JPH04314771A - Film-forming agent composition - Google Patents
Film-forming agent compositionInfo
- Publication number
- JPH04314771A JPH04314771A JP10860091A JP10860091A JPH04314771A JP H04314771 A JPH04314771 A JP H04314771A JP 10860091 A JP10860091 A JP 10860091A JP 10860091 A JP10860091 A JP 10860091A JP H04314771 A JPH04314771 A JP H04314771A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- integer
- film
- group
- same
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 10
- 125000001033 ether group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000000962 organic group Chemical group 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 4
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 4
- 239000005052 trichlorosilane Substances 0.000 description 4
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 description 2
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BCQZXOMGPXTTIC-UHFFFAOYSA-N halothane Chemical compound FC(F)(F)C(Cl)Br BCQZXOMGPXTTIC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【０００１】0001
【従来の技術】硬化することにより、撥水性および撥油
性を有する硬化皮膜を形成する組成物としてシリコーン
組成物（特公平３−１１２４８ 号、特公平２−９０６
９号など）が公知である。シラザン組成物のコーティン
グ材として（特開昭６２−２８３１６４号、特開平１−
２０３４７６号、特開平１−２２１４６６号など）が公
知である。2. Description of the Related Art Silicone compositions (Japanese Patent Publication No. 3-11248, Japanese Patent Publication No. 2-906
No. 9 etc.) are publicly known. As a coating material for silazane compositions (JP-A-62-283164, JP-A-1-1999)
203476, JP-A-1-221466, etc.) are publicly known.
【０００２】0002
【発明が解決しようとする課題】しかし、上記の組成物
を硬化して得られる硬化皮膜は、撥水性と撥油性が未だ
満足できるレベルではない。そこで本発明の課題は、硬
化して得られる硬化物が良好な、撥水性および撥油性を
有する組成物を提供することである。[Problems to be Solved by the Invention] However, the cured film obtained by curing the above composition does not yet have a satisfactory level of water repellency and oil repellency. Therefore, an object of the present invention is to provide a composition that has good water and oil repellency, resulting in a cured product that has good water and oil repellency.
【０００３】0003
【課題を解決するための手段】本発明は、（ａ） 下記
の一般単位式［１］：
（Ｒ １ Ｑ）ａ Ｒ ２ ｂ Ｓｉ（ＮＲ ３ ）
（４−ａ−ｂ）／２ ［１］（式中、 Ｒ１
は同じでも異なってもよく、パーフロオロアルキル基も
しくはパーフルオロアルキルエーテル基を表し、 Ｒ２
および Ｒ３ は同じでも異なってもよく、水素原子
または置換もしくは非置換の１価の炭化水素基を表し、
Ｑは同じでも異なってもよく、２価の有機基を表し、ａ
は１〜３の整数を表し、ｂは０〜２の整数を表す。ただ
し、ａ＋ｂは１〜３の整数である。）で表される単位、
および下記の一般単位式［２］：Ｒ ２ ｃ Ｓｉ（Ｎ
Ｒ ３ ） （４−ｃ）／２ ［２］（式中、 Ｒ２
および Ｒ３ は前記のとおりであり、ｃは１〜３の
整数を表す。）で表される単位からなり、単位式［１］
と［２］ のモル比が ［１］／［２］ ＝９５／５
〜５０／５０であるオルガノシラザン共重合体、（ｂ
） 上記 （ａ）成分のオルガノシラザン共重合体を溶
解することが可能な有機溶剤、以上の （ａ）および
（ｂ）成分を必須の構成成分として含む硬化性皮膜形成
剤組成物を提供するものである。[Means for Solving the Problems] The present invention provides (a) the following general unit formula [1]: (R 1 Q)a R 2 b Si(NR 3 )
(4-a-b)/2 [1] (wherein, R1
may be the same or different and represent a perfluoroalkyl group or a perfluoroalkyl ether group, R2
and R3 may be the same or different and represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group,
Q may be the same or different and represents a divalent organic group, a
represents an integer of 1 to 3, and b represents an integer of 0 to 2. However, a+b is an integer from 1 to 3. ),
and the following general unit formula [2]: R 2 c Si(N
R3) (4-c)/2 [2] (wherein, R2
and R3 are as described above, and c represents an integer of 1 to 3. ), and the unit formula [1]
The molar ratio of and [2] is [1]/[2] =95/5
~50/50 organosilazane copolymer, (b
) An organic solvent capable of dissolving the organosilazane copolymer of component (a) above, and
The present invention provides a curable film-forming agent composition containing component (b) as an essential component.
