filters of freezers and air conditioning equipment. Since a film excellent in water slidability is difficult for water droplets to adhere to it, facilities, devices, instruments, parts, and the like that are subjected to water washing are suitable as the article of the present invention.

以下、実施例を示して本発明を詳細に説明する。ただし、本発明は以下の記載によっては限定されない。「％」は、特に規定のない限り、「質量％」を示す。なお、例１〜７が比較例、例８〜１３が実施例である。
各例で使用した評価方法および材料を以下に示す。 Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited by the following description. “%” Indicates “mass%” unless otherwise specified. Examples 1 to 7 are comparative examples, and examples 8 to 13 are examples.
The evaluation methods and materials used in each example are shown below.

〔評価方法〕
（接触角）
２５℃、４０％ＲＨの環境下、膜付きガラス基板の膜の表面に水（イオン交換水）またはノルマルヘキサデカンの約２μＬを滴下して、接触角計（協和界面科学社製ＤＭ−５００）で接触角を測定した。水の接触角の値が大きいものほど撥水性が高く、ノルマルヘキサデカンの接触角の値が大きいものほど撥油性が高い。〔Evaluation method〕
(Contact angle)
In an environment of 25 ° C. and 40% RH, about 2 μL of water (ion exchange water) or normal hexadecane is dropped on the surface of the film-coated glass substrate, and a contact angle meter (DM-500 manufactured by Kyowa Interface Science Co., Ltd.) is used. The contact angle was measured. The greater the water contact angle value, the higher the water repellency, and the higher the normal hexadecane contact angle value, the higher the oil repellency.

（水転落角）
２５℃、４０％ＲＨの環境下、膜付きガラス基板の膜の表面にイオン交換水の１０μＬを滴下し、接触角計（協和界面科学社製ＤＭ−５００）を用いて、膜付きガラス基板を水平面に対して０°から９０°まで、１．６°／秒の速度で傾けた。この際、水滴が転がり始めたときの膜付きガラス基板の水平面に対する傾斜角度を水転落角とした。この値が小さいほど、滑水性が高いことになる。９０°傾けても水滴が滑落しないものは「転落せず」と記載した。 (Water falling angle)
In an environment of 25 ° C. and 40% RH, 10 μL of ion-exchanged water is dropped on the surface of the film-coated glass substrate, and the glass substrate with the film is formed using a contact angle meter (DM-500 manufactured by Kyowa Interface Science Co., Ltd.). It was tilted at a rate of 1.6 ° / second from 0 ° to 90 ° with respect to the horizontal plane. Under the present circumstances, the inclination angle with respect to the horizontal surface of the glass substrate with a film when a water droplet began to roll was made into the water fall angle. The smaller this value, the higher the lubricity. Those in which water droplets did not slide even when tilted by 90 ° were described as “no falls”.

〔材料〕
（第１のアルコキシシラン）
化合物（１−１）：テトラメトキシシラン
化合物（５−１）：ドデシルトリエトキシシラン
（第２のアルコキシシラン）
化合物（１１−１）：テトラメトキシシラン
化合物（１５−１）：（ＣＦ_３）（ＣＨ_２）−Ｓｉ−（ＯＣＨ_３）_３
化合物（１５−２）：ＨＳ（ＣＨ_２）_３−Ｓｉ−（ＯＣ_２Ｈ_５）_３
化合物（１５−３）：（Ｃ_３Ｈ_７）−Ｓｉ−（ＯＣＨ_３）_３
化合物（１５−４）：ＨＯ（ＣＨ_２）−Ｓｉ−（ＯＣ_２Ｈ_５）_３
化合物（１５−５）：ＨＣ（＝Ｏ）（Ｃ_４Ｈ_８）−Ｓｉ−（ＯＣ_２Ｈ_５）_３
化合物（１５−６）：Ｃｌ（ＣＨ_２）_３−Ｓｉ−（ＯＣ_２Ｈ_５）_３〔material〕
(First alkoxysilane)
Compound (1-1): Tetramethoxysilane Compound (5-1): Dodecyltriethoxysilane (second alkoxysilane)
Compound (11-1): Tetramethoxysilane Compound (15-1): (CF ₃ ) (CH ₂ ) —Si— (OCH ₃ ) ₃
Compound _{_{(15-2): HS (CH 2}} ) 3 -Si- (OC 2 H 5) 3
Compound _{_{(15-3) :( C 3 H 7}} ) -Si- (OCH 3) 3
Compound _{(15-4): HO (CH 2} ) -Si- (OC 2 H 5) 3
Compound _{_{(15-5): HC (= O}} ) (C 4 H 8) -Si- (OC 2 H 5) 3
Compound _{_{(15-6): Cl (CH 2}} ) 3 -Si- (OC 2 H 5) 3

