JP2014234506A - New compound, composition for forming water repellent film and substrate with water repellent film and article for transportation equipment - Google Patents
New compound, composition for forming water repellent film and substrate with water repellent film and article for transportation equipment Download PDFInfo
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本発明は、新規化合物およびそれを含有する撥水膜形成用組成物、該組成物を用いて形成される撥水膜を有する撥水膜付き基体および輸送機器用物品に関する。 The present invention relates to a novel compound, a composition for forming a water-repellent film containing the compound, a substrate having a water-repellent film having a water-repellent film formed using the composition, and an article for a transportation device.
従来から、各種技術分野において、基体の表面に撥水性を付与することが強く求められている。撥水性には静的撥水性(水滴が付着しにくい性質)と動的撥水性(水滴が転がりやすい性質、滑水性)とがあり、用途により多少の違いがあるがその両方が求められることが多い。特に、自動車ガラス等の輸送機器用物品においては、静的撥水性および動的撥水性の双方に優れたものが求められている。 Conventionally, in various technical fields, it has been strongly required to impart water repellency to the surface of a substrate. There are two types of water repellency: static water repellency (a property that prevents water droplets from sticking) and dynamic water repellency (a property that allows water droplets to easily roll, water slidability). Many. In particular, articles for transportation equipment such as automobile glass are required to be excellent in both static water repellency and dynamic water repellency.
基体表面に撥水性を付与する方法としては、基体の表面に撥水性の被膜を形成することが一般的に行われており、優れた撥水性を有する被膜(以下、「撥水膜」という)を形成するための組成物に関する技術開発がなされている。 As a method for imparting water repellency to the surface of a substrate, a water-repellent coating is generally formed on the surface of the substrate, and a coating having excellent water repellency (hereinafter referred to as “water-repellent film”). Technological developments have been made on compositions for forming sucrose.
上記撥水膜形成用の組成物において、静的撥水性に加えて動的撥水性にも優れた撥水膜を形成するための組成物として、加水分解性基を有するジメチルシリコーン化合物を用いた組成物が知られている。このような組成物として、例えば、特許文献1には、一方の末端にフルオロアルキル基やアルキル基を有し他方の末端に1個の加水分解性基を有する直鎖状のジメチルシリコーン化合物を含有する表面処理剤が記載されている。 In the composition for forming a water repellent film, a dimethyl silicone compound having a hydrolyzable group was used as a composition for forming a water repellent film having excellent dynamic water repellency in addition to static water repellency. Compositions are known. As such a composition, for example, Patent Document 1 contains a linear dimethylsilicone compound having a fluoroalkyl group or an alkyl group at one end and one hydrolyzable group at the other end. A surface treatment agent is described.
特許文献1に記載の表面処理剤により得られる機能層は、静的撥水性および動的撥水性ともに優れた機能層であるが経時安定性等の耐久性が十分でない。そこで、特許文献1ではさらに撥水性の耐久性を高めるために基体表面と該機能層との間に3官能または4官能の加水分解性シラン化合物を用いて形成される下地層を設けている。特許文献1では、このような下地層を設けることで経時安定性等の耐久性の向上は図られているが、耐湿性や耐アルカリ性の点で十分ではなかった。 The functional layer obtained by the surface treating agent described in Patent Document 1 is a functional layer that is excellent in both static water repellency and dynamic water repellency, but has insufficient durability such as stability over time. Therefore, in Patent Document 1, a base layer formed using a trifunctional or tetrafunctional hydrolyzable silane compound is provided between the surface of the substrate and the functional layer in order to further improve the water repellency durability. In Patent Document 1, such an underlayer is provided to improve durability such as stability over time, but it is not sufficient in terms of moisture resistance and alkali resistance.
本発明は、上記観点からなされたものであって、静的撥水性および動的撥水性の双方に優れるととともに、耐湿性や耐アルカリ性等の耐久性にも優れた硬化膜を形成可能なシリコーン化合物、およびそのシリコーン化合物を含有する撥水膜形成用組成物の提供を目的とする。
本発明は、さらに、静的撥水性および動的撥水性の双方に優れるととともに、耐湿性や耐アルカリ性等の耐久性にも優れた撥水膜を有する撥水膜付き基体および該撥水膜付き基体からなる輸送機器用物品の提供を目的とする。
The present invention has been made from the above viewpoint, and is capable of forming a cured film that is excellent in both static water repellency and dynamic water repellency, and has excellent durability such as moisture resistance and alkali resistance. An object is to provide a compound and a composition for forming a water-repellent film containing the silicone compound.
The present invention further provides a substrate with a water-repellent film having a water-repellent film excellent in both static water repellency and dynamic water repellency, and also excellent in durability such as moisture resistance and alkali resistance, and the water-repellent film An object of the present invention is to provide an article for a transportation device comprising a substrate with an attachment.
本発明は、以下の構成を有する化合物、撥水膜形成用組成物、撥水膜付き基体および輸送機器用物品を提供する。
[1]下記式(1)で表される化合物。
−Si(R1)3−n(X1)n…(2)
ただし、式(2)中、R1はそれぞれ独立して1価の炭化水素基を、X1はそれぞれ独立して加水分解性基を表す。nは1〜3の整数である。
The present invention provides a compound having the following constitution, a composition for forming a water repellent film, a substrate with a water repellent film, and an article for transport equipment.
[1] A compound represented by the following formula (1).
-Si (R 1 ) 3-n (X 1 ) n (2)
In the formula (2), R 1 is independently a monovalent hydrocarbon group, X 1 is represents a hydrolyzable group independently. n is an integer of 1 to 3.
[2]式(1)中のR2は、メチル基である[1]記載の化合物。
[3]式(1)中のZは、下記式(Z3)または式(Z4)で表わされる1価オルガノシリル基である[1]または[2]記載の化合物。
[3] The compound according to [1] or [2], wherein Z in the formula (1) is a monovalent organosilyl group represented by the following formula (Z 3 ) or formula (Z 4 ).
[4]式(Z3)および式(Z4)中、R4はメチル基であり、Y2はC2H4である[3]記載の化合物。
[5]式(1)中のZは、式(Z3)で表わされ、iは0、nは3であり、X1はそれぞれ独立して塩素原子、メトキシ基およびエトキシ基から選ばれる[3]または[4]記載の化合物。
[6]式(1)中のZは、式(Z3)で表わされ、iは0、mは3、nは3であり、X1はそれぞれ独立して塩素原子またはメトキシ基である[3]または[4]記載の化合物。
[4] The compound according to [3], wherein in formula (Z 3 ) and formula (Z 4 ), R 4 is a methyl group and Y 2 is C 2 H 4 .
[5] Z in the formula (1) is represented by the formula (Z 3 ), i is 0, n is 3, and X 1 is independently selected from a chlorine atom, a methoxy group, and an ethoxy group. The compound according to [3] or [4].
[6] Z in the formula (1) is represented by the formula (Z 3 ), i is 0, m is 3, n is 3, and X 1 is independently a chlorine atom or a methoxy group. The compound according to [3] or [4].
[7]式(1)中のR3はメチル基、Y1はC2H4、kは20〜100であり、Zは下記式(Z31)または(Z41)で表される基(ただし、X1はそれぞれ独立して塩素原子またはメトキシ基)である[2]記載の化合物。
[8]前記[1]〜[7]のいずれかに記載の化合物および/またはその部分加水分解縮合物からなる(A)成分と有機溶剤を含む撥水膜形成用組成物。
[9]全固形分が実質的に前記(A)成分のみからなる[8]記載の撥水膜形成用組成物。
[10]基体と、前記基体の少なくとも一部の表面に[8]または[9]記載の撥水膜形成用組成物を用いて形成された撥水膜とを有する撥水膜付き基体。
[11]前記撥水膜付き基体が、撥水膜と基体の間に、シリカを主成分とする下地層を有する[10]記載の撥水膜付き基体。
[12]前記下地層は、下記式(3)で表される化合物および/またはその部分加水分解縮合物からなる(B)成分を含む下地層形成用組成物を用いて形成された下地層である[11]記載の撥水膜付き基体。
Si(X2)4 …(3)
(ただし、式(3)中、X2はそれぞれ独立して、ハロゲン原子、アルコキシ基またはイソシアネート基を示す。)
[8] A composition for forming a water-repellent film comprising the component (A) comprising the compound according to any one of [1] to [7] and / or a partially hydrolyzed condensate thereof and an organic solvent.
[9] The composition for forming a water-repellent film according to [8], wherein the total solid content is substantially composed only of the component (A).
[10] A substrate with a water-repellent film, comprising a substrate and a water-repellent film formed on at least a part of the surface of the substrate using the water-repellent film-forming composition according to [8] or [9].
[11] The substrate with a water-repellent film according to [10], wherein the substrate with a water-repellent film has an underlayer mainly composed of silica between the water-repellent film and the substrate.
[12] The underlayer is an underlayer formed using a composition for forming an underlayer containing a component (B) composed of a compound represented by the following formula (3) and / or a partially hydrolyzed condensate thereof. A substrate with a water-repellent film according to [11].
Si (X 2 ) 4 (3)
(However, in formula (3), each X 2 independently represents a halogen atom, an alkoxy group or an isocyanate group.)
[13]前記下地層形成用組成物は、前記(B)成分と、下記式(4)で表わされる化合物および/またはその部分加水分解縮合物からなる(C)成分とを含む、もしくは、前記(B)成分と前記(C)成分の部分加水分解共縮合物(ただし、前記(B)成分および/または前記(C)成分を含んでもよい)を含む、[12]記載の撥水膜付き基体。
X3 3Si−(CH2)p−SiX3 3 …(4)
(ただし、式(4)中、X3はそれぞれ独立して加水分解性基または水酸基を示し、pは1〜8の整数である。)
[14]式(4)において、X3はアルコキシ基であり、pは1〜3の整数である、[13]記載の撥水膜付き基体。
[13] The underlayer-forming composition includes the component (B) and the component (C) composed of a compound represented by the following formula (4) and / or a partial hydrolysis condensate thereof, or With a water repellent film according to [12], comprising a partially hydrolyzed cocondensate of component (B) and component (C) (however, the component (B) and / or component (C) may be included) Substrate.
X 3 3 Si- (CH 2) p -SiX 3 3 ... (4)
(However, in Formula (4), X < 3 > shows a hydrolysable group or a hydroxyl group each independently, and p is an integer of 1-8.)
[14] The substrate with a water-repellent film according to [13], wherein in formula (4), X 3 is an alkoxy group, and p is an integer of 1 to 3.
[15]前記下地層形成用組成物は、全固形分が実質的に前記式(3)で表される化合物由来成分と式(4)で表される化合物由来成分のみからなる、[13]または[14]に記載の撥水膜付き基体。
[16]基体の材質がガラスである、[10]〜[15]のいずれかに記載の撥水膜付き基体。
[17]前記[10]〜[16]のいずれかに記載の撥水膜付き基体を備えた輸送機器用物品。
[15] The composition for forming an underlayer comprises only a compound-derived component having a total solid content substantially represented by the formula (3) and a compound-derived component represented by the formula (4). [13] Or the base | substrate with a water-repellent film as described in [14].
[16] The substrate with a water-repellent film according to any one of [10] to [15], wherein the substrate is made of glass.
[17] An article for transportation equipment comprising the substrate with a water-repellent film according to any one of [10] to [16].
本発明によれば、静的撥水性および動的撥水性の双方に優れるととともに、耐湿性や耐アルカリ性等の耐久性にも優れた硬化膜を形成可能なシリコーン化合物、およびそのシリコーン化合物を含有する撥水膜形成用組成物の提供ができる。
本発明によれば、さらに、静的撥水性および動的撥水性の双方に優れるととともに、耐湿性等の耐久性にも優れた撥水膜を有する撥水膜付き基体および該撥水膜付き基体からなる輸送機器用物品の提供ができる。
According to the present invention, a silicone compound capable of forming a cured film that is excellent in both static water repellency and dynamic water repellency, and also excellent in durability such as moisture resistance and alkali resistance, and the silicone compound is contained. A composition for forming a water-repellent film can be provided.
According to the present invention, the substrate with a water-repellent film having a water-repellent film that is excellent in both static water repellency and dynamic water repellency and also excellent in durability such as moisture resistance, and the water-repellent film attached. An article for transportation equipment comprising a substrate can be provided.
以下に本発明の実施の形態を説明する。なお、本発明は、下記説明に限定して解釈されるものではない。
本明細書における式(1)で表される化合物を、化合物(1)という。式(2)で表される基を、基(2)という。他の化合物、基も同様である。本明細書における「化合物(3)由来成分」は、化合物(3)の部分加水分解縮合物や化合物(3)と他の加水分解性シラン化合物の部分加水分解共縮合物における化合物(3)に由来する単位と未反応の化合物(3)を総称する用語として用いる。また、本明細書において全固形分とは、各層形成用組成物が含有する成分のうち、最終的に層構成成分となる成分をいい、有機溶剤等の層形成過程における加熱等により揮発する揮発性成分以外の全成分を示す。
Embodiments of the present invention will be described below. In addition, this invention is limited to the following description and is not interpreted.
The compound represented by Formula (1) in this specification is called compound (1). The group represented by formula (2) is referred to as group (2). The same applies to other compounds and groups. The “component derived from the compound (3)” in the present specification refers to the compound (3) in the partially hydrolyzed condensate of the compound (3) and the partially hydrolyzed condensate of the compound (3) and other hydrolyzable silane compounds. The derived unit and the unreacted compound (3) are used as a generic term. Moreover, in this specification, the total solid content means the component which finally becomes a layer constituent component among the components which each composition for layer formation contains, and is volatilization which volatilizes by the heating in layer formation processes, such as an organic solvent. All components other than sex components are shown.
[化合物]
本発明は、下記式(1)で表される化合物を提供する。
The present invention provides a compound represented by the following formula (1).
ただし、式(1)中、R3は炭素原子数10以下のアルキル基またはポリフルオロアルキル基を、R2はそれぞれ独立して炭素原子数3以下のアルキル基を、Y1は炭素原子数2〜4のアルキレン基を表し、kは10〜200の整数である。Zは、オキソ基(−O−)を介して結合する3〜20個のケイ素原子を有し、前記ケイ素原子に連結基を介して結合する下記式(2)で表わされる加水分解性シリル基を2〜10個有する1価オルガノシリル基である。
−Si(R1)3−n(X1)n…(2)
ただし、式(2)中、R1はそれぞれ独立して1価の炭化水素基を、X1はそれぞれ独立して加水分解性基を表す。nは1〜3の整数である。
In the formula (1), R 3 is an alkyl group or polyfluoroalkyl group having 10 or less carbon atoms, R 2 is independently an alkyl group having 3 or less carbon atoms, and Y 1 is 2 carbon atoms. Represents an alkylene group of -4, and k is an integer of 10-200. Z has 3 to 20 silicon atoms bonded via an oxo group (—O—), and is a hydrolyzable silyl group represented by the following formula (2) bonded to the silicon atom via a linking group. Is a monovalent organosilyl group having 2 to 10.
-Si (R 1 ) 3-n (X 1 ) n (2)
In the formula (2), R 1 is independently a monovalent hydrocarbon group, X 1 is represents a hydrolyzable group independently. n is an integer of 1 to 3.