【０００４】（ａ） オルガノシラザン共重合体（ａ）
成分のオルガノシラザン共重合体は、本発明による組成
物のベースポリマーとなる成分である。前記の式［Ｉ］
中、 Ｒ１ は同じでも異なってもよく、パーフロオ
ロアルキル基もしくはパーフルオロアルキルエーテル基
を表す。かかるパーフルオロアルキル基としては、炭素
原子数が１〜２０のものが好ましく、具体的にはＣ ８
Ｆ １７−などが挙げられる。中でも炭素原子数が４
〜１０のものが特に好ましい。一方、かかるパーフルオ
ロアルキルエーテル基としては、炭素原子数が２〜３５
のものが好ましく、例えば下記の一般式：
Ｆ−［ＣＦ（ ＣＦ３ ） ＣＦ２ Ｏ］ｅ ＣＦ（
ＣＦ３）−（式中、ｅは１〜１０の整数を表す）で表さ
れるものなどが挙げられる。中でも炭素原子数が５〜２
０のものが特に好ましい。(a) Organosilazane copolymer (a)
The component organosilazane copolymer is the component that becomes the base polymer of the composition according to the invention. The above formula [I]
Among them, R1 may be the same or different and represent a perfluoroalkyl group or a perfluoroalkyl ether group. The perfluoroalkyl group preferably has 1 to 20 carbon atoms, specifically C 8
Examples include F 17-. Among them, the number of carbon atoms is 4
-10 are particularly preferred. On the other hand, the perfluoroalkyl ether group has 2 to 35 carbon atoms.
Those of the following general formula are preferable, for example: F-[CF(CF3)CF2O]e CF(
Examples include those represented by CF3)-(in the formula, e represents an integer of 1 to 10). Among them, the number of carbon atoms is 5 to 2
0 is particularly preferred.
【０００５】Ｒ２ および Ｒ３ は同じでも異なって
もよく、水素原子または置換もしくは非置換の１価の炭
化水素基を表す。かかる置換もしくは非置換の１価の炭
化水素基としては、炭素原子数が１〜１０のものが好ま
しく、特に好ましくは１〜６である。具体的にはメチル
基、エチル基、プロピル基、ブチル基などのアルキル基
、ビニル基、アリル基などのアルケニル基、フェニル基
、トリル基などのアリール基、シクロヘキシル基などの
シクロアルキル基、およびこれらの基の炭素原子に結合
した水素原子の一部もしくは全部がハロゲン原子で置換
されたものなどが挙げられる。中でも Ｒ２ としては
メチル基が好ましく、 Ｒ３ としては水素原子が好ま
しい。R2 and R3 may be the same or different and represent a hydrogen atom or a substituted or unsubstituted monovalent hydrocarbon group. The substituted or unsubstituted monovalent hydrocarbon group preferably has 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, alkenyl groups such as vinyl group and allyl group, aryl groups such as phenyl group and tolyl group, cycloalkyl groups such as cyclohexyl group, and these Examples include those in which part or all of the hydrogen atoms bonded to the carbon atoms of the group are replaced with halogen atoms. Among these, R2 is preferably a methyl group, and R3 is preferably a hydrogen atom.