〔製造例１〕
化合物（５−１）の１．６６ｇ（０．００５モル）、化合物（１−１）の３．８１ｇ（０．０２５モル）を、エタノールの１１．５２ｇに溶解し、０．００１Ｎ塩酸水溶液の１．９８ｇを添加した。この溶液を室温で２４時間撹拌し、第１の縮合物（１）を含む第１の組成物（１）を得た。 [Production Example 1]
1.66 g (0.005 mol) of compound (5-1) and 3.81 g (0.025 mol) of compound (1-1) were dissolved in 11.52 g of ethanol, and 0.001N hydrochloric acid aqueous solution was added. 1.98 g was added. This solution was stirred at room temperature for 24 hours to obtain a first composition (1) containing the first condensate (1).

〔製造例２〕
化合物（１５−１）の１．０９ｇ（０．００５モル）、化合物（１１−１）の３．８１ｇ（０．０２５モル）を、エタノールの１１．５２ｇに溶解し、０．００１Ｎ塩酸水溶液の１．９８ｇを添加した。この溶液を室温で２４時間撹拌し、第２の縮合物（１）を含む第２の組成物（１）を得た。 [Production Example 2]
1.09 g (0.005 mol) of compound (15-1) and 3.81 g (0.025 mol) of compound (11-1) were dissolved in 11.52 g of ethanol, and 0.001N hydrochloric acid aqueous solution was added. 1.98 g was added. This solution was stirred at room temperature for 24 hours to obtain a second composition (1) containing the second condensate (1).

〔製造例３〕
製造例２において、化合物（１５−１）を化合物（１５−２）の１．１９ｇ（０．００５モル）に変更したほかは同様にして第２の縮合物（２）を含む第２の組成物（２）を得た。
〔製造例４〕
製造例２において、化合物（１５−１）を化合物（１５−３）の０．８２ｇ（０．００５モル）に変更したほかは同様にして第２の縮合物（３）を含む第２の組成物（３）を得た。
〔製造例５〕
製造例２において、化合物（１５−１）を化合物（１５−４）の０．９７ｇ（０．００５モル）に変更したほかは同様にして第２の縮合物（４）を含む第２の組成物（４）を得た。
〔製造例６〕
製造例２において、化合物（１５−１）を化合物（１５−５）の１．１７ｇ（０．００５モル）に変更したほかは同様にして第２の縮合物（５）を含む第２の組成物（５）を得た。
〔製造例７〕
製造例２において、化合物（１５−１）を化合物（１５−６）の０．９９ｇ（０．００５モル）に変更したほかは同様にして第２の縮合物（６）を含む第２の組成物（６）を得た。 [Production Example 3]
The second composition containing the second condensate (2) in the same manner as in Production Example 2, except that the compound (15-1) was changed to 1.19 g (0.005 mol) of the compound (15-2). A product (2) was obtained.
[Production Example 4]
The second composition containing the second condensate (3) in the same manner as in Production Example 2, except that the compound (15-1) was changed to 0.82 g (0.005 mol) of the compound (15-3). A product (3) was obtained.
[Production Example 5]
The second composition containing the second condensate (4) in the same manner as in Production Example 2, except that the compound (15-1) was changed to 0.97 g (0.005 mol) of the compound (15-4). A product (4) was obtained.
[Production Example 6]
The second composition containing the second condensate (5) in the same manner as in Production Example 2, except that the compound (15-1) was changed to 1.17 g (0.005 mol) of the compound (15-5). A product (5) was obtained.
[Production Example 7]
The second composition containing the second condensate (6) in the same manner as in Production Example 2, except that the compound (15-1) was changed to 0.99 g (0.005 mol) of the compound (15-6). A product (6) was obtained.