化合物(1)は、一方の末端に複数個の加水分解性シリル基を有し、他方の末端に疎水性基を有する直鎖状のポリオルガノシロキサンである。化合物(1)を用いて基体等の表面に被膜を形成すれば、化合物(1)の加水分解性シリル基を有する末端が反応して強固に基体等の表面に密着し被膜を形成する。被膜形成に際して、化合物(1)の疎水性基側の末端は反応せずに被膜の表面に表出する。このようにして得られる被膜は、静的撥水性および動的撥水性の双方に優れるものであり、かつ基体等の表面との密着性が強固なことから耐湿性や耐アルカリ性等の耐久性にも優れるものである。 Compound (1) is a linear polyorganosiloxane having a plurality of hydrolyzable silyl groups at one end and a hydrophobic group at the other end. When a film is formed on the surface of the substrate or the like using the compound (1), the terminal having a hydrolyzable silyl group of the compound (1) reacts to firmly adhere to the surface of the substrate or the like to form a film. When forming the film, the end of the compound (1) on the hydrophobic group side does not react and appears on the surface of the film. The film thus obtained is excellent in both static water repellency and dynamic water repellency, and has high durability such as moisture resistance and alkali resistance because of its strong adhesion to the surface of the substrate and the like. Is also excellent.
式(1)のR3は炭素原子数10以下のアルキル基またはポリフルオロアルキル基を示す。ポリフルオロアルキル基とは、アルキル基の水素原子の2個以上がフッ素原子に置換された基である。ポリフルオロアルキル基は、アルキル基の水素原子が全てフッ素原子に置換されたペルフルオロアルキル基であってもよく、その場合は環境負荷の観点から炭素原子数は7以下が好ましい。化合物(1)に求められる特性に応じて式(1)のR3は適宜調整される。 R 3 in the formula (1) represents an alkyl group or polyfluoroalkyl group having 10 or less carbon atoms. A polyfluoroalkyl group is a group in which two or more hydrogen atoms of an alkyl group are substituted with fluorine atoms. The polyfluoroalkyl group may be a perfluoroalkyl group in which all the hydrogen atoms of the alkyl group are substituted with fluorine atoms. In that case, the number of carbon atoms is preferably 7 or less from the viewpoint of environmental burden. R 3 in the formula (1) is appropriately adjusted according to the properties required for the compound (1).
化合物(1)を用いて形成される被膜に優れた静的撥水性および動的撥水性を付与する観点からは、R3は炭素原子数1〜5のアルキル基が好ましく、炭素原子数1〜5の直鎖状アルキル基がより好ましく、メチル基、エチル基がさらに好ましく、メチル基が特に好ましい。 From the viewpoint of imparting excellent static water repellency and dynamic water repellency to the film formed using the compound (1), R 3 is preferably an alkyl group having 1 to 5 carbon atoms, and 1 to 1 carbon atoms. 5 linear alkyl groups are more preferred, methyl groups and ethyl groups are more preferred, and methyl groups are particularly preferred.
式(1)において、SiR2 2Oの繰り返し単位、およびそれに連結する−SiR2 2−におけるR2はそれぞれ独立して炭素原子数3以下のアルキル基であり、炭素原子数3以下の直鎖状のアルキル基が好ましく、メチル基がより好ましい。R2はそれぞれ異なってもよいが、同一であるのが好ましい。SiR2 2Oの繰り返し数であるkは、10〜200の整数であり、10〜150が好ましく、15〜120がより好ましく、20〜100が特に好ましい。 In formula (1), R 2 in the repeating unit of SiR 2 2 O and —SiR 2 2 — linked thereto are each independently an alkyl group having 3 or less carbon atoms, and a straight chain having 3 or less carbon atoms. The alkyl group is preferably a methyl group. R 2 may be different from each other, but is preferably the same. K which is the repeating number of SiR 2 2 O is an integer of 10 to 200, preferably 10 to 150, more preferably 15 to 120, and particularly preferably 20 to 100.
kの数が上記範囲にあれば、化合物(1)を用いて形成される被膜において静的撥水性および動的撥水性の両立が可能となる。なお、化合物(1)は、SiR2 2Oの繰り返し単位の数が異なる混合物として用いられることが多い。化合物(1)がこのような混合物の場合、各繰り返し単位の数は平均値で示される。平均値で示す場合、繰り返し単位の数は必ずしも整数で示されるわけではないが、好ましい数値の範囲は上記同様である。 If the number of k is in the above range, it is possible to achieve both static water repellency and dynamic water repellency in a film formed using the compound (1). The compound (1) is often used as a mixture in which the number of repeating units of SiR 2 2 O is different. When compound (1) is such a mixture, the number of each repeating unit is shown by an average value. In the case of an average value, the number of repeating units is not necessarily an integer, but a preferable range of numerical values is the same as described above.
式(1)においてY1は、(SiR2 2O)k−SiR2 2−と、Zで示される加水分解性シリル基(2)を2〜10個有する1価オルガノシリル基を連結する基であり、炭素原子数2〜4のアルキレン基を示す。Y1としては炭素原子数2または3のアルキレン基が好ましい。Y1が炭素原子数2のアルキレン基の場合、本明細書では式(1)の分子式において−C2H4−と示すが、これは−CH2CH2−と−CH(CH3)−のような混合物であってもよい。これらは、製法上分離が困難な混合物であって、混合物として用いても本発明の効果に影響を与えないものである。同様にY1が炭素原子数3のアルキレン基の場合、式(1)の分子式において−C3H6−と示すが、これは−CH2CH2CH2−と−CH(CH3)CH2−の混合物、−CH2CH2CH2−と−CH2CH(CH3)−の混合物、あるいは−CH(CH3)CH2−と−CH2CH(CH3)−の混合物であってもよい。 In Formula (1), Y 1 is a group linking (SiR 2 2 O) k —SiR 2 2 — and a monovalent organosilyl group having 2 to 10 hydrolyzable silyl groups (2) represented by Z. And represents an alkylene group having 2 to 4 carbon atoms. Y 1 is preferably an alkylene group having 2 or 3 carbon atoms. When Y 1 is an alkylene group having 2 carbon atoms, in the present specification, it is represented as —C 2 H 4 — in the molecular formula of formula (1), which is represented by —CH 2 CH 2 — and —CH (CH 3 ) —. A mixture such as These are mixtures that are difficult to separate in the production process, and even if used as a mixture, the effects of the present invention are not affected. Similarly, when Y 1 is an alkylene group having 3 carbon atoms, it is represented as —C 3 H 6 — in the molecular formula of formula (1), which represents —CH 2 CH 2 CH 2 — and —CH (CH 3 ) CH. 2 - mixture, -CH 2 CH 2 CH 2 of - and -CH 2 CH (CH 3) - mixtures, or -CH (CH 3) CH 2 - and -CH 2 CH (CH 3) - a mixture of May be.
このように、Y1は分岐状のアルキレン基と直鎖状のアルキレン基の混合物であってもよいが、全部が直鎖状のアルキレン基であることが最も好ましい。Y1における分岐状のアルキレン基と直鎖状のアルキレン基の割合は全体を100としたときの直鎖状のアルキレン基の割合として50〜100が好ましく、75〜100がより好ましい。 As described above, Y 1 may be a mixture of a branched alkylene group and a linear alkylene group, but it is most preferable that all of them are linear alkylene groups. The ratio of the branched alkylene group and the linear alkylene group in Y 1 is preferably 50 to 100, more preferably 75 to 100, as the ratio of the linear alkylene group when the whole is 100.
式(1)においてZは、オキソ基(−O−)を介して結合する3〜20個のケイ素原子を有し、前記ケイ素原子に連結基を介して結合する上記式(2)で表わされる加水分解性シリル基(2)を2〜10個有する1価オルガノシリル基である。 In the formula (1), Z is represented by the above formula (2) having 3 to 20 silicon atoms bonded via an oxo group (—O—) and bonded to the silicon atom via a linking group. It is a monovalent organosilyl group having 2 to 10 hydrolyzable silyl groups (2).
Zが有するオキソ基(−O−)を介して結合するケイ素原子(以下、「骨格を形成するケイ素原子」ともいう。)の数は3〜12個が好ましく、3〜7個がより好ましい。Zが有する加水分解性シリル基(2)の数は、2〜8個が好ましく、2〜6個がより好ましい。 The number of silicon atoms bonded to Z through an oxo group (—O—) (hereinafter, also referred to as “silicon atom forming a skeleton”) is preferably 3 to 12, and more preferably 3 to 7. 2-8 are preferable and, as for the number of the hydrolysable silyl groups (2) which Z has, 2-6 are more preferable.
加水分解性シリル基(2)をWで示し連結基をY2で示すと、Zは−SiR4O2/2または−SiR4 2O1/2をY1側に有し、(R4 2SiO2/2)単位、(SiO4/2)単位、(R4 n1(Y2W)2−n1SiO2/2)単位、(SiR4 n2(Y2W)3−n2O1/2)単位を組合せて構成される基が好ましい。 When showing a hydrolyzable silyl group (2) a linking group shown by W in Y 2, Z has -SiR 4 O 2/2 or -SiR 4 2 O 1/2 in Y 1 side, (R 4 2 SiO 2/2 ) unit, (SiO 4/2 ) unit, (R 4 n1 (Y 2 W) 2-n1 SiO 2/2 ) unit, (SiR 4 n2 (Y 2 W) 3-n2 O 1 / 2 ) A group constituted by combining units is preferred.
ただし、上記Zにおいて、骨格を形成するケイ素原子の数は合計で3〜20個であり、R4はそれぞれ独立して炭素原子数3以下のアルキル基であり、Y2はそれぞれ独立して炭素原子数2〜4のアルキレン基である。R4としては、炭素原子数3以下の直鎖状のアルキル基が好ましく、メチル基がより好ましい。Y2としては炭素原子数2または3のアルキレン基が好ましい。n1は0または1であり、1が好ましい。n2は0、1または2であり、2が好ましい。すなわち、骨格を形成するケイ素原子に結合するY2Wの数は、該ケイ素原子1個につき1個が好ましい。 However, in Z, the total number of silicon atoms forming the skeleton is 3 to 20, R 4 is independently an alkyl group having 3 or less carbon atoms, and Y 2 is independently carbon. An alkylene group having 2 to 4 atoms. R 4 is preferably a linear alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Y 2 is preferably an alkylene group having 2 or 3 carbon atoms. n1 is 0 or 1, and 1 is preferable. n2 is 0, 1 or 2, and 2 is preferable. That is, the number of Y 2 W bonded to the silicon atoms forming the skeleton is preferably one for each silicon atom.
ここで、Zにおいて、加水分解性シリル基(2)と骨格を形成するケイ素原子を連結するY2は、上記Y1と同様に、例えば、Y2が炭素原子数2のアルキレン基の場合、分子式において−C2H4−と示すが、これは−CH2CH2−と−CH(CH3)−のような混合物であってもよい。同様にY2が炭素原子数3のアルキレン基の場合、分子式において−C3H6−と示すが、これは−CH2CH2CH2−と−CH(CH3)CH2−の混合物、−CH2CH2CH2−と−CH2CH(CH3)−の混合物、あるいは−CH(CH3)CH2−と−CH2CH(CH3)−の混合物であってもよい。 Here, in Z, Y 2 linking the hydrolyzable silyl group (2) and the silicon atom forming the skeleton is the same as Y 1 above, for example, when Y 2 is an alkylene group having 2 carbon atoms, Although represented by —C 2 H 4 — in the molecular formula, this may be a mixture such as —CH 2 CH 2 — and —CH (CH 3 ) —. Similarly, when Y 2 is an alkylene group having 3 carbon atoms, it is represented as —C 3 H 6 — in the molecular formula, which is a mixture of —CH 2 CH 2 CH 2 — and —CH (CH 3 ) CH 2 —, It may be a mixture of —CH 2 CH 2 CH 2 — and —CH 2 CH (CH 3 ) —, or a mixture of —CH (CH 3 ) CH 2 — and —CH 2 CH (CH 3 ) —.
このように、Y2は分岐状のアルキレン基と直鎖状のアルキレン基の混合物であってもよいが、全部が直鎖状のアルキレン基であることが最も好ましい。Y2における分岐状のアルキレン基と直鎖状のアルキレン基の割合は全体を100としたときの直鎖状のアルキレン基の割合として50〜100が好ましく、75〜100がより好ましい。 As described above, Y 2 may be a mixture of a branched alkylene group and a linear alkylene group, but it is most preferable that all of them are linear alkylene groups. The ratio of the branched alkylene group and the linear alkylene group in Y 2 is preferably 50 to 100, more preferably 75 to 100 as the ratio of the linear alkylene group when the whole is 100.
−Si(R1)3−n(X1)nで示される加水分解性シリル基(2)においてX1は加水分解性基である。加水分解性基とは、Si−X1基の加水分解によって、Si−OHを形成し得る基である。 -Si (R 1) 3-n (X 1) X 1 in the hydrolyzable silyl group (2) represented by n is a hydrolyzable group. The hydrolyzable group is a group that can form Si—OH by hydrolysis of the Si—X 1 group.
X1で示される加水分解性基としては、アルコキシ基、アシロキシ基、ケトオキシム基、アルケニルオキシ基、アミノ基、アミノキシ基、アミド基、イソシアネート基、ハロゲン原子等が挙げられる。化合物(1)の安定性と加水分解のし易さとのバランスの点から、X1としては、アルコキシ基、イソシアネート基およびハロゲン原子が好ましい。ハロゲン原子としては、塩素原子が好ましい。アルコキシ基としては、炭素原子数1〜4のアルコキシ基が好ましく、メトキシ基またはエトキシ基がより好ましい。化合物(1)におけるX1としては、塩素原子、メトキシ基、エトキシ基が好ましく、塩素原子、メトキシ基が特に好ましい。これらは、製造上の目的、用途等に応じて適宜選択され用いられる。加水分解性シリル基(2)中にX1が複数個存在する場合には、X1が同じ基でも異なる基でもよく、同じ基であることが製造のしやすさ等の点で好ましい。 Examples of the hydrolyzable group represented by X 1 include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, and a halogen atom. X 1 is preferably an alkoxy group, an isocyanate group or a halogen atom from the viewpoint of the balance between the stability of the compound (1) and the ease of hydrolysis. As the halogen atom, a chlorine atom is preferable. As an alkoxy group, a C1-C4 alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. X 1 in the compound (1) is preferably a chlorine atom, a methoxy group or an ethoxy group, particularly preferably a chlorine atom or a methoxy group. These are appropriately selected and used according to the purpose of manufacture, application and the like. When a plurality of X 1 are present in the hydrolyzable silyl group (2), X 1 may be the same group or different groups, and the same group is preferable from the viewpoint of ease of production.
nは、加水分解性シリル基(2)中の加水分解性基(X1)の個数を示し、その数は1〜3の整数である。化合物(1)を用いて形成される被膜に優れた密着耐久性を付与する観点からは、nは2または3が好ましく、3が特に好ましい。 n represents the number of hydrolyzable groups (X 1 ) in the hydrolyzable silyl group (2), and the number is an integer of 1 to 3. From the viewpoint of imparting excellent adhesion durability to a film formed using the compound (1), n is preferably 2 or 3, and particularly preferably 3.