〔例１〕
前記製造例で得た第１の組成物（１）を、固形分濃度が２質量％となるようにエタノールで希釈してコーティング液とした。
得られたコーティング液２ｍＬを、５ｃｍ角のガラス基板上にスピンコート法（毎分５００回転、１０秒間）により塗布し、１２０℃に温度調節したオーブン内で１５分間乾燥して膜を形成し、膜付きガラス基板（物品）を得た。この膜について、水転落角、水の接触角、およびノルマルヘキサデカンの接触角を測定し、前記の方法で固体の表面自由エネルギーγＳの分散力成分（γＳ^ｄ）と極性力成分（γＳ^ｐ）を求めた。結果を表１に示す（以下、同様。）。
得られた極性力成分（γＳ^ｐ）の値が、第１の組成物（１）中の第１の縮合物の極性力成分（γＳ^ｐ）である。 [Example 1]
The 1st composition (1) obtained by the said manufacture example was diluted with ethanol so that solid content concentration might be 2 mass%, and it was set as the coating liquid.
2 mL of the obtained coating solution was applied onto a 5 cm square glass substrate by spin coating (500 rpm, 10 seconds), and dried in an oven adjusted to 120 ° C. for 15 minutes to form a film. A glass substrate (article) with a film was obtained. With respect to this film, the water falling angle, the water contact angle, and the normal hexadecane contact angle were measured, and the dispersion force component (γS ^d ) and the polar force component (γS ^p ) of the solid surface free energy γS were measured by the above-described method. Asked. The results are shown in Table 1 (the same applies hereinafter).
The value of the resulting polar force component (gammaS ^p) is the polar force component of the first composition (1) a first condensate in (gammaS ^p).

〔例２〜７〕
前記製造例で得た第２の組成物（１）〜（６）を、それぞれ固形分濃度が２質量％となるようにエタノールで希釈してコーティング液とした。例１と同様にして膜付きガラス基板を作製し、測定を行った。
得られた極性力成分（γＳ^ｐ）の値が、第２の組成物（１）〜（６）中の各第２の縮合物の極性力成分（γＳ^ｐ）である。 [Examples 2 to 7]
The second compositions (1) to (6) obtained in the above production examples were each diluted with ethanol so that the solid content concentration was 2% by mass to obtain a coating solution. A glass substrate with a film was produced in the same manner as in Example 1 and measured.
The value of the resulting polar force component (gammaS ^p) is the polar force component in the second composition (1) to (6) each of the second condensate in (gammaS ^p).

〔例８〜１３〕
前記製造例で得た第１の組成物と第２の組成物とを、それぞれの反応終了後直ちに、表１に示す比率で混合した。次いで固形分濃度が２質量％となるようにエタノールで希釈してコーティング液とした。
表１に、第１の組成物と第２の組成物との質量比（第１の組成物／第２の組成物）、第１の縮合物と第２の縮合物との質量比（第１の縮合物／第２の縮合物）、およびコーティング液中に存在する、Ｒ^３とＲ^４とのモル比（Ｒ^３／Ｒ^４）を示す。
例１と同様にして膜付きガラス基板を作製し、測定を行った。 [Examples 8 to 13]
The first composition and the second composition obtained in the production example were mixed at the ratio shown in Table 1 immediately after the completion of each reaction. Subsequently, it diluted with ethanol so that solid content concentration might be 2 mass%, and it was set as the coating liquid.
Table 1 shows the mass ratio between the first composition and the second composition (first composition / second composition), and the mass ratio between the first condensate and the second condensate (first 1 of condensate / second condensate), and present in the coating liquid shows the molar ratio of ^{R 3} and ^{R 4} a ^(R 3 / ^{R 4).}
A glass substrate with a film was produced in the same manner as in Example 1 and measured.

表１に示されるように、極性力成分（γＳ^ｐ）が５ｍＮ／ｍ未満である第１の縮合物を含む第１の組成物（１）と、極性力成分（γＳ^ｐ）が５ｍＮ／ｍ以上である第２の縮合物を含む第２の組成物（１）〜（６）とを含む例８〜１３のコーティング液で形成された膜は、第２の縮合物を含まない例１、または第１の縮合物を含まない例２〜７のコーティング液で形成された膜と比べて、水転落角が小さく滑水性に優れる。
また第１の縮合物と第２の縮合物を含む例８〜１３のコーティング液で形成された膜は、水接触角が充分に大きく撥水性にも優れる。 As shown in Table 1, the first composition (1) containing the first condensate having a polar force component (γS ^p ) of less than 5 mN / m, and the polar force component (γS ^p ) of 5 mN / m The film formed with the coating liquids of Examples 8 to 13 including the second compositions (1) to (6) containing the second condensate as described above does not contain the second condensate. Or compared with the film | membrane formed with the coating liquid of Examples 2-7 which does not contain a 1st condensate, a water fall angle is small and it is excellent in lubricity.
Moreover, the film | membrane formed with the coating liquid of Examples 8-13 containing a 1st condensate and a 2nd condensate has a sufficiently large water contact angle, and is excellent also in water repellency.