R1はそれぞれ独立して1価の炭化水素基である。1価の炭化水素基としては、アルキル基、シクロアルキル基、アルケニル基またはアリール基等が挙げられる。R1は1価の飽和炭化水素基が好ましい。1価の飽和炭化水素基の炭素原子数は1〜6が好ましく、1〜3がより好ましく、1〜2が特に好ましい。R1としては、合成が簡便であることから、炭素原子数が1〜6のアルキル基が好ましく、原料の入手や取り扱いが容易である点から、炭素原子数が1〜3のアルキル基がより好ましく、炭素原子数が1〜2のアルキル基が特に好ましい。加水分解性シリル基(2)中のR1の個数は3−n個である。加水分解性シリル基中にR1が複数個存在する場合には、R1が同じ基でも異なる基でもよく、同じ基であることが製造のしやすさ等の点で好ましい。 Each R 1 is independently a monovalent hydrocarbon group. Examples of the monovalent hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, and an aryl group. R 1 is preferably a monovalent saturated hydrocarbon group. 1-6 are preferable, as for the carbon atom number of a monovalent saturated hydrocarbon group, 1-3 are more preferable, and 1-2 are especially preferable. R 1 is preferably an alkyl group having 1 to 6 carbon atoms because synthesis is simple, and an alkyl group having 1 to 3 carbon atoms is more preferable in terms of easy availability and handling of raw materials. An alkyl group having 1 to 2 carbon atoms is particularly preferable. The number of R 1 in the hydrolyzable silyl group (2) is 3-n. When a plurality of R 1 are present in the hydrolyzable silyl group, R 1 may be the same group or different groups, and the same group is preferable from the viewpoint of ease of production.
化合物(1)がZ中に複数個有する加水分解性シリル基(2)は、同じ基でも異なる基でもよく、同じ基であることが製造のしやすさ等の点で好ましい。また、Zの骨格を形成するケイ素原子と加水分解性シリル基(2)とを連結する基Y2についてもZ内で同じ基でも異なる基でもよく、同じ基であることが製造のしやすさ等の点で好ましい。 The plurality of hydrolyzable silyl groups (2) that compound (1) has in Z may be the same group or different groups, and the same group is preferred from the standpoint of ease of production. In addition, the group Y 2 linking the silicon atom forming the skeleton of Z and the hydrolyzable silyl group (2) may be the same or different in Z, and the same group is easy to produce. Etc. are preferable.
化合物(1)を用いて形成される被膜に優れた密着耐久性を付与する観点からは、Zが有する複数個の加水分解性シリル基(2)は、化合物(1)の末端に高密度に存在することが好ましい。そのために、Zは骨格を形成するケイ素原子がオキソ基(−O−)を介して環状に結合しているか、あるいは分枝状に結合していることが好ましい。このようなZとして、具体的には、下記式(Z3)または式(Z4)で表わされる1価オルガノシリル基が挙げられる。 From the viewpoint of imparting excellent adhesion durability to a film formed using the compound (1), the plurality of hydrolyzable silyl groups (2) possessed by Z are densely formed at the ends of the compound (1). Preferably it is present. For this purpose, it is preferable that the silicon atom forming the skeleton is bonded cyclically via an oxo group (—O—) or is branched in Z. Specific examples of such Z include monovalent organosilyl groups represented by the following formula (Z 3 ) or formula (Z 4 ).
ただし、式(Z3)中、mは2〜10の整数、0≦i≦mである。iおよびmはそれぞれ括弧で囲まれる単位の式(Z3)における合計の単位数であって、各単位の並びは連続、交互またはランダムであってよい。式(Z3)および式(Z4)中、R4、Y2、R1、X1、およびnは好ましい態様を含めて上記と同様である。 In the formula (Z 3), m is an integer from 2 to 10, a 0 ≦ i ≦ m. i and m are the total number of units in the formula (Z 3 ) of units enclosed in parentheses, and the arrangement of each unit may be continuous, alternating, or random. In formula (Z 3 ) and formula (Z 4 ), R 4 , Y 2 , R 1 , X 1 , and n are the same as described above, including preferred embodiments.
Zが式(Z3)で表わされるオルガノシリル基(Z3)の場合、mは2〜7が好ましく、2〜5がより好ましく、3が特に好ましい。iはmの単位数以下であって0〜3が好ましく、0が特に好ましい。オルガノシリル基(Z3)およびZが式(Z4)で表わされるオルガノシリル基(Z4)において、R4はメチル基であり、Y2はC2H4であり、nは3であって、X1はそれぞれ独立して塩素原子、メトキシ基またはエトキシ基であることが好ましい。X1としては塩素原子またはメトキシ基が特に好ましい。 When Z is an organosilyl group (Z 3 ) represented by the formula (Z 3 ), m is preferably 2 to 7, more preferably 2 to 5, and particularly preferably 3. i is the number of units of m or less, preferably 0 to 3, and particularly preferably 0. In the organosilyl group (Z 3 ) and the organosilyl group (Z 4 ) in which Z is represented by the formula (Z 4 ), R 4 is a methyl group, Y 2 is C 2 H 4 , and n is 3. X 1 is preferably independently a chlorine atom, a methoxy group or an ethoxy group. X 1 is particularly preferably a chlorine atom or a methoxy group.
上記説明した化合物(1)において、化合物(1)を用いて形成される被膜に優れた静的撥水性および動的撥水性さらに密着耐久性を付与する観点からは、式(1)中のR3はメチル基、Y1はC2H4、kは20〜100であり、かつZは下記式(Z31)または(Z41)で表される基(ただし、X1はそれぞれ独立して塩素原子またはメトキシ基)であることが好ましい。なお、式(Z31)、(Z41)において、Meはメチル基を示す。 In the compound (1) described above, from the viewpoint of imparting excellent static water repellency and dynamic water repellency and adhesion durability to a film formed using the compound (1), R in the formula (1) 3 is a methyl group, Y 1 is C 2 H 4 , k is 20 to 100, and Z is a group represented by the following formula (Z 31 ) or (Z 41 ) (where X 1 is independently A chlorine atom or a methoxy group). In formulas (Z 31 ) and (Z 41 ), Me represents a methyl group.
化合物(1)は、例えば、以下の方法で製造できる。
化合物(1)として、R3およびR2がともにメチル基であり、Y1がC2H4であり、Zが式(Z31)で示されるオルガノシリル基(Z31)である下記式(11)で示される化合物(11)を製造する場合の例を以下に説明する。あわせて、化合物(11)においてオルガノシリル基(Z31)のかわりに式(Z41)で示されるオルガノシリル基(Z41)を有する下記式(12)で示される化合物(12)を製造する場合の例を説明する。
CH3(Si(CH3)2O)kSi(CH3)2C2H4−Z31 …(11)
CH3(Si(CH3)2O)kSi(CH3)2C2H4−Z41 …(12)
式(11)および(12)におけるkは上記式(1)の場合と好ましい態様を含めて同様である。
Compound (1) can be produced, for example, by the following method.
As the compound (1), an R 3 and R 2 are both methyl groups, Y 1 is C 2 H 4, the following formula Z is an expression organosilyl group represented by (Z 31) (Z 31) ( The example in the case of manufacturing the compound (11) shown by 11) is demonstrated below. In addition, in the compound (11), a compound (12) represented by the following formula (12) having an organosilyl group (Z 41 ) represented by the formula (Z 41 ) instead of the organosilyl group (Z 31 ) is produced. An example of the case will be described.
CH 3 (Si (CH 3) 2 O) k Si (CH 3) 2 C 2 H 4 -Z 31 ... (11)
CH 3 (Si (CH 3) 2 O) k Si (CH 3) 2 C 2 H 4 -Z 41 ... (12)
K in the formulas (11) and (12) is the same as in the case of the formula (1), including the preferred embodiment.
(ビニルポリジメチルシロキサンの製造)
トリメチルシラノールにヘキサメチルシクロトリシロキサンを反応させ、さらにクロロジメチルビニルシランを反応させて、下式(1a)で表わされるビニルポリジメチルシロキサン(1a)を得る。式(1a)におけるkは上記式(1)の場合と好ましい態様を含めて同様である。なお、kの数は反応に用いるヘキサメチルシクロトリシロキサンの量と反応時間で調整できる。
CH3(Si(CH3)2O)kSi(CH3)2CH=CH2 …(1a)
(Manufacture of vinyl polydimethylsiloxane)
Hexamethylcyclotrisiloxane is reacted with trimethylsilanol and further reacted with chlorodimethylvinylsilane to obtain vinylpolydimethylsiloxane (1a) represented by the following formula (1a). K in the formula (1a) is the same as that in the formula (1), including the preferred embodiment. The number of k can be adjusted by the amount of hexamethylcyclotrisiloxane used for the reaction and the reaction time.
CH 3 (Si (CH 3) 2 O) k Si (CH 3) 2 CH = CH 2 ... (1a)
(環状または分枝状メチルハイドロジェンシロキサン構造の導入)
上記ビニルポリジメチルシロキサン(1a)に白金触媒存在下で1,3,5,7−テトラメチルシクロテトラシロキサンを反応させ、末端に下式(Zh1)で表わされる環状メチルハイドロジェンシロキサン構造を有する、下式(1b)で表わされるポリジメチルシロキサン誘導体(1b)を得る。
(Introduction of cyclic or branched methylhydrogensiloxane structure)
The vinyl polydimethylsiloxane (1a) is reacted with 1,3,5,7-tetramethylcyclotetrasiloxane in the presence of a platinum catalyst, and has a cyclic methylhydrogensiloxane structure represented by the following formula (Z h1 ) at the terminal. A polydimethylsiloxane derivative (1b) represented by the following formula (1b) is obtained.
上記において、1,3,5,7−テトラメチルシクロテトラシロキサンの代わりに下記式(D)で示される化合物(D)を反応させ、末端に下式(Zh2)で表わされる分枝状メチルハイドロジェンシロキサン構造を有する、下式(1c)で表わされるポリジメチルシロキサン誘導体(1c)を得る。 In the above, the compound (D) represented by the following formula (D) is reacted in place of 1,3,5,7-tetramethylcyclotetrasiloxane, and the branched methyl represented by the following formula (Z h2 ) at the terminal A polydimethylsiloxane derivative (1c) represented by the following formula (1c) having a hydrogensiloxane structure is obtained.
(加水分解性シリル基の導入)
上記ポリジメチルシロキサン誘導体(1b)に白金触媒存在下でビニルトリクロロシランまたはビニルトリメトキシシランを反応させることで、上記(Zh1)で表わされる環状メチルハイドロジェンシロキサン構造のオルガノシリル基(Zh1)において、水素原子が−C2H4Si(X1)3(X1は塩素原子またはメトキシ基)に置換されて、オルガノシリル基(Z31)となった化合物(11)が得られる。
(Introduction of hydrolyzable silyl group)
By reacting the vinyltrichlorosilane or vinyl trimethoxysilane a platinum catalyst presence in the polydimethylsiloxane derivative (1b), the organosilyl group cyclic methylhydrogensiloxane structure represented by (Z h1) (Z h1) , The hydrogen atom is replaced with —C 2 H 4 Si (X 1 ) 3 (where X 1 is a chlorine atom or a methoxy group) to obtain a compound (11) having an organosilyl group (Z 31 ).
同様に、上記ポリジメチルシロキサン誘導体(1c)に白金触媒存在下でビニルトリクロロシランまたはビニルトリメトキシシランを反応させることで、上記(Zh2)で表わされる分枝状メチルハイドロジェンシロキサン構造のオルガノシリル基(Zh2)において、水素原子が−C2H4Si(X1)3(X1は塩素原子またはメトキシ基)に置換されて、オルガノシリル基(Z41)となった化合物(12)が得られる。 Similarly, by reacting the polydimethylsiloxane derivative (1c) with vinyltrichlorosilane or vinyltrimethoxysilane in the presence of a platinum catalyst, an organosilyl having a branched methylhydrogensiloxane structure represented by (Z h2 ) above. In the group (Z h2 ), a compound in which a hydrogen atom is substituted with —C 2 H 4 Si (X 1 ) 3 (X 1 is a chlorine atom or a methoxy group) to form an organosilyl group (Z 41 ) Is obtained.
[撥水膜形成用組成物]
本発明の撥水膜形成用組成物は、上記化合物(1)および/またはその部分加水分解縮合物からなる(A)成分と有機溶剤を含む組成物である。化合物(1)は、加水分解性シリル基(2)を複数個有する化合物であって、加水分解・縮合反応によって基体等の表面に撥水性の硬化膜を形成しうる化合物である。
[Composition for water-repellent film formation]
The composition for forming a water-repellent film of the present invention is a composition comprising the component (A) composed of the compound (1) and / or a partial hydrolysis condensate thereof and an organic solvent. The compound (1) is a compound having a plurality of hydrolyzable silyl groups (2), and can form a water-repellent cured film on the surface of a substrate or the like by a hydrolysis / condensation reaction.
本発明の撥水膜形成用組成物が含有する化合物(1)は、上記式(1)で示される化合物の1種であってもよく、2種以上であってもよい。撥水膜形成用組成物に含まれる(A)成分は、化合物(1)の部分加水分解縮合物であってもよい。化合物(1)のような加水分解性シリル基(2)を有する化合物の部分加水分解縮合物とは、溶媒中で酸触媒やアルカリ触媒などの触媒と水の存在下に該化合物が有する加水分解性基の全部または一部が加水分解し、次いで脱水縮合することによって生成するオリゴマー(多量体)をいう。酸触媒としては、塩酸、硝酸、酢酸、硫酸、燐酸、スルホン酸、メタンスルホン酸、p−トルエンスルホン酸等を使用できる。アルカリ触媒としては、水酸化ナトリウム、水酸化カリウム、アンモニア等を使用できる。なお、これら触媒の水溶液を使用することにより、加水分解に必要な水を反応系に存在させることも可能である。 The compound (1) contained in the composition for forming a water repellent film of the present invention may be one of the compounds represented by the above formula (1), or may be two or more. The component (A) contained in the composition for forming a water repellent film may be a partially hydrolyzed condensate of compound (1). A partially hydrolyzed condensate of a compound having a hydrolyzable silyl group (2) such as compound (1) is a hydrolysis that the compound has in the presence of a catalyst such as an acid catalyst or an alkali catalyst and water in a solvent. An oligomer (multimer) produced by hydrolysis or dehydration condensation of all or part of a functional group. As the acid catalyst, hydrochloric acid, nitric acid, acetic acid, sulfuric acid, phosphoric acid, sulfonic acid, methanesulfonic acid, p-toluenesulfonic acid and the like can be used. As the alkali catalyst, sodium hydroxide, potassium hydroxide, ammonia or the like can be used. In addition, it is also possible to make water required for a hydrolysis exist in a reaction system by using the aqueous solution of these catalysts.
部分加水分解縮合物の縮合度(多量化度)は、生成物が溶媒に溶解する程度である必要がある。(A)成分としては、化合物(1)であっても、化合物(1)の部分加水分解縮合物であってもよく、化合物(1)とその部分加水分解縮合物との混合物、例えば、未反応の化合物(1)が含まれる化合物(1)の部分加水分解縮合物であってもよい。 The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate must be such that the product is dissolved in the solvent. The component (A) may be the compound (1) or a partial hydrolysis condensate of the compound (1), and a mixture of the compound (1) and the partial hydrolysis condensate, for example, It may be a partially hydrolyzed condensate of compound (1) containing compound (1) of the reaction.