Claims

This is a condensate of a hydrolyzate of alkoxysilane, which has a branched siloxane bond and a monovalent organic group, and the polar force component (γS ^p ) of the solid surface free energy determined by the following measurement method is 5 mN A first condensate that is less than / m;
This is a condensate of a hydrolyzate of alkoxysilane, which has a branched siloxane bond and a monovalent organic group, and the polar force component (γS ^p ) of the solid surface free energy determined by the following measurement method is 5 mN A second condensate that is at least / m;
The composition characterized by including.
Method for measuring polar force component (γS ^p ) of surface free energy of solid: forming a film made of a condensate to be measured, and the first liquid having the following γL ¹ , γL ^d1 and γL ^p1 and the film contact angle (theta ¹⁾ was measured in the following γL ^2, γL ^d2 and GanmaL ^p2 to measure the contact angle (theta ²⁾ of the second liquid and the film is known. Then, these values are substituted into the following formula (I-1) and the following formula (I-2). Next, the dispersion force component (γS ^d ) and the polar force component (γS ^p ) of the surface free energy γS of the solid are obtained from the simultaneous equations of the following formulas (I-1) and (I-2).
(ΓS ^d · γL ^d1 ) ^1/2 + (γS ^p · γL ^p1 ) ^1/2 = γL ¹ (1 + cos θ ¹ ) / 2 (I-1)
(ΓS ^d · γL ^d2 ) ^1/2 + (γS ^p · γL ^p2 ) ^1/2 = γL ² (1 + cos θ ² ) / 2 (I-2)
γS ^d : Dispersion force component of the surface free energy γS of the solid.
γS ^p : Polar force component of solid surface free energy γS.
γL ¹ : surface tension of the first liquid.
γL ² : surface tension of the second liquid.
θ ¹ : contact angle of the first liquid.
θ ² : contact angle of the second liquid.
γL ^d1 : Dispersive force component of the surface tension of the first liquid.
γL ^p1 : Polar force component of the surface tension of the first liquid.
γL ^d2 : Dispersion force component of the surface tension of the second liquid.
γL ^p2 : Polar force component of the surface tension of the second liquid.

A composition comprising: a first condensate that is a condensate of a hydrolyzate of a first alkoxysilane; and a second condensate that is a condensate of a hydrolyzate of a second alkoxysilane,
Said first alkoxysilane, an alkoxysilane having no following R ³ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^3, having the following R ³ Which does not include an alkoxysilane having the following R ⁴ :
Said second alkoxysilane, an alkoxysilane having no following R ⁴ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^4, having the following R ⁴ include alkoxysilanes having not contain an alkoxysilane having the following R ^3,
The composition characterized by the above-mentioned.
R ³ : an alkyl group having 8 or more carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 8 or more carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a fluoroalkyl having 8 or more carbon atoms A group having an etheric oxygen atom between carbon-carbon atoms of the group.
R ⁴ : a group in which one or more hydrogen atoms of an alkyl group having 1 to 20 carbon atoms are substituted with a polar group, and a group in which one or more hydrogen atoms of an alkyl group having 1 to 20 carbon atoms are substituted with a polar group A group having an etheric oxygen atom between carbon-carbon atoms, an alkyl group having 3 to 6 carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, 3 carbon atoms Or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkyl group of -6 or a C3-C6 fluoroalkyl group.

A composition comprising: a first condensate that is a condensate of a hydrolyzate of a first alkoxysilane; and a second condensate that is a condensate of a hydrolyzate of a second alkoxysilane,
The first alkoxysilane comprises one or more selected from the group consisting of compounds represented by the following formulas (1) to (5), and at least a compound represented by formula (1) and formula (4) ), Or a compound represented by formula (5),
The second alkoxysilane comprises at least one selected from the group consisting of compounds represented by the following formulas (11) to (15), and at least a compound represented by the formula (11) and the formula (14): ) Or a compound represented by formula (15),
The composition characterized by the above-mentioned.
Si- (OR ¹ ) ₄ (1)
R ² ₂ —Si— (OR ¹ ) ₂ (2)
R ² ₃ —Si— (OR ¹ ) (3)
R ³ —Si—R ² (OR ¹ ) ₂ (4)
R ³ —Si— (OR ¹ ) ₃ (5)
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is an alkyl group having 8 or more carbon atoms, or a carbon atom of an alkyl group having 8 or more carbon atoms) A group having an etheric oxygen atom between carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkyl group having 8 or more carbon atoms. ^When there are a plurality of ¹ and R ^2, they may be the same or different.)
Si- (OR ¹¹ ) ₄ (11)
R ²¹ ₂ —Si— (OR ¹¹ ) ₂ (12)
R ²¹ ₃ —Si— (OR ¹¹ ) (13)
R ⁴ —Si—R ²¹ (OR ¹¹ ) ₂ (14)
R ⁴ —Si— (OR ¹¹ ) ₃ (15)
Wherein R ¹¹ is an alkyl group having 1 to 4 carbon atoms, R ²¹ is a methyl group or an ethyl group, and R ⁴ is one or more hydrogen atoms of the alkyl group having 1 to 20 carbon atoms. A group having 1 to 20 carbon atoms, a group having at least one hydrogen atom of an alkyl group having 1 to 20 carbon atoms, and a group having an etheric oxygen atom between carbon-carbon atoms of a group having a polar group substituted, and having 3 to 6 carbon atoms Carbon-carbon of an alkyl group, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 6 carbon atoms, or a fluoroalkyl group having 3 to 6 carbon atoms (It is a group having an etheric oxygen atom between atoms, and when there are a plurality of OR ¹¹ and R ^21, they may be the same or different.)

It said polar _{group, -SH, -OH, -C (=} O) H, -Cl, -CN, -F, -CF 3, -CF 2 H, -COOH, -COOR 5, -PO 3 H, - SO ₃ H, -NH ₂ and ^-NR _{6 2} (provided ^that, R 5, ^{R 6} is an alkyl group having 1 to 6 carbon atoms) is at least one selected from the group consisting of, according to claim 2 or 3 Composition.

The molar ratio (R ³ / R ⁴ ) between the R ³ and the R ⁴ present in the composition is 1/2 to 1,000 / 1, according to any one of claims 2 to 4. The composition as described.

The mass ratio of the first condensate to the second condensate (first condensate / second condensate) is 1/2 to 1,000 / 1. A composition according to claim 1.

The composition according to any one of claims 1 to 6, further comprising a solvent.

An article having a film formed from the composition according to any one of claims 1 to 7 on a surface of a substrate.

The article according to claim 8, wherein a water drop angle of a water droplet having a volume of 10 μL dropped on the film is 25 ° or less.

A two-component composition comprising the following first composition and the following second composition.
First composition: Condensate of hydrolyzate of alkoxysilane, having a branched siloxane bond and a monovalent organic group, and a polar force component of solid surface free energy obtained by the following measurement method A composition comprising a first condensate having a (γS ^p ) of less than 5 mN / m and a solvent.
Second composition: Condensate of hydrolyzate of alkoxysilane, having a branched siloxane bond and a monovalent organic group, and a polar force component of solid surface free energy obtained by the following measurement method A composition comprising a second condensate having a (γS ^p ) of 5 mN / m or more and a solvent.
Method for measuring polar force component (γS ^p ) of surface free energy of solid: forming a film made of a condensate to be measured, and the first liquid having the following γL ¹ , γL ^d1 and γL ^p1 and the film contact angle (theta ¹⁾ was measured in the following γL ^2, γL ^d2 and GanmaL ^p2 to measure the contact angle (theta ²⁾ of the second liquid and the film is known. Then, these values are substituted into the following formula (I-1) and the following formula (I-2). Next, the dispersion force component (γS ^d ) and the polar force component (γS ^p ) of the surface free energy γS of the solid are obtained from the simultaneous equations of the following formulas (I-1) and (I-2).
(ΓS ^d · γL ^d1 ) ^1/2 + (γS ^p · γL ^p1 ) ^1/2 = γL ¹ (1 + cos θ ¹ ) / 2 (I-1)
(ΓS ^d · γL ^d2 ) ^1/2 + (γS ^p · γL ^p2 ) ^1/2 = γL ² (1 + cos θ ² ) / 2 (I-2)
γS ^d : Dispersion force component of surface free energy γS of solid.
γS ^p : Polar force component of solid surface free energy γS.
γL ¹ : surface tension of the first liquid.
γL ² : surface tension of the second liquid.
θ ¹ : contact angle of the first liquid.
θ ² : contact angle of the second liquid.
γL ^d1 : Dispersive force component of the surface tension of the first liquid.
γL ^p1 : Polar force component of the surface tension of the first liquid.
γL ^d2 : Dispersion force component of the surface tension of the second liquid.
γL ^p2 : Polar force component of the surface tension of the second liquid.