撥水膜形成用組成物は、本発明の効果を損なわない範囲で、目的に応じて、金属酸化物の超微粒子、染料または顔料等の着色用材料、防汚性材料、各種樹脂等の任意成分として機能性添加剤を含んでもよい。ただし、撥水膜形成用組成物への機能性添加剤の添加はその量によっては、得られる撥水膜の性能の低下を招くおそれがある。よって、撥水膜形成用組成物は、全固形成分が実質的に(A)成分のみからなることが好ましい。なお、本明細書において、全固形分が実質的に、ある成分のみからなるとは、全固形分中の該成分の含有割合が90質量%以上であることをいう。 The composition for forming a water-repellent film is an arbitrary material such as a metal oxide ultrafine particle, a coloring material such as a dye or a pigment, an antifouling material, and various resins depending on the purpose within a range not impairing the effects of the present invention. A functional additive may be included as a component. However, depending on the amount of the functional additive added to the composition for forming a water-repellent film, the performance of the resulting water-repellent film may be deteriorated. Therefore, in the composition for forming a water repellent film, it is preferable that the total solid component consists essentially of the component (A). In the present specification, that the total solid content is substantially composed of only a certain component means that the content ratio of the component in the total solid content is 90% by mass or more.
撥水膜形成用組成物は、撥水膜構成成分となる固形分の他に、経済性、作業性、得られる撥水膜の厚さ制御のしやすさ等を考慮して、有機溶剤を含む。有機溶剤は、撥水膜形成用組成物が含有する固形分を溶解するものであれば特に制限されない。有機溶剤は、撥水膜形成用組成物が含有する固形分を溶解するものであれば特に制限されない。有機溶剤としては、アルコール類、エーテル類、ケトン類、芳香族炭化水素類、パラフィン系炭化水素類、酢酸エステル類等が好ましい。有機溶剤は1種に限定されず、極性、蒸発速度等の異なる2種以上の溶剤を混合して使用してもよい。 The composition for forming a water-repellent film contains an organic solvent in consideration of economic efficiency, workability, ease of controlling the thickness of the resulting water-repellent film, etc., in addition to the solids that constitute the water-repellent film. Including. The organic solvent is not particularly limited as long as it dissolves the solid content contained in the composition for forming a water repellent film. The organic solvent is not particularly limited as long as it dissolves the solid content contained in the composition for forming a water repellent film. As the organic solvent, alcohols, ethers, ketones, aromatic hydrocarbons, paraffinic hydrocarbons, acetate esters and the like are preferable. The organic solvent is not limited to one kind, and two or more kinds of solvents having different polarities and evaporation rates may be mixed and used.
撥水膜形成用組成物が部分加水分解縮合物を含有する場合、これを製造するために使用した溶媒を含んでもよい。また、このような溶媒と撥水膜形成用組成物が含有する有機溶剤は同じものであってもよい。撥水膜形成用組成物は、さらに、部分加水分解縮合で用いた触媒などの成分を含んでいてもよい。撥水膜形成用組成物の全固形分が実質的に(A)成分のみからなる場合に、化合物(1)の部分加水分解縮合物を用いる際には、撥水膜形成用組成物は、化合物(1)の部分加水分解縮合物の製造で得られた部分加水分解縮合物の溶液そのものであることが好ましい。 When the composition for forming a water-repellent film contains a partially hydrolyzed condensate, it may contain a solvent used for producing it. Moreover, the organic solvent which such a solvent and the composition for water-repellent film formation contain may be the same. The composition for forming a water-repellent film may further contain components such as a catalyst used in partial hydrolysis condensation. When the total solid content of the composition for forming a water repellent film is substantially composed only of the component (A), when using the partially hydrolyzed condensate of the compound (1), the composition for forming a water repellent film is It is preferable that it is the solution of the partial hydrolysis-condensation product obtained by manufacture of the partial hydrolysis-condensation product of compound (1) itself.
撥水膜形成用組成物における有機溶剤の割合は、(A)成分の100質量部に対して、400〜100,000質量部が好ましい。有機溶剤の含有量が上記範囲であれば、撥水膜に処理ムラが発生するおそれもなく、経済性、作業性、処理層の厚さ制御のしやすさ等においても問題がない。撥水膜形成用組成物における有機溶剤の量は、さらに、(A)成分の100質量部に対して、500〜10,000質量部がより好ましく、600〜2,000質量部が特に好ましい。 The proportion of the organic solvent in the composition for forming a water-repellent film is preferably 400 to 100,000 parts by mass with respect to 100 parts by mass of the component (A). If the content of the organic solvent is within the above range, there is no risk of processing unevenness occurring in the water-repellent film, and there is no problem in economic efficiency, workability, ease of controlling the thickness of the processing layer, and the like. The amount of the organic solvent in the composition for forming a water-repellent film is more preferably from 500 to 10,000 parts by mass, particularly preferably from 600 to 2,000 parts by mass based on 100 parts by mass of the component (A).
撥水膜形成用組成物においては、部分加水分解縮合物を含まないものであっても、(A)成分の加水分解縮合反応を促進させるために、上記で部分加水分解縮合の反応において使用したのと同様の酸触媒等の触媒を配合しておくことも好ましい。部分加水分解縮合物を含む場合であっても、それらの製造に使用した触媒が組成物中に残存していない場合は、触媒を配合することが好ましい。触媒としては、酸触媒が好ましい。触媒の量としては、(A)成分の100質量部に対して、0.01〜10質量部が好ましい。 In the composition for forming a water-repellent film, even if it does not contain a partial hydrolysis-condensation product, it was used in the above-mentioned partial hydrolysis-condensation reaction in order to promote the hydrolysis-condensation reaction of component (A). It is also preferable to blend a catalyst such as an acid catalyst similar to the above. Even when the partial hydrolysis-condensation product is contained, when the catalyst used for the production thereof does not remain in the composition, it is preferable to blend the catalyst. As the catalyst, an acid catalyst is preferable. As a quantity of a catalyst, 0.01-10 mass parts is preferable with respect to 100 mass parts of (A) component.
撥水膜形成用組成物は、上記含有成分が加水分解縮合反応するための水を含んでいてもよい。撥水膜形成用組成物における水の含有量は、(A)成分の100質量部に対して、1〜50質量部が好ましい。なお、撥水膜形成用組成物は水を含有しなくとも、以下の撥水膜を形成する過程において雰囲気中の水分を利用して含有成分の加水分解縮合反応を行わせることができる。 The composition for forming a water-repellent film may contain water for the above-described components to undergo a hydrolytic condensation reaction. The water content in the composition for forming a water repellent film is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). Even if the composition for forming a water-repellent film does not contain water, it can cause the hydrolysis and condensation reaction of the contained components using moisture in the atmosphere in the process of forming the following water-repellent film.
ここで、撥水膜形成用組成物が、(A)成分として、化合物(1)の加水分解性基が塩素原子である化合物(1)や部分加水分解縮合物等を含有する場合、これらは反応性が高いことから貯蔵安定性を考慮すると上記触媒および水を実質的に含有しないことが好ましい。実質的に含有しないとは、撥水膜形成用組成物の全量に対する含有量が触媒については0.001質量%以下であることを、水については0.3質量%以下あることをいう。 Here, when the composition for forming a water-repellent film contains, as the component (A), the compound (1) in which the hydrolyzable group of the compound (1) is a chlorine atom, a partially hydrolyzed condensate, or the like, Considering storage stability because of high reactivity, it is preferable that the catalyst and water are not substantially contained. “Substantially not contained” means that the content of the water repellent film-forming composition is 0.001% by mass or less for the catalyst and 0.3% by mass or less for water.
[撥水膜付き基体]
本発明の撥水膜付き基体は、基体と、該基体の少なくとも一部の表面に上記本発明の撥水膜形成用組成物を用いて形成された撥水膜とを有する撥水膜付き基体である。なお、本発明の撥水膜付き基体において用いる上記撥水膜形成用組成物は全固形分が実質的に上記(A)成分のみからなるものが好ましい。また、本発明の撥水膜付き基体は、撥水膜と基体の間に、シリカを主成分とする下地層を有してもよい。
以下、本発明の撥水膜付き基体の構成要素を説明する。
[Substrate with water-repellent film]
The substrate with a water-repellent film of the present invention comprises a substrate and a substrate with a water-repellent film having a substrate and a water-repellent film formed on the surface of at least a part of the substrate using the water-repellent film-forming composition of the present invention. It is. The water repellent film-forming composition used in the substrate with a water repellent film of the present invention preferably has a total solid content substantially consisting only of the component (A). In addition, the substrate with a water-repellent film of the present invention may have an underlayer mainly composed of silica between the water-repellent film and the substrate.
Hereinafter, the components of the substrate with a water-repellent film of the present invention will be described.
(基体)
本発明の撥水膜付き基体に用いる基体は、一般に撥水性の付与が求められている材質からなる基体であれば特に限定されず、金属、プラスチック、ガラス、セラミック、またはその組み合わせ(複合材料、積層材料等)からなる基体が好ましく使用される。ガラスまたはプラスチック等の透明な基体が好ましく、特にガラスが好ましい。
(Substrate)
The substrate used for the substrate with a water-repellent film of the present invention is not particularly limited as long as it is a substrate made of a material that is generally required to impart water repellency. Metal, plastic, glass, ceramic, or a combination thereof (composite material, A substrate made of a laminated material or the like is preferably used. A transparent substrate such as glass or plastic is preferred, and glass is particularly preferred.
ガラスとしては、通常のソーダライムガラス、ホウ珪酸ガラス、無アルカリガラス、石英ガラス等が挙げられ、これらのうちでもソーダライムガラスが特に好ましい。また、プラスチックとしては、ポリメチルメタクリレートなどのアクリル系樹脂やポリフェニレンカーボネートなどの芳香族ポリカーボネート系樹脂、ポリエチレンテレフタレート(PET)などの芳香族ポリエステル系樹脂等が挙げられ、これらのうちでもポリエチレンテレフタレート(PET)が好ましい。 Examples of the glass include ordinary soda lime glass, borosilicate glass, non-alkali glass, and quartz glass. Among these, soda lime glass is particularly preferable. Examples of the plastic include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as polyphenylene carbonate, and aromatic polyester resins such as polyethylene terephthalate (PET). Among these, polyethylene terephthalate (PET) ) Is preferred.
基体の形状は平板でもよく、全面または一部が曲率を有していてもよい。基体の厚さは撥水膜付き基体の用途により適宜選択できるが、一般的には1〜10mmであることが好ましい。 The shape of the substrate may be a flat plate, or the entire surface or a part thereof may have a curvature. The thickness of the substrate can be appropriately selected depending on the use of the substrate with a water-repellent film, but is generally preferably 1 to 10 mm.
基体がソーダライムガラスである場合は、Naイオンの溶出を防止する膜を設けることが耐久性の点で好ましい。基体がフロート法で製造されたガラスである場合は、表面錫量の少ないトップ面に撥水膜を設けることが耐久性の点で好ましい。 When the substrate is soda lime glass, it is preferable in terms of durability to provide a film that prevents elution of Na ions. In the case where the substrate is glass manufactured by a float process, it is preferable in terms of durability to provide a water-repellent film on the top surface with a small amount of surface tin.
本発明の撥水膜付き基体において、撥水膜は上記基体の少なくとも一部の表面に形成される。基体表面の撥水膜が形成される領域は特に限定されず、用途に応じて必要とされる領域に形成すればよい。基体が板状である場合、通常、基体の両方の主面またはいずれか一方の主面の全面に形成される。 In the substrate with a water-repellent film of the present invention, the water-repellent film is formed on at least a part of the surface of the substrate. The region where the water-repellent film on the substrate surface is formed is not particularly limited, and may be formed in a region required according to the application. In the case where the substrate is plate-shaped, it is usually formed on both main surfaces of the substrate or one of the main surfaces.
(撥水膜)
撥水膜付き基体が有する撥水膜は、上記本発明の撥水膜形成用組成物を用いて形成される。該撥水膜形成用組成物は、好ましくは、全固形分が実質的に上記(A)成分のみからなる組成物である。
撥水膜形成用組成物を用いて撥水膜を形成する方法としては、オルガノシラン化合物系の表面処理剤における公知の方法を用いることが可能である。
(Water repellent film)
The water repellent film of the substrate with the water repellent film is formed using the water repellent film forming composition of the present invention. The water repellent film-forming composition is preferably a composition whose total solid content is substantially composed of only the component (A).
As a method of forming a water-repellent film using the composition for forming a water-repellent film, a known method for an organosilane compound-based surface treatment agent can be used.
例えば、はけ塗り、流し塗り、回転塗布、浸漬塗布、スキージ塗布、スプレー塗布、手塗り等の方法で撥水膜形成用組成物を基体の表面または下地層を有する場合には下地層の表面に塗布し、大気中または窒素雰囲気中において、必要に応じて乾燥した後、硬化させることで、撥水膜を形成できる。 For example, if the composition for forming a water-repellent film has the surface of the base or the base layer by a method such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, or hand coating, the surface of the base layer A water-repellent film can be formed by applying to the substrate, drying in the air or in a nitrogen atmosphere as necessary, and then curing.
硬化の条件は、用いる組成物の種類、濃度等により適宜制御されるが、好ましい条件として、温度:20〜50℃、湿度:50〜90%RHの条件が挙げられる。硬化のための時間は、用いる組成物の種類、濃度、硬化条件等によるが、概ね1〜72時間が好ましい。撥水膜の厚さは、撥水膜として機能する厚さ、好ましくは、静的撥水性および動的撥水性の双方に優れる性能を発揮できる厚さであれば特に限定されない。経済性を考慮すると、50nm以下の厚さが好ましく、その下限は単分子層の厚さである。 The curing conditions are appropriately controlled depending on the type and concentration of the composition to be used. Preferred conditions include a temperature of 20 to 50 ° C. and a humidity of 50 to 90% RH. The time for curing depends on the type, concentration, curing conditions and the like of the composition to be used, but is generally preferably 1 to 72 hours. The thickness of the water-repellent film is not particularly limited as long as it is a thickness that functions as a water-repellent film, preferably a thickness that can exhibit performances excellent in both static water repellency and dynamic water repellency. In consideration of economy, a thickness of 50 nm or less is preferable, and the lower limit is the thickness of the monomolecular layer.
このようにして得られる本発明の撥水膜付き基体の撥水膜は、化合物(1)を用いて形成されていることから静的撥水性および動的撥水性の双方に優れるととともに、耐湿性や耐アルカリ性等の耐久性にも優れるものである。なお撥水膜における耐久性は、以下のシリカを主成分とする下地層を撥水膜と基体の間に設けることで、より向上させられる。 Since the water-repellent film of the substrate with a water-repellent film of the present invention thus obtained is formed using the compound (1), it is excellent in both static water repellency and dynamic water repellency. It also has excellent durability such as resistance and alkali resistance. The durability of the water-repellent film can be further improved by providing a base layer mainly composed of the following silica between the water-repellent film and the substrate.
(下地層)
シリカを主成分とする下地層としては、下記式(3)で表される化合物および/またはその部分加水分解縮合物からなる(B)成分を含む下地層形成用組成物を用いて形成された層が好ましい。
Si(X2)4 …(3)
(ただし、式(3)中、X2はそれぞれ独立して、ハロゲン原子、アルコキシ基またはイソシアネート基を示す。)
(Underlayer)
The underlayer mainly composed of silica was formed using an underlayer-forming composition containing a component (B) composed of a compound represented by the following formula (3) and / or a partially hydrolyzed condensate thereof. A layer is preferred.
Si (X 2 ) 4 (3)
(However, in formula (3), each X 2 independently represents a halogen atom, an alkoxy group or an isocyanate group.)