Two liquids comprising a first composition comprising a condensate of a hydrolyzate of a first alkoxysilane and a solvent, and a second composition comprising a condensate of a hydrolyzate of a second alkoxysilane and a solvent A mold composition comprising:
Said first alkoxysilane, an alkoxysilane having no following R ³ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^3, having the following R ³ Which does not include an alkoxysilane having the following R ⁴ :
Said second alkoxysilane, an alkoxysilane having no following R ⁴ has the alkoxy group three or more, alkoxy and a silane or a alkoxy group of 3 or more and below R ^4, having the following R ⁴ include alkoxysilanes having not contain an alkoxysilane having the following R ^3,
A two-part composition characterized by that.
R ³ : an alkyl group having 8 or more carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 8 or more carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a fluoroalkyl having 8 or more carbon atoms A group having an etheric oxygen atom between carbon-carbon atoms of the group.
R ⁴ : a group in which one or more hydrogen atoms of an alkyl group having 1 to 20 carbon atoms are substituted with a polar group, and a group in which one or more hydrogen atoms of an alkyl group having 1 to 20 carbon atoms are substituted with a polar group A group having an etheric oxygen atom between carbon-carbon atoms, an alkyl group having 3 to 6 carbon atoms, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, 3 carbon atoms Or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkyl group of -6 or a C3-C6 fluoroalkyl group.

Two liquids comprising a first composition comprising a condensate of a hydrolyzate of a first alkoxysilane and a solvent, and a second composition comprising a condensate of a hydrolyzate of a second alkoxysilane and a solvent A mold composition comprising:
The first alkoxysilane comprises one or more selected from the group consisting of compounds represented by the following formulas (1) to (5), and at least a compound represented by formula (1) and formula (4) ), Or a compound represented by formula (5),
The second alkoxysilane comprises at least one selected from the group consisting of compounds represented by the following formulas (11) to (15), and at least a compound represented by the formula (11) and the formula (14): ) Or a compound represented by formula (15),
A two-part composition characterized by that.
Si- (OR ¹ ) ₄ (1)
R ² ₂ —Si— (OR ¹ ) ₂ (2)
R ² ₃ —Si— (OR ¹ ) (3)
R ³ —Si—R ² (OR ¹ ) ₂ (4)
R ³ —Si— (OR ¹ ) ₃ (5)
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a methyl group or an ethyl group, R ³ is an alkyl group having 8 or more carbon atoms, or a carbon atom of an alkyl group having 8 or more carbon atoms) A group having an etheric oxygen atom between carbon atoms, a fluoroalkyl group having 8 or more carbon atoms, or a group having an etheric oxygen atom between carbon-carbon atoms of a fluoroalkyl group having 8 or more carbon atoms. ^When there are a plurality of ¹ and R ^2, they may be the same or different.)
Si- (OR ¹¹ ) ₄ (11)
R ²¹ ₂ —Si— (OR ¹¹ ) ₂ (12)
R ²¹ ₃ —Si— (OR ¹¹ ) (13)
R ⁴ —Si—R ²¹ (OR ¹¹ ) ₂ (14)
R ⁴ —Si— (OR ¹¹ ) ₃ (15)
Wherein R ¹¹ is an alkyl group having 1 to 4 carbon atoms, R ²¹ is a methyl group or an ethyl group, and R ⁴ is one or more hydrogen atoms of the alkyl group having 1 to 20 carbon atoms. A group having 1 to 20 carbon atoms, a group having at least one hydrogen atom of an alkyl group having 1 to 20 carbon atoms, and a group having an etheric oxygen atom between carbon-carbon atoms of a group having a polar group substituted, and having 3 to 6 carbon atoms Carbon-carbon of an alkyl group, a group having an etheric oxygen atom between carbon-carbon atoms of an alkyl group having 3 to 6 carbon atoms, a fluoroalkyl group having 3 to 6 carbon atoms, or a fluoroalkyl group having 3 to 6 carbon atoms (It is a group having an etheric oxygen atom between atoms, and when there are a plurality of OR ¹¹ and R ^21, they may be the same or different.)

The two-component composition according to any one of claims 10 to 12, wherein the first composition and the second composition are mixed and then applied to a surface of a substrate. A method for producing an article, comprising forming a film on a surface of a material.