上記式(3)中、X2は、塩素原子、炭素原子数1〜4のアルコキシ基またはイソシアネート基であることが好ましく、さらに4個のX2が同一であることが好ましい。 In the above formula (3), X 2 is chlorine atom, is preferably an alkoxy group or an isocyanate group having 1 to 4 carbon atoms, preferably further four X 2 are identical.
このような上記一般式(3)で示される化合物として、具体的には、Si(NCO)4、Si(OCH3)4、Si(OC2H5)4等が好ましく用いられる。本発明において、化合物(3)は1種を単独で用いてもよく、2種以上を併用してもよい。 Specifically, Si (NCO) 4 , Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 and the like are preferably used as the compound represented by the general formula (3). In this invention, a compound (3) may be used individually by 1 type, and may use 2 or more types together.
下地層形成用組成物に含まれる(B)成分は、化合物(3)の部分加水分解縮合物であってもよい。化合物(3)の部分加水分解縮合物は、化合物(1)の部分加水分解縮合物の製造において説明したのと同様の方法で得ることができる。ただし、部分加水分解縮合物の縮合度(多量化度)は、生成物が溶媒に溶解する程度である必要がある。(B)成分としては、化合物(3)であっても、化合物(3)の部分加水分解縮合物であってもよく、化合物(3)とその部分加水分解縮合物との混合物、例えば、未反応の化合物(3)が含まれる化合物(3)の部分加水分解縮合物であってもよい。なお、一般式(3)で示される化合物やその部分加水分解縮合物としては市販品があり、本発明にはこのような市販品を用いることが可能である。 Component (B) contained in the underlayer-forming composition may be a partially hydrolyzed condensate of compound (3). The partially hydrolyzed condensate of compound (3) can be obtained by the same method as described in the production of the partially hydrolyzed condensate of compound (1). However, the degree of condensation (degree of multimerization) of the partially hydrolyzed condensate needs to be such that the product is dissolved in the solvent. The component (B) may be the compound (3) or a partial hydrolysis condensate of the compound (3), and a mixture of the compound (3) and the partial hydrolysis condensate, for example, It may be a partial hydrolysis-condensation product of the compound (3) including the reaction compound (3). In addition, there exists a commercial item as a compound shown by General formula (3), or its partial hydrolysis-condensation product, It is possible to use such a commercial item for this invention.
また、下地層形成用組成物は、上記(B)成分と、下記式(4)で表わされる化合物および/またはその部分加水分解縮合物からなる(C)成分とを含む、もしくは、上記(B)成分と上記(C)成分の部分加水分解共縮合物(ただし、上記(B)成分および/または上記(C)成分を含んでもよい)を含む組成物であることがより好ましい。
X3 3Si−(CH2)p−SiX3 3 …(4)
(ただし、式(4)中、X3はそれぞれ独立して加水分解性基または水酸基を示し、pは1〜8の整数である。)
The underlayer-forming composition includes the component (B) and a component (C) composed of a compound represented by the following formula (4) and / or a partial hydrolysis condensate thereof, or the component (B) ) Component and the partially hydrolyzed cocondensate of the component (C) (however, the composition may contain the component (B) and / or the component (C)).
X 3 3 Si- (CH 2) p -SiX 3 3 ... (4)
(However, in Formula (4), X < 3 > shows a hydrolysable group or a hydroxyl group each independently, and p is an integer of 1-8.)
化合物(4)は、2価有機基を挟んで両末端に加水分解性シリル基またはシラノール基を有する化合物である。このような化合物(4)と化合物(3)を組合せて用いて形成される下地層は、化合物(4)由来の該有機基の作用により疎水性が発現され湿度の高い環境下におかれても撥水膜が基体から剥離することなく撥水性を維持することが可能と考えられる。 Compound (4) is a compound having hydrolyzable silyl groups or silanol groups at both ends with a divalent organic group interposed therebetween. The underlayer formed by combining the compound (4) and the compound (3) is placed in a high humidity environment where hydrophobicity is expressed by the action of the organic group derived from the compound (4). It is considered that water repellency can be maintained without the water repellent film peeling from the substrate.
式(4)中X3で示される加水分解性基としては、上記X1と同様の基または原子が挙げられる。化合物(4)の安定性と加水分解のし易さとのバランスの点から、X3としては、アルコキシ基およびイソシアネート基が好ましく、アルコキシ基が特に好ましい。アルコキシ基としては、炭素原子数1〜4のアルコキシ基が好ましく、メトキシ基またはエトキシ基がより好ましい。これらは、製造上の目的、用途等に応じて適宜選択され用いられる。化合物(4)中に複数個存在するX3は同じ基でも異なる基でもよく、同じ基であることが入手しやすさの点で好ましい。なお、化合物(3)との組み合わせにおいて、化合物(4)は加水分解性基が化合物(3)の加水分解性基と同じ基または原子であることが好ましい。 Examples of the hydrolyzable group represented by X 3 in formula (4) include the same groups or atoms as those of X 1 above. In view of the balance between the stability of the compound (4) and the ease of hydrolysis, X 3 is preferably an alkoxy group or an isocyanate group, and particularly preferably an alkoxy group. As an alkoxy group, a C1-C4 alkoxy group is preferable, and a methoxy group or an ethoxy group is more preferable. These are appropriately selected and used according to the purpose of manufacture, application and the like. A plurality of X 3 present in the compound (4) may be the same group or different groups, and the same group is preferable from the viewpoint of availability. In combination with the compound (3), the compound (4) preferably has a hydrolyzable group that is the same group or atom as the hydrolyzable group of the compound (3).
式(4)において、pは加水分解性シリル基またはシラノール基に挟まれた、2価の炭化水素基の炭素原子数を示す。pは1〜8の整数であり、1〜3の整数が好ましい。2価の炭化水素基の炭素原子数が上記範囲にあることで、下地層は適度に疎水性を有し撥水膜の耐湿性を向上させることが可能となる。なお、pが9以上になると動的撥水性が悪化する点で問題である。 In the formula (4), p represents the number of carbon atoms of a divalent hydrocarbon group sandwiched between hydrolyzable silyl groups or silanol groups. p is an integer of 1 to 8, and an integer of 1 to 3 is preferable. When the number of carbon atoms of the divalent hydrocarbon group is in the above range, the underlayer has an appropriate hydrophobicity and can improve the moisture resistance of the water-repellent film. Incidentally, when p is 9 or more, there is a problem in that the dynamic water repellency is deteriorated.
化合物(4)として、具体的には、(CH3O)3SiCH2CH2Si(OCH3)3、(OCN)3SiCH2CH2Si(NCO)3、Cl3SiCH2CH2SiCl3、(C2H5O)3SiCH2CH2Si(OC2H5)3、(CH3O)3SiCH2CH2CH2CH2CH2CH2Si(OCH3)3等が挙げられる。本発明において、化合物(4)は1種を単独で用いてもよく、2種以上を併用してもよい。 Specifically, as the compound (4), (CH 3 O) 3 SiCH 2 CH 2 Si (OCH 3 ) 3 , (OCN) 3 SiCH 2 CH 2 Si (NCO) 3 , Cl 3 SiCH 2 CH 2 SiCl 3 include (C 2 H 5 O) 3 SiCH 2 CH 2 Si (OC 2 H 5) 3, (CH 3 O) 3 SiCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 Si (OCH 3) 3 , etc. . In this invention, a compound (4) may be used individually by 1 type, and may use 2 or more types together.
下地層形成用組成物に含まれる(C)成分は、化合物(4)の部分加水分解縮合物であってもよい。化合物(4)の部分加水分解縮合物は、化合物(1)の部分加水分解縮合物の製造において説明したのと同様の方法で得ることができる。部分加水分解縮合物の縮合度(多量化度)は、生成物が溶媒に溶解する程度である必要がある。(C)成分としては、化合物(4)であっても、化合物(4)の部分加水分解縮合物であってもよく、化合物(4)とその部分加水分解縮合物との混合物、例えば、未反応の化合物(4)が含まれる化合物(4)の部分加水分解縮合物であってもよい。 Component (C) contained in the underlayer-forming composition may be a partially hydrolyzed condensate of compound (4). The partially hydrolyzed condensate of compound (4) can be obtained by the same method as described in the production of the partially hydrolyzed condensate of compound (1). The degree of condensation (degree of multimerization) of the partially hydrolyzed condensate must be such that the product is dissolved in the solvent. Component (C) may be compound (4) or a partial hydrolysis condensate of compound (4), and a mixture of compound (4) and its partial hydrolysis condensate, for example, It may be a partial hydrolysis-condensation product of the compound (4) including the reaction compound (4).
一般式(4)で示される化合物やその部分加水分解縮合物としては市販品があり、本発明にはこのような市販品を用いることが可能である。 There are commercially available compounds represented by the general formula (4) and partially hydrolyzed condensates thereof, and such commercially available products can be used in the present invention.
下地層形成用組成物が(B)成分に加えて(C)成分を含む場合、下地層形成用組成物は、(C)成分と(B)成分をそれぞれ単独で含有してもよく、これらの部分加水分解共縮合物を含有してもよい。下地層形成用組成物が、(C)成分と(B)成分の部分加水分解共縮合物を含む場合、これとは別に(C)成分および/または(B)成分を含んでもよい。 When the composition for forming the underlayer contains the component (C) in addition to the component (B), the composition for forming the underlayer may contain the component (C) and the component (B) alone, The partially hydrolyzed cocondensate may be contained. When the composition for base layer formation contains the partial hydrolysis cocondensate of (C) component and (B) component, you may contain (C) component and / or (B) component separately from this.
下地層形成用組成物が(B)成分と(C)成分の両方を含む場合、これらの部分加水分解共縮合物を使用することが好ましく、化合物(3)と化合物(4)の部分加水分解共縮合物を使用することがより好ましい。部分加水分解共縮合物を用いることにより、下地層を両化合物に由来する単位が均一に分布した層として形成できると考えられる。 When the underlayer-forming composition contains both the component (B) and the component (C), it is preferable to use these partial hydrolysis cocondensates, and partial hydrolysis of the compounds (3) and (4). It is more preferable to use a cocondensate. By using a partially hydrolyzed cocondensate, it is considered that the underlayer can be formed as a layer in which units derived from both compounds are uniformly distributed.
下地層形成用組成物は、上記のようにして化合物(3)由来成分に加えて化合物(4)由来成分を含むことで、得られる撥水膜の耐湿性や耐アルカリ性等の耐久性が向上する点で好ましい。下地層形成用組成物における、化合物(3)由来成分と化合物(4)由来成分との含有割合は、[化合物(3)由来成分:化合物(4)由来成分]で示される質量比として、0.1:0.9〜0.9:0.1の範囲にあることが好ましく、0.4:0.6〜0.9:0.1の範囲にあることがより好ましい。下地層形成用組成物が化合物(3)由来成分と化合物(4)由来成分とをこのような質量比で含有することにより、下地層の上に形成される撥水膜における耐湿性の向上と微小な水滴に対する滑落性の向上のいずれもが可能となる。 By including the compound (4) -derived component in addition to the compound (3) -derived component as described above, the underlayer-forming composition improves the durability of the resulting water-repellent film such as moisture resistance and alkali resistance. This is preferable. The content ratio of the compound (3) -derived component and the compound (4) -derived component in the composition for forming an underlayer is 0 as a mass ratio represented by [compound (3) -derived component: compound (4) -derived component]. It is preferably in the range of 1: 0.9 to 0.9: 0.1, and more preferably in the range of 0.4: 0.6 to 0.9: 0.1. When the composition for forming the underlayer contains the compound (3) -derived component and the compound (4) -derived component at such a mass ratio, the moisture resistance of the water-repellent film formed on the underlayer is improved. It is possible to improve sliding properties against minute water droplets.
なお、下地層形成用組成物における化合物(3)由来成分と化合物(4)由来成分との含有割合は、部分加水分解縮合物や部分加水分解共縮合物を用いた場合、それらを製造する際に用いた化合物(3)および化合物(4)の量から算出できる。 In addition, the content ratio of the component derived from the compound (3) and the component derived from the compound (4) in the composition for forming an underlayer is determined when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is used. It can be calculated from the amount of the compound (3) and the compound (4) used in the above.
下地層形成用組成物は、本発明の効果を損なわない範囲で、目的に応じて、金属酸化物の超微粒子、染料または顔料等の着色用材料、防汚性材料、各種樹脂等の任意成分として機能性添加剤を含んでもよい。ただし、下地層形成用組成物への機能性添加剤の添加はその量によっては、得られる下地層の上に形成される撥水膜の性能を低下させるおそれがある。よって、下地層形成用組成物は、化合物(4)由来成分を含まない場合は、全固形成分が実質的に化合物(3)由来成分のみからなることが好ましく、化合物(4)由来成分を含む場合は、全固形成分が実質的に化合物(3)由来成分と化合物(4)由来成分のみからなることが好ましい。 The composition for forming the underlayer is an optional component such as a metal oxide ultrafine particle, a coloring material such as a dye or a pigment, an antifouling material, various resins, etc., as long as the effects of the present invention are not impaired. A functional additive may be included. However, depending on the amount of the functional additive added to the underlayer-forming composition, the performance of the water-repellent film formed on the obtained underlayer may be deteriorated. Therefore, when the composition for base layer formation does not contain the component derived from the compound (4), it is preferable that the total solid component consists essentially of the component derived from the compound (3), and includes the component derived from the compound (4). In this case, it is preferred that the total solid component consists essentially of the compound (3) -derived component and the compound (4) -derived component.
下地層形成用組成物は、通常、層構成成分となる固形分の他に、経済性、作業性、得られる下地層の厚さ制御のしやすさ等を考慮して、有機溶剤を含む。有機溶剤は、下地層形成用組成物が含有する固形分を溶解するものであれば特に制限されない。有機溶剤としては、撥水膜形成用組成物と同様の化合物が挙げられる。有機溶剤は1種に限定されず、極性、蒸発速度等の異なる2種以上の溶剤を混合して使用してもよい。 The composition for forming an underlayer usually contains an organic solvent in consideration of economic efficiency, workability, ease of control of the thickness of the obtained underlayer, and the like in addition to the solid content as a layer constituent component. The organic solvent is not particularly limited as long as it dissolves the solid content contained in the underlayer-forming composition. As an organic solvent, the same compound as the composition for water-repellent film formation is mentioned. The organic solvent is not limited to one kind, and two or more kinds of solvents having different polarities and evaporation rates may be mixed and used.
下地層形成用組成物は、部分加水分解縮合物や部分加水分解共縮合物を含有する場合、これらを製造するために使用した溶媒を含んでもよい。また、このような溶媒と下地層形成用組成物が含有する有機溶剤は同じものであってもよい。下地層形成用組成物は、さらに、部分加水分解縮合や部分加水分解共縮合で用いた触媒などの成分を含んでいてもよい。下地層形成用組成物の全固形分が実質的に化合物(3)由来成分のみからなる場合に、化合物(3)の部分加水分解縮合物を用いる際には、下地層形成用組成物は、化合物(3)の部分加水分解縮合物の製造で得られた部分加水分解縮合物の溶液そのものであることが好ましい。同様に、下地層形成用組成物の全固形分が実質的に化合物(3)由来成分と化合物(4)由来成分のみからなる場合に、(B)成分と(C)成分の部分加水分解縮合物を用いる際には、下地層形成用組成物は、(B)成分と(C)成分の部分加水分解共縮合物の製造で得られた部分加水分解共縮合物の溶液そのものであることが好ましい。 When the composition for base layer formation contains a partial hydrolysis-condensation product and a partial hydrolysis-condensation product, it may contain the solvent used in order to manufacture these. Moreover, the organic solvent which such a solvent and the composition for base layer formation contain may be the same. The underlayer-forming composition may further contain a component such as a catalyst used in partial hydrolysis condensation or partial hydrolysis cocondensation. When the total solid content of the composition for forming the underlayer is substantially composed only of the component derived from the compound (3), when using the partially hydrolyzed condensate of the compound (3), the composition for forming the underlayer is It is preferable that it is the solution of the partial hydrolysis-condensation product obtained by manufacture of the partial hydrolysis-condensation product of a compound (3) itself. Similarly, when the total solid content of the composition for forming the underlayer is substantially composed only of the component derived from the compound (3) and the component derived from the compound (4), partial hydrolysis condensation of the component (B) and the component (C) When using the product, the composition for forming the underlayer is a solution of the partially hydrolyzed cocondensate obtained by the production of the partially hydrolyzed cocondensate of the component (B) and the component (C). preferable.
下地層形成用組成物における有機溶剤の割合は、化合物(3)由来成分と化合物(4)由来成分の合量質量の100質量部に対して、400〜100,000質量部が好ましい。有機溶剤の含有量が上記範囲であれば、下地層に処理ムラが発生するおそれもなく、経済性、作業性、処理層の厚さ制御のしやすさ等においても問題がない。下地層形成用組成物における有機溶剤の量は、さらに、化合物(3)由来成分と化合物(4)由来成分の合量質量の100質量部に対して、900〜3,500質量部がより好ましく、1,100〜2,500質量部が特に好ましい。 The proportion of the organic solvent in the composition for forming the underlayer is preferably 400 to 100,000 parts by mass with respect to 100 parts by mass of the total mass of the component derived from the compound (3) and the component derived from the compound (4). If the content of the organic solvent is within the above range, there is no risk of processing unevenness occurring in the underlayer, and there is no problem in economic efficiency, workability, ease of controlling the thickness of the processing layer, and the like. The amount of the organic solvent in the underlayer-forming composition is more preferably 900 to 3,500 parts by mass with respect to 100 parts by mass of the total mass of the component derived from the compound (3) and the component derived from the compound (4). 1,100 to 2,500 parts by mass is particularly preferable.
さらに、下地層形成用組成物においては、部分加水分解縮合物や部分加水分解共縮合物を含まないものであっても、(B)成分の加水分解縮合反応、または(B)成分と(C)成分の加水分解共縮合反応を促進させるために、上記で部分加水分解縮合の反応において使用したのと同様の酸触媒等の触媒を配合しておくことも好ましい。部分加水分解縮合物や部分加水分解共縮合物を含む場合であっても、それらの製造に使用した触媒が組成物中に残存していない場合は、触媒を配合することが好ましい。触媒としては、酸触媒が好ましい。触媒の量としては、化合物(3)由来成分と化合物(4)由来成分の合計質量100質量部に対して、0.01〜5質量部が好ましい。なお、下地層形成用組成物において、触媒の量は固形分量に含めない。 Furthermore, in the composition for forming an underlayer, even if it does not contain a partial hydrolysis condensate or a partial hydrolysis cocondensate, the hydrolysis condensation reaction of component (B), or component (B) and (C In order to promote the hydrolysis co-condensation reaction of the component, it is also preferable to add a catalyst such as the same acid catalyst as used in the partial hydrolysis-condensation reaction described above. Even when a partially hydrolyzed condensate or a partially hydrolyzed cocondensate is included, when the catalyst used for the production thereof does not remain in the composition, it is preferable to add a catalyst. As the catalyst, an acid catalyst is preferable. As a quantity of a catalyst, 0.01-5 mass parts is preferable with respect to 100 mass parts of total mass of a component (3) origin component and a compound (4) origin component. In the underlayer forming composition, the amount of the catalyst is not included in the solid content.
下地層形成用組成物は、上記含有成分が加水分解縮合反応や加水分解共縮合反応するための水を含んでいてもよい。下地層形成用組成物における水の含有量は、化合物(3)由来成分と化合物(4)由来成分の合計質量100質量部に対して、1〜50質量部が好ましい。なお、下地層形成用組成物は水を含有しなくとも、以下の下地層を形成する過程において雰囲気中の水分を利用して含有成分の加水分解縮合反応や加水分解共縮合反応を行わせることができる。 The underlayer-forming composition may contain water for the above-mentioned components to undergo a hydrolysis condensation reaction or a hydrolysis cocondensation reaction. 1-50 mass parts is preferable with respect to 100 mass parts of total mass of the component (3) origin component and the compound (4) origin component of water in the composition for base layer formation. In addition, even if the composition for forming the underlayer does not contain water, in the process of forming the following underlayer, the moisture in the atmosphere is used to perform hydrolysis condensation reaction and hydrolysis cocondensation reaction of the contained components. Can do.
ここで、下地層形成用組成物が、(B)成分や(C)成分として、化合物(3)や化合物(4)の加水分解性基が塩素原子である化合物やこれらの部分加水分解縮合物、部分加水分解共縮合物等を含有する場合、これらは反応性が高いことから貯蔵安定性を考慮すると上記触媒および水を実質的に含有しないことが好ましい。実質的に含有しないとは、下地層形成用組成物の全量に対する含有量が触媒については0.001質量%以下であること、水については0.5質量%以下であることをいう。 Here, the composition for forming the underlayer is a compound in which the hydrolyzable group of the compound (3) or compound (4) is a chlorine atom, or a partial hydrolysis condensate thereof, as the component (B) or the component (C). In the case of containing a partially hydrolyzed cocondensate or the like, since these have high reactivity, it is preferable that the catalyst and water are not substantially contained in consideration of storage stability. “Substantially not contained” means that the content relative to the total amount of the composition for forming the underlayer is 0.001% by mass or less for the catalyst and 0.5% by mass or less for water.
下地層形成用組成物を用いて下地層を形成する方法としては、オルガノシラン化合物系の表面処理剤における公知の方法を用いることが可能である。例えば、はけ塗り、流し塗り、回転塗布、浸漬塗布、スキージ塗布、スプレー塗布、手塗り等の方法で下地層形成用組成物を基体の表面に塗布し、大気中または窒素雰囲気中において、必要に応じて乾燥した後、硬化させることで、下地層を形成できる。硬化の条件は、用いる組成物の種類、濃度等により適宜制御されるが、好ましい条件として、温度:20〜50℃、湿度:50〜90%RHの条件が挙げられる。硬化のための時間は、用いる組成物の種類、濃度、硬化条件等によるが、概ね1〜72時間が好ましい。下地層の厚さは、その上に形成される撥水膜に耐湿性、密着性、基体からのアルカリ等のバリア性を付与できる厚さであれば特に限定されない。経済性を考慮すると、50nm以下の厚さが好ましく、その下限は単分子層の厚さである。 As a method for forming the underlayer using the underlayer-forming composition, a known method for an organosilane compound-based surface treatment agent can be used. For example, the composition for forming the underlayer is applied to the surface of the substrate by methods such as brush coating, flow coating, spin coating, dip coating, squeegee coating, spray coating, and hand coating, and is necessary in the air or in a nitrogen atmosphere. The base layer can be formed by curing after drying according to the above. The curing conditions are appropriately controlled depending on the type and concentration of the composition to be used. Preferred conditions include a temperature of 20 to 50 ° C. and a humidity of 50 to 90% RH. The time for curing depends on the type, concentration, curing conditions and the like of the composition to be used, but is generally preferably 1 to 72 hours. The thickness of the underlayer is not particularly limited as long as it can provide moisture resistance, adhesion, and barrier properties such as alkali from the substrate to the water-repellent film formed thereon. In consideration of economy, a thickness of 50 nm or less is preferable, and the lower limit is the thickness of the monomolecular layer.
なお、下地層形成用組成物の硬化は、上記に説明した撥水膜形成用組成物の硬化と同時に行ってもよい。具体的には、下地層形成用組成物を基体表面の所定領域に塗布し、必要に応じて乾燥した後、この表面に撥水膜形成用組成物を塗布し、必要に応じて乾燥した後、上記同様にして硬化処理を施すことで、下地層と撥水膜を同時に硬化させることができる。 In addition, you may perform hardening of the composition for base layer formation simultaneously with hardening of the composition for water-repellent film formation demonstrated above. Specifically, after the base layer forming composition is applied to a predetermined region of the substrate surface and dried as necessary, the water repellent film forming composition is applied to the surface and dried as necessary. By applying the curing process in the same manner as described above, the base layer and the water repellent film can be cured simultaneously.
[輸送機器用物品]
本発明の撥水膜付き基体は、これを具備する輸送機器用物品としての用途に好適に用いられる。輸送機器用物品とは、電車、自動車、船舶、航空機等におけるボディー、窓ガラス(フロントガラス、サイドガラス、リアガラス)、ミラー、バンパー等が好ましく挙げられる。
[Transportation Equipment Items]
The substrate with a water-repellent film of the present invention is suitably used for use as an article for transport equipment comprising the same. Preferred examples of the article for transportation equipment include bodies in trains, automobiles, ships, aircrafts, window glass (front glass, side glass, rear glass), mirrors, bumpers, and the like.
本発明の撥水膜付き基体またはこの基体を具備する輸送機器用物品は、その撥水膜表面が静的撥水性および動的撥水性の双方に優れるため、表面への水滴の付着が少なく、付着した水滴がすみやかに除去される。加えて輸送機器の運行に伴う風圧との相互作用により、付着した水滴は表面を急速に移動し、水滴として溜ることはない。このため、水分が誘発する悪影響を排除できる。また、上記撥水膜は、耐アルカリ性、耐湿性等の耐久性にも優れるため、例えば、輸送機器用物品としての屋外での使用を含む各種使用条件下での長期使用においてもこの撥水性を維持することができる。 Since the water-repellent film surface is excellent in both static water repellency and dynamic water repellency, the substrate with a water-repellent film of the present invention or the article for transport equipment comprising the substrate has less adhesion of water droplets to the surface, Adhering water droplets are removed immediately. In addition, due to the interaction with the wind pressure associated with the operation of the transport equipment, the attached water droplets move rapidly on the surface and do not accumulate as water droplets. For this reason, the bad influence which a water induces can be excluded. In addition, the water-repellent film is excellent in durability such as alkali resistance and moisture resistance. For example, the water-repellent film exhibits this water repellency even in long-term use under various usage conditions including outdoor use as an article for transport equipment. Can be maintained.
本発明の撥水膜付き基体またはこの基体を具備する輸送機器用物品は、特に、各種窓ガラス等の透視野部での用途において、水滴の飛散により視野の確保が非常に容易となり、車輌等の運行において安全性が向上できる。また、水滴が氷結するような環境下でも撥水膜表面には着氷しにくく、着氷したとしても付着力が小さいため自然落下し易い。さらに、水滴の付着がほとんどないため、清浄の作業回数を少なくでき、しかも清浄作業を容易に行うことができる。 The substrate with a water-repellent film of the present invention or an article for transport equipment comprising this substrate is very easy to secure a field of view by scattering of water droplets, particularly in applications in a transparent field portion such as various window glasses. Safety can be improved in operation. Further, even in an environment where water droplets freeze, the surface of the water-repellent film is difficult to be iced, and even when icing, it has a low adhesive force and is likely to fall naturally. Furthermore, since there is almost no adhesion of water droplets, the number of cleaning operations can be reduced, and the cleaning operation can be easily performed.
以下に、本発明の実施例を示すが、本発明はこれらの例によって限定されるものではない。例1〜5、例8〜13が実施例であり、例6、7、例14〜17が比較例である。 Examples of the present invention are shown below, but the present invention is not limited to these examples. Examples 1 to 5 and Examples 8 to 13 are examples, and Examples 6 and 7 and Examples 14 to 17 are comparative examples.
[化合物(1)]
式(1)に示される本発明の化合物として、以下の式(13)、(14)、(15)でそれぞれ示される化合物(13)、(14)、(15)を製造した。
[Compound (1)]
As the compounds of the present invention represented by the formula (1), compounds (13), (14) and (15) represented by the following formulas (13), (14) and (15) were produced.
CH3(Si(CH3)2O)61Si(CH3)2C2H4−Z32 …(13)
CH3(Si(CH3)2O)61Si(CH3)2C2H4−Z33 …(14)
CH3(Si(CH3)2O)61Si(CH3)2C2H4−Z42 …(15)
(例1)化合物(13)の合成
(ビニルポリジメチルシロキサン(1a−1)の製造)
撹拌機、滴下ロートを備えた反応器(内容積300mL、ガラス製)にトリメチルシラノール(1.50g)を投入し、氷浴中で攪拌した。これにn−ブチルリチウムのヘキサン溶液(1.5mol/L)の11.1mLを滴下した。1時間攪拌後、ヘキサメチルシクロトリシロキサン(74.0g)をTHF(74g)に溶解した溶液をゆっくりと滴下した。滴下終了後、氷浴を外して5時間攪拌し、これにクロロジメチルビニルシラン(3.01g)を滴下して、さらに12時間攪拌した。
Example 1 Synthesis of Compound (13) (Production of Vinyl Polydimethylsiloxane (1a-1))
Trimethylsilanol (1.50 g) was charged into a reactor equipped with a stirrer and a dropping funnel (internal volume 300 mL, made of glass) and stirred in an ice bath. To this was added dropwise 11.1 mL of a n-butyllithium hexane solution (1.5 mol / L). After stirring for 1 hour, a solution of hexamethylcyclotrisiloxane (74.0 g) dissolved in THF (74 g) was slowly added dropwise. After completion of the dropwise addition, the ice bath was removed and the mixture was stirred for 5 hours. Chlorodimethylvinylsilane (3.01 g) was added dropwise thereto, and the mixture was further stirred for 12 hours.
得られた反応粗液に10質量%炭酸水素ナトリウム水溶液を加えて2層に分離させ、有機層を蒸留水で洗浄した。この有機層を硫酸マグネシウムで脱水し、揮発成分を50℃/10mmHgの条件下に除去し、下式(1a−1)で表わされる化合物(1a−1)の76.3gを得た。収率は99%であった。なお、(Si(CH3)2O)の繰り返し単位の数は1H−NMRから求めた平均値であり、以下、実施例で示す繰り返し単位数についても全て同様である。
CH3(Si(CH3)2O)61Si(CH3)2CH=CH2 …(1a−1)
A 10% by mass aqueous sodium hydrogen carbonate solution was added to the resulting reaction crude liquid to separate it into two layers, and the organic layer was washed with distilled water. This organic layer was dehydrated with magnesium sulfate, and the volatile component was removed under the condition of 50 ° C./10 mmHg to obtain 76.3 g of the compound (1a-1) represented by the following formula (1a-1). The yield was 99%. In addition, the number of repeating units of (Si (CH 3 ) 2 O) is an average value obtained from 1 H-NMR, and the same applies to the number of repeating units shown in the following examples.
CH 3 (Si (CH 3 ) 2 O) 61 Si (CH 3 ) 2 CH═CH 2 (1a-1)
得られた化合物(1a−1)の1H−NMR(300.4MHz、基準:C6D6(=7.00ppm))の測定結果を以下に示す。なお、各測定値は、測定値に続く()内に示す基に由来する測定値を意味する。以下、実施例で示すNMRの測定結果については、全て同様である。
1H−NMR(溶媒:C6D6)δ(ppm):5.6〜6.1(3H、m、H−Si)、0.0〜0.3(375H、m、CH3−Si)。
The measurement result of 1 H-NMR (300.4 MHz, standard: C 6 D 6 (= 7.00 ppm)) of the obtained compound (1a-1) is shown below. In addition, each measured value means the measured value derived from the group shown in () following a measured value. Hereinafter, the NMR measurement results shown in the examples are all the same.
1 H-NMR (solvent: C 6 D 6 ) δ (ppm): 5.6 to 6.1 (3H, m, H—Si), 0.0 to 0.3 (375 H, m, CH 3 —Si) ).
(環状メチルハイドロジェンシロキサン化合物(1b−1)の製造)
攪拌機、ジムロートを備えた反応器(内容積50mL)に、上記で得られた化合物(1a−1)(10.0g)、1,3,5,7−テトラメチルシクロテトラシロキサン(2.60g)、およびPt触媒(Ptの1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体の2質量%キシレン溶液)(0.002g)を投入して、室温にて24時間攪拌した。
(Production of cyclic methyl hydrogen siloxane compound (1b-1))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), the compound (1a-1) (10.0 g) obtained above, 1,3,5,7-tetramethylcyclotetrasiloxane (2.60 g) , And a Pt catalyst (a 2 mass% xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of Pt) (0.002 g) were added and stirred at room temperature for 24 hours. .
得られた反応粗液から揮発成分を50℃/10mmHgの条件下に除去し、末端に上記式(Zh1)で表わされる構造を有する、下式(1b−1)で表わされる化合物(1b−1)の10.4gを得た。収率は99%であった。
CH3(Si(CH3)2O)61Si(CH3)2C2H4−Zh1 …(1b−1)
Volatile components were removed from the obtained reaction crude liquid under the conditions of 50 ° C./10 mmHg, and the compound represented by the following formula (1b-1) having a structure represented by the above formula (Z h1 ) at the terminal (1b- 10.4 g of 1) was obtained. The yield was 99%.
CH 3 (Si (CH 3) 2 O) 61 Si (CH 3) 2 C 2 H 4 -Z h1 ... (1b-1)
得られた化合物(1b−1)の1H−NMR(300.4MHz、基準:C6D6(=7.00ppm))の測定結果を以下に示す。
1H−NMR(溶媒:C6D6)δ(ppm):4.86〜4.92(3H、m、SiH)、0.56〜0.63(4H、m、SiCH2CH2Si)、0.0〜0.3(387H、m、CH3−Si)。
The measurement result of 1 H-NMR (300.4 MHz, standard: C 6 D 6 (= 7.00 ppm)) of the obtained compound (1b-1) is shown below.
1 H-NMR (solvent: C 6 D 6 ) δ (ppm): 4.86 to 4.92 (3H, m, SiH), 0.56 to 0.63 (4H, m, SiCH 2 CH 2 Si) , 0.0~0.3 (387H, m, CH 3 -Si).
(化合物(13)の製造)
攪拌機、ジムロートを備えた反応器(内容積50mL)に、上記で得られた化合物(1b−1)(5.0g)、ビニルトリクロロシラン(1.55g)、およびPt触媒(Ptの1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体の2質量%キシレン溶液)(0.002g)を投入して、室温にて24時間攪拌した。
得られた反応粗液から揮発成分を50℃/2mmHgの条件下に除去し、上記式(13)で表わされる化合物(13)の5.5gを得た。収率は95%であった。
(Production of Compound (13))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), the compound (1b-1) (5.0 g) obtained above, vinyltrichlorosilane (1.55 g), and Pt catalyst (Pt 1,3) -2% by weight xylene solution of divinyl-1,1,3,3-tetramethyldisiloxane complex) (0.002 g) was added and stirred at room temperature for 24 hours.
Volatile components were removed from the obtained reaction crude liquid under the conditions of 50 ° C./2 mmHg to obtain 5.5 g of the compound (13) represented by the above formula (13). The yield was 95%.
得られた化合物(13)の1H−NMR(300.4MHz、基準:C6D6(=7.00ppm))の測定結果を以下に示す。
1H−NMR(溶媒:C6D6)δ(ppm):0.0〜1.0(403H、m、CH3−SiおよびSi−CH2)。
The measurement result of 1 H-NMR (300.4 MHz, standard: C 6 D 6 (= 7.00 ppm)) of the obtained compound (13) is shown below.
1 H-NMR (solvent: C 6 D 6 ) δ (ppm): 0.0 to 1.0 (403H, m, CH 3 —Si and Si—CH 2 ).
(例2)化合物(14)の合成
(化合物(14)の製造)
攪拌機、ジムロートを備えた反応器(内容積50mL)に、上記例1と同様に製造した化合物(1b−1)(5.0g)、ビニルトリメトキシシラン(1.90g)、およびPt触媒(Ptの1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体の2質量%キシレン溶液)(0.041g)を投入して、室温にて24時間攪拌した。
得られた反応粗液から揮発成分を50℃/2mmHgの条件下に除去し、上記式(14)で表わされる化合物(14)の5.6gを得た。収率は99%であった。
Example 2 Synthesis of Compound (14) (Production of Compound (14))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), the compound (1b-1) (5.0 g), vinyltrimethoxysilane (1.90 g) produced in the same manner as in Example 1 above, and Pt catalyst (Pt Of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in 2% by mass xylene) (0.041 g) was added and stirred at room temperature for 24 hours.
Volatile components were removed from the obtained reaction crude liquid under the conditions of 50 ° C./2 mmHg to obtain 5.6 g of the compound (14) represented by the above formula (14). The yield was 99%.
得られた化合物(14)の1H−NMR(300.4MHz、基準:C6D6(=7.00ppm))の測定結果を以下に示す。
1H−NMR(溶媒:C6D6)δ(ppm):3.3(27H、m、CH3O−Si)、0.0〜1.2(403H、m、CH3−SiおよびSi−CH2)。
The measurement result of 1 H-NMR (300.4 MHz, standard: C 6 D 6 (= 7.00 ppm)) of the obtained compound (14) is shown below.
1 H-NMR (solvent: C 6 D 6 ) δ (ppm): 3.3 (27H, m, CH 3 O—Si), 0.0 to 1.2 (403H, m, CH 3 —Si and Si -CH 2).
(例3)化合物(15)の合成
(分枝状メチルハイドロジェンシロキサン化合物(1c−1)の製造)
攪拌機、ジムロートを備えた反応器(内容積50mL)に、上記例1と同様に製造した化合物(1a−1)(5.0g)、上記式(D)で表わされる分枝状ハイドロジェンシロキサン(1.77g)、およびPt触媒(Ptの1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体の2質量%キシレン溶液)(0.002g)を投入して、室温にて24時間攪拌した。
Example 3 Synthesis of Compound (15) (Production of Branched Methylhydrogensiloxane Compound (1c-1))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), the compound (1a-1) (5.0 g) produced in the same manner as in Example 1 above, a branched hydrogensiloxane represented by the above formula (D) ( 1.77 g) and a Pt catalyst (a 2 mass% xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of Pt) (0.002 g) were added at room temperature. Stir for 24 hours.
得られた反応粗液から揮発成分を50℃/10mmHgの条件下に除去し、末端に上記式(Zh2)で表わされる構造を有する、下式(1c−1)で表わされる化合物(1c−1)の5.2gを得た。収率は99%であった。
CH3(Si(CH3)2O)61Si(CH3)2C2H4−Zh2 …(1c−1)
Volatile components were removed from the obtained reaction crude liquid under the conditions of 50 ° C./10 mmHg, and the compound represented by the following formula (1c-1) having a structure represented by the above formula (Z h2 ) at the terminal (1c- 5.2 g of 1) was obtained. The yield was 99%.
CH 3 (Si (CH 3) 2 O) 61 Si (CH 3) 2 C 2 H 4 -Z h2 ... (1c-1)
得られた化合物(1c−1)の1H−NMR(300.4MHz、基準:C6D6(=7.00ppm))の測定結果を以下に示す。
1H−NMR(溶媒:C6D6)δ(ppm):4.85〜4.90(3H、m、SiH)、0.61〜0.64(4H、m、SiCH2CH2Si)、0.0〜0.3(399H、m、CH3−Si)。
The measurement result of 1 H-NMR (300.4 MHz, standard: C 6 D 6 (= 7.00 ppm)) of the obtained compound (1c-1) is shown below.
1 H-NMR (solvent: C 6 D 6 ) δ (ppm): 4.85 to 4.90 (3H, m, SiH), 0.61 to 0.64 (4H, m, SiCH 2 CH 2 Si) , 0.0~0.3 (399H, m, CH 3 -Si).
(化合物(15)の製造)
攪拌機、ジムロートを備えた反応器(内容積50mL)に、上記で得られた化合物(1c−1)(5.0g)、ビニルトリクロロシラン(1.60g)、およびPt触媒(Ptの1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体の2質量%キシレン溶液)(0.002g)を投入して、室温にて24時間攪拌した。
得られた反応粗液から揮発成分を50℃/2mmHgの条件下に除去し、上記式(15)で表わされる化合物(15)の5.6gを得た。収率は97%であった。
(Production of Compound (15))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), the compound (1c-1) (5.0 g) obtained above, vinyltrichlorosilane (1.60 g), and a Pt catalyst (Pt 1,3 -2% by weight xylene solution of divinyl-1,1,3,3-tetramethyldisiloxane complex) (0.002 g) was added and stirred at room temperature for 24 hours.
Volatile components were removed from the obtained reaction crude liquid under conditions of 50 ° C./2 mmHg to obtain 5.6 g of the compound (15) represented by the above formula (15). The yield was 97%.
得られた化合物(15)の1H−NMR(300.4MHz、基準:C6D6(=7.00ppm))の測定結果を以下に示す。
1H−NMR(溶媒:C6D6)δ(ppm):0.0〜1.1(415H、m、CH3−SiおよびSi−CH2)。
The measurement result of 1 H-NMR (300.4 MHz, standard: C 6 D 6 (= 7.00 ppm)) of the obtained compound (15) is shown below.
1 H-NMR (solvent: C 6 D 6 ) δ (ppm): 0.0 to 1.1 (415H, m, CH 3 —Si and Si—CH 2 ).
[撥水膜形成用組成物]
以下に、上記で得られた化合物(13)、化合物(14)を含有する実施例の撥水膜形成用組成物を調製した。また、比較例として、下記式(cf1)、式(cf2)でそれぞれ示される化合物(cf1)、および化合物(cf2)を含有する撥水膜形成用組成物を調製した。
CH3(Si(CH3)2O)61Si(CH3)2C2H4SiCl3 …(cf1)
Cl3SiC2H4(Si(CH3)2O)60Si(CH3)2C2H4SiCl …(cf2)
[Composition for water-repellent film formation]
Below, the composition for water-repellent film formation of the Example containing the compound (13) obtained above and a compound (14) was prepared. Moreover, the composition for water-repellent film formation containing the compound (cf1) shown by the following formula (cf1) and a formula (cf2), respectively, and a compound (cf2) as a comparative example was prepared.
CH 3 (Si (CH 3) 2 O) 61 Si (CH 3) 2 C 2 H 4 SiCl 3 ... (cf1)
Cl 3 SiC 2 H 4 (Si (CH 3 ) 2 O) 60 Si (CH 3 ) 2 C 2 H 4 SiCl (cf2)
(化合物(cf1)の製造)
攪拌機、ジムロートを備えた反応器(内容積50mL)に、上記例1と同様に製造した化合物(1a−1)(20.0g)、トリクロロシラン(1.17g)、およびPt触媒(Ptの1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体の2質量%キシレン溶液)(0.015g)を投入して、室温にて24時間攪拌した。
得られた反応粗液から揮発成分を50℃/10mmHgの条件下に除去し、上記式(cf1)で表わされる化合物(cf1)の20.2gを得た。収率は98%であった。
(Production of Compound (cf1))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), the compound (1a-1) (20.0 g), trichlorosilane (1.17 g) and Pt catalyst (Pt 1 , 3-divinyl-1,1,3,3-tetramethyldisiloxane complex in 2% by mass xylene solution) (0.015 g) was added and stirred at room temperature for 24 hours.
Volatile components were removed from the obtained reaction crude liquid under the conditions of 50 ° C./10 mmHg to obtain 20.2 g of the compound (cf1) represented by the above formula (cf1). The yield was 98%.
得られた化合物(cf1)の1H−NMR(300.4MHz、基準:C6D6(=7.00ppm))の測定結果を以下に示す。
1H−NMR(溶媒:C6D6)δ(ppm):0.55〜1.05(4H、m、SiC2H4Si)、0.0〜0.3(375H、m、CH3−Si)。
The measurement result of 1 H-NMR (300.4 MHz, standard: C 6 D 6 (= 7.00 ppm)) of the obtained compound (cf1) is shown below.
1 H-NMR (solvent: C 6 D 6 ) δ (ppm): 0.55 to 1.05 (4H, m, SiC 2 H 4 Si), 0.0 to 0.3 (375 H, m, CH 3 -Si).
(化合物(cf2)の製造)
攪拌機、ジムロートを備えた反応器(内容積50mL)に、DMS−V21(商品名、Gelest社製、両末端ビニルポリジメチルシロキサン、(Si(CH3)2O)単位の繰り返し数60)(20.0g)、トリクロロシラン(2.02g)、およびPt触媒(Ptの1,3−ジビニル−1,1,3,3−テトラメチルジシロキサン錯体の2質量%キシレン溶液)(0.021g)を投入して、室温にて24時間攪拌した。
得られた反応粗液から揮発成分を50℃/10mmHgの条件下に除去し、上記式(cf2)で表わされる化合物(cf2)の10.1gを得た。収率は98%であった。
(Production of Compound (cf2))
In a reactor equipped with a stirrer and a Dimroth (internal volume 50 mL), DMS-V21 (trade name, manufactured by Gelest, vinyl polydimethylsiloxane at both ends, the number of repetitions of (Si (CH 3 ) 2 O) units of 60) (20 0.0 g), trichlorosilane (2.02 g), and Pt catalyst (2 mass% xylene solution of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of Pt) (0.021 g) The mixture was charged and stirred at room temperature for 24 hours.
Volatile components were removed from the obtained reaction crude liquid under the conditions of 50 ° C./10 mmHg to obtain 10.1 g of the compound (cf2) represented by the above formula (cf2). The yield was 98%.
得られた化合物(cf2)の1H−NMR(300.4MHz、基準:C6D6(=7.00ppm))の測定結果を以下に示す。
1H−NMR(溶媒:C6D6)δ(ppm):0.55〜1.05(8H、m、SiC2H4SiCl3)、0.0〜0.3(366H、m、CH3−Si)。
The measurement result of 1 H-NMR (300.4 MHz, standard: C 6 D 6 (= 7.00 ppm)) of the obtained compound (cf2) is shown below.
1 H-NMR (solvent: C 6 D 6 ) δ (ppm): 0.55 to 1.05 (8H, m, SiC 2 H 4 SiCl 3 ), 0.0 to 0.3 (366H, m, CH 3- Si).
(例4)撥水膜形成用組成物1の調製
撹拌機、温度計がセットされたガラス容器で、それぞれ、上記例1で得られた化合物(13)が11.6質量%、酢酸ブチル(純正化学社製)が13.2質量%、オクタン(純正化学社製)が75.2質量%となる割合で混合し、25℃にて5分間撹拌して、撥水膜形成用組成物1を得た。
(Example 4) Preparation of composition 1 for forming water-repellent film In a glass container in which a stirrer and a thermometer were set, the compound (13) obtained in Example 1 was 11.6% by mass, butyl acetate ( Junsei Chemical Co., Ltd.) was mixed at a ratio of 13.2% by mass and Octane (Junsei Chemical Co., Ltd.) was 75.2% by mass. The mixture was stirred at 25 ° C. for 5 minutes to form a water-repellent film-forming composition 1 Got.
(例5)撥水膜形成用組成物2の調製
撹拌機、温度計がセットされたガラス容器で、上記例2で得られた化合物(14)が10質量%、イソプロピルアルコール(純正化学社製)が16.7質量%、酢酸ブチルが68.3質量%となる割合で混合し、25℃にて1分間撹拌した後、10質量%硝酸水溶液を5質量%添加し25℃にて3時間撹拌して、撥水膜形成用組成物2を得た。なお、各成分の含有量(質量%)は撥水膜形成用組成物2の全量に対する質量%である。
(Example 5) Preparation of water repellent film forming composition 2 In a glass container in which a stirrer and a thermometer were set, the compound (14) obtained in Example 2 was 10% by mass, isopropyl alcohol (manufactured by Junsei Chemical Co., Ltd.). ) Is 16.7% by mass and butyl acetate is 68.3% by mass, stirred at 25 ° C. for 1 minute, added with 5% by mass of 10% by mass nitric acid aqueous solution, and then at 25 ° C. for 3 hours. By stirring, a water-repellent film-forming composition 2 was obtained. In addition, content (mass%) of each component is mass% with respect to the whole quantity of the composition 2 for water-repellent film formation.
(例6、7)撥水膜形成用組成物3、4の調製
上記例4において化合物(13)を化合物(cf1)または化合物(cf2)に変えた以外は同様にして、撥水膜形成用組成物3、撥水膜形成用組成物4を得た。
(Examples 6 and 7) Preparation of water-repellent film-forming compositions 3 and 4 In the same manner as in Example 4 except that compound (13) was changed to compound (cf1) or compound (cf2), Composition 3 and water repellent film-forming composition 4 were obtained.
[下地層形成用組成物の調製]
(下地層形成用組成物1)
撹拌機、温度計がセットされたガラス容器で、SI−400(テトライソシアネートシラン(Si(NCO)4);マツモトファインケミカル社製)5質量%、酢酸ブチル(純正化学社製)95質量%となるように混合し、25℃にて3分間撹拌することで下地層形成用組成物1を得た。なお、各成分の含有量(質量%)は下地層形成用組成物1の全量に対する質量%である。
[Preparation of composition for forming underlayer]
(Underlayer forming composition 1)
In a glass container in which a stirrer and a thermometer are set, SI-400 (tetraisocyanate silane (Si (NCO) 4 ); Matsumoto Fine Chemical Co., Ltd.) 5 mass%, butyl acetate (Pure Chemical Co., Ltd.) 95 mass% The composition 1 for base layer formation was obtained by stirring for 3 minutes at 25 degreeC. In addition, content (mass%) of each component is the mass% with respect to the whole quantity of the composition 1 for base layer formation.
(下地層形成用組成物2)
撹拌機、温度計がセットされたガラス容器で、ビストリメトキシシリルエタン(東京化成社製)1.6質量%、テトラエトキシシラン(関東化学社製)3.2質量%、エタノール(純正化学社製)86.8質量%となる割合で混合し25℃にて3分間撹拌した後、0.463質量%硝酸水溶液を8.4質量%となる量滴下し、25℃にて3時間撹拌することで下地層形成用組成物2を得た。なお、各成分の含有量(質量%)は下地層形成用組成物2の全量に対する質量%である。
(Underlayer forming composition 2)
A glass container in which a stirrer and a thermometer are set. 1.6% by mass of bistrimethoxysilylethane (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.2% by mass of tetraethoxysilane (manufactured by Kanto Chemical Co., Ltd.), ethanol (manufactured by Junsei Chemical Co., Ltd.) ) After mixing at a rate of 86.8% by mass and stirring at 25 ° C. for 3 minutes, add 0.463% by mass nitric acid aqueous solution dropwise to an amount of 8.4% by mass and stirring at 25 ° C. for 3 hours. Thus, a composition 2 for forming an underlayer was obtained. In addition, content (mass%) of each component is the mass% with respect to the whole quantity of the composition 2 for base layer formation.
[撥水膜付き基体]
上記で得られた撥水膜形成用組成物1〜4および下地層形成用組成物1、2を用いて以下のようにして、実施例(例8〜13)および比較例(例14〜17)の撥水膜付き基体を製造した。
[Substrate with water-repellent film]
Examples (Examples 8 to 13) and Comparative Examples (Examples 14 to 17) were prepared as follows using the water-repellent film-forming compositions 1 to 4 and the underlayer-forming compositions 1 and 2 obtained above. ) Was produced.
(例8〜例17)
基体として、酸化セリウムで表面を研磨洗浄し、乾燥した清浄なソーダライムガラス基板(水接触角5度、300mm×300mm×厚さ3mm)を用い、該ガラス基板の表面に、下記表1に示すとおり下地層を設ける場合は上記で得られた下地層形成用組成物1、2のいずれかの0.5gをスキージコート法によって塗布し、25℃で1分間乾燥し下地層(未硬化)を形成した。次いで、形成した下地層(未硬化)の表面に、表1に示すとおり上記で得られた撥水膜形成用組成物1〜4のいずれかの0.5gをスキージコート法によって塗布し、50℃、60%RHに設定された恒温恒湿槽で48時間保持して撥水膜を形成すると同時に下地層の硬化を行った。その後、撥水膜の表面を2−プロパノールを染み込ませた紙ウェスで拭き上げることで、撥水膜付き基体を得た。なお、下地層を有する場合は、基体側から順に下地層/撥水膜の順に積層された撥水膜付き基体であった。
(Examples 8 to 17)
As a substrate, a clean soda lime glass substrate (water contact angle 5 degrees, 300 mm × 300 mm × thickness 3 mm), which was polished and cleaned with cerium oxide, was used, and the surface of the glass substrate is shown in Table 1 below. When the underlayer is provided as described above, 0.5 g of any of the underlayer-forming compositions 1 and 2 obtained above is applied by a squeegee coating method and dried at 25 ° C. for 1 minute to form an underlayer (uncured). Formed. Next, 0.5 g of any of the water-repellent film-forming compositions 1 to 4 obtained above as shown in Table 1 was applied to the surface of the formed underlayer (uncured) by the squeegee coating method. The water-repellent film was formed by holding in a constant temperature and humidity chamber set to ° C. and 60% RH for 48 hours, and at the same time, the base layer was cured. Thereafter, the surface of the water-repellent film was wiped with a paper waste soaked with 2-propanol to obtain a substrate with a water-repellent film. In addition, when it had a base layer, it was a base | substrate with a water repellent film | membrane laminated | stacked in order of the base layer / water-repellent film in order from the base | substrate side.
[評価]
上記の例8〜17で得られた撥水膜付き基体の評価を、以下のように行った。なお、各測定の前には、エタノールを含ませた紙ウェスで膜表面の汚れの除去を行った。
[Evaluation]
Evaluation of the substrate with a water-repellent film obtained in Examples 8 to 17 was performed as follows. In addition, before each measurement, the dirt on the film surface was removed with a paper waste containing ethanol.
<初期撥水性>
撥水性は、静的撥水性については以下の方法で測定した水接触角(CA)で、動的撥水性(滑水性)については以下の方法で測定した水転落角(SA)で評価した。まず、以下の各試験を行う前に初期値を測定した。
<Initial water repellency>
The water repellency was evaluated by the water contact angle (CA) measured by the following method for static water repellency, and the water falling angle (SA) measured by the following method for dynamic water repellency (water slidability). First, initial values were measured before each of the following tests.
(水接触角(CA))
撥水膜付き基体の撥水膜表面に置いた、直径1mmの水滴の接触角をDM−701(協和界面科学社製)を用いて測定した。撥水膜表面における異なる5ヶ所で測定を行い、その平均値を算出した。
(Water contact angle (CA))
The contact angle of a water droplet having a diameter of 1 mm placed on the surface of the water-repellent film substrate was measured using DM-701 (manufactured by Kyowa Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface of the water-repellent film, and the average value was calculated.
(水転落角(SA))
水平に保持した撥水膜付き基体の撥水膜表面に50μLの水滴を滴下した後、基体を徐々に傾け、水滴が転落しはじめた時の撥水膜付き基体と水平面との角度(転落角)をSA−11(協和界面科学社製)を用いて測定した。撥水膜表面における異なる5ヶ所で測定を行い、その平均値を算出した。転落角が小さいほど動的撥水性(滑水性)に優れる。
(Water drop angle (SA))
After dropping 50 μL of water droplets on the surface of the water repellent film substrate held horizontally, the substrate is gradually tilted, and the angle between the water repellent film-coated substrate and the horizontal plane when the water droplet starts to fall (the falling angle) ) Was measured using SA-11 (manufactured by Kyowa Interface Science Co., Ltd.). Measurement was performed at five different locations on the surface of the water-repellent film, and the average value was calculated. The smaller the sliding angle, the better the dynamic water repellency (slidability).
<耐摩耗性>
例8〜17で得られた撥水膜付き基体を、下記試験条件にて耐ネル布摩耗性試験を行った後、上記方法により水接触角(CA)および水転落角(SA)を測定した。
<Abrasion resistance>
The substrates with water repellent films obtained in Examples 8 to 17 were subjected to a flannel cloth abrasion resistance test under the following test conditions, and then the water contact angle (CA) and the water falling angle (SA) were measured by the above methods. .
(耐ネル布摩耗性試験)
JIS L0849に準拠して下記試験機を用いて下記試験条件で耐ネル布摩耗性試験を行った。
試験機:往復式トラバース試験機(ケイエヌテー社製)
試験条件:綿布(JIS L0803に準拠)、荷重1.2kg、摩耗回数3000回
(Nel cloth abrasion resistance test)
In accordance with JIS L0849, a flannel cloth abrasion resistance test was performed using the following test machine under the following test conditions.
Testing machine: Reciprocating traverse testing machine (manufactured by KT Corporation)
Test conditions: Cotton cloth (conforming to JIS L0803), load 1.2kg, number of wear 3000 times
<耐湿性試験>
例8〜17で得られた撥水膜付き基体を、80℃、95%RHの環境下70時間暴露する耐湿性試験を行った後、上記同様の方法により水接触角(CA)、水転落角(SA)を測定した。
<Moisture resistance test>
The substrate with water repellent film obtained in Examples 8 to 17 was subjected to a moisture resistance test in which the substrate was exposed for 70 hours in an environment of 80 ° C. and 95% RH, and then subjected to water contact angle (CA) and water falling by the same method as described above. The angle (SA) was measured.
<耐アルカリ性試験(pH13)>
例8〜17で得られた撥水膜付き基体を、20℃の0.1N水酸化ナトリウム水溶液に3時間浸漬後、水洗いして、耐アルカリ性試験(pH13)とした。試験後の撥水膜付き基体を上記同様の方法により水接触角(CA)、水転落角(SA)を測定した。
<Alkali resistance test (pH 13)>
The substrate with a water-repellent film obtained in Examples 8 to 17 was immersed in a 0.1N aqueous sodium hydroxide solution at 20 ° C. for 3 hours and then washed with water to make an alkali resistance test (pH 13). The substrate with water-repellent film after the test was measured for water contact angle (CA) and water fall angle (SA) by the same method as described above.
<耐アルカリ性試験(pH14)>
例8〜17で得られた撥水膜付き基体を、20℃の1N水酸化ナトリウム水溶液に2時間浸漬後、水洗いして、耐アルカリ性試験(pH14)とした。試験後の撥水膜付き基体を上記同様の方法により水接触角(CA)、水転落角(SA)を測定した。
<Alkali resistance test (pH 14)>
The substrate with a water-repellent film obtained in Examples 8 to 17 was immersed in a 1N aqueous sodium hydroxide solution at 20 ° C. for 2 hours and then washed with water to make an alkali resistance test (pH 14). The substrate with water-repellent film after the test was measured for water contact angle (CA) and water fall angle (SA) by the same method as described above.
本発明の撥水膜付き基体は、静的撥水性および動的撥水性の双方に優れるととともに、耐アルカリ性、耐湿性等の耐久性にも優れるものであって、電車、自動車、船舶、航空機等の輸送機器におけるボディー、窓ガラス(フロントガラス、サイドガラス、リアガラス)、ミラー、バンパー等の物品としての用途に好適に用いられる。 The substrate with a water-repellent film of the present invention is excellent in both static water repellency and dynamic water repellency, and has excellent durability such as alkali resistance and moisture resistance. It is suitably used for applications as articles such as bodies, window glass (front glass, side glass, rear glass), mirrors, bumpers and the like in transportation equipment such as.
Claims (17)
−Si(R1)3−n(X1)n…(2)
ただし、式(2)中、R1はそれぞれ独立して1価の炭化水素基を、X1はそれぞれ独立して加水分解性基を表す。nは1〜3の整数である。 A compound represented by the following formula (1).
-Si (R 1 ) 3-n (X 1 ) n (2)
In the formula (2), R 1 is independently a monovalent hydrocarbon group, X 1 is represents a hydrolyzable group independently. n is an integer of 1 to 3.
Si(X2)4 …(3)
(ただし、式(3)中、X2はそれぞれ独立して、ハロゲン原子、アルコキシ基またはイソシアネート基を示す。) The base layer is a base layer formed using a composition for forming a base layer containing a component (B) comprising a compound represented by the following formula (3) and / or a partial hydrolysis condensate thereof: 11. A substrate with a water-repellent film according to 11.
Si (X 2 ) 4 (3)
(However, in formula (3), each X 2 independently represents a halogen atom, an alkoxy group or an isocyanate group.)
X3 3Si−(CH2)p−SiX3 3 …(4)
(ただし、式(4)中、X3はそれぞれ独立して加水分解性基または水酸基を示し、pは1〜8の整数である。) The underlayer-forming composition includes the component (B) and the component (C) composed of a compound represented by the following formula (4) and / or a partial hydrolysis condensate thereof, or the component (B) The substrate with a water-repellent film according to claim 12, comprising a partially hydrolyzed cocondensate of a component and the component (C) (however, the component (B) and / or the component (C) may be included).
X 3 3 Si- (CH 2) p -SiX 3 3 ... (4)
(However, in Formula (4), X < 3 > shows a hydrolysable group or a hydroxyl group each independently, and p is an integer of 1-8.)
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US20210147681A1 (en) | 2016-07-22 | 2021-05-20 | Momentive Performance Materials Japan Llc | Thermally conductive polysiloxane composition |
US11118056B2 (en) | 2016-07-22 | 2021-09-14 | Momentive Performance Materials Japan Llc | Thermally conductive polysiloxane composition |
US11286349B2 (en) * | 2016-07-22 | 2022-03-29 | Momentive Performance Materials Japan Llc | Surface treatment agent for thermally conductive polyorganosiloxane composition |
US11359124B2 (en) | 2017-05-31 | 2022-06-14 | Momentive Performance Materials Japan Llc | Thermally conductive polysiloxane composition |
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