【０００６】Ｑは同じでも異なってもよく、２価の有機
基を表す。かかる２価の有機基としては、炭素原子数が
２〜５のものが好ましく、具体的には−ＣＨ２ ＣＨ２
−、− （ＣＨ２ ） ３ −などのアルキレン基、
式：−ＣＨ２ Ｏ ＣＨ２ ＣＨ２ ＣＨ２ −などの
酸素原子を含有するエーテル基などが挙げられる。ａは
１〜３の整数を表し、ｂは０〜２の整数を表す。ただし
、ａ＋ｂは１〜３の整数である。Q may be the same or different and represents a divalent organic group. The divalent organic group preferably has 2 to 5 carbon atoms, specifically -CH2CH2
-, -(CH2)3- and other alkylene groups,
Examples include ether groups containing an oxygen atom such as the formula: -CH2OCH2CH2CH2-. a represents an integer of 1 to 3, and b represents an integer of 0 to 2. However, a+b is an integer from 1 to 3.
【０００７】（ａ）成分のオルガノシラザン共重合体中
、前記の一般単位式［１］ で表される単位と一般単位
式［２］ で表される単位との存在割合は、モル比：（
式［１］ で表される単位／式［２］ で表される単位
）が９５／５ 〜５０／５０の範囲であることが好まし
い。特に好ましくは９０／１０〜６０／４０の範囲であ
る。上記のモル比が大きすぎると、得られる硬化皮膜が
有する撥水性および撥油性が低下してしまい、水滴およ
び油滴の落下角が大きくなる。また、小さすぎると、撥
水性および撥油性が低下してしまうので、得られる硬化
皮膜が有する接触角が小さくなる。In the organosilazane copolymer of component (a), the proportion of the units represented by the general unit formula [1] and the units represented by the general unit formula [2] is determined by the molar ratio: (
The ratio of units represented by formula [1]/units represented by formula [2] is preferably in the range of 95/5 to 50/50. Particularly preferred is a range of 90/10 to 60/40. If the above-mentioned molar ratio is too large, the water repellency and oil repellency of the resulting cured film will decrease, and the falling angle of water droplets and oil droplets will increase. On the other hand, if it is too small, the water repellency and oil repellency will decrease, and the contact angle of the resulting cured film will become small.
【０００８】（ａ）成分のオルガノシラザン共重合体を
得る方法としては、例えば下記の一般式［３］：（Ｒ
１ Ｑ）ａ Ｒ ２ ｂ ＳｉＸ （４−ａ−ｂ）
［３］（式中、Ｘはハロゲン原子を表し、 Ｒ１
、 Ｒ２ 、Ｑ、ａおよびｂは前記のとおりである）
で表されるオルガノハロシラン、並びに下記の一般式［
４］：
Ｒ ２ ｃ ＳｉＸ ４−ｃ
［４］（式中、 Ｒ２ 、ｃおよびＸは前記のと
おり）で表されるオルガノハロシランの混合物を、有機
溶剤中で式：
Ｒ ３ ＮＨ２
（ここで Ｒ３ は前記のとおり）
で表されるアンモニアもしくは１級アミンと反応させる
方法が挙げられる。上記の一般式［３］ で表されるオ
ルガノハロシランとしては、具体的には下記の化学式：
As a method for obtaining the organosilazane copolymer of component (a), for example, the following general formula [3]: (R
1 Q) a R 2 b SiX (4-a-b)
[3] (wherein, X represents a halogen atom, R1
, R2, Q, a and b are as described above), and the following general formula [
4]: R2cSiX4-c
[4] A mixture of organohalosilanes represented by the formula: R 3 NH2 (wherein R 3 is as described above) in an organic solvent. Examples include a method of reacting with ammonia or a primary amine. Specifically, the organohalosilane represented by the above general formula [3] has the following chemical formula:
【化１】で表されるものなどが挙げられる。また、上記
の一般式［４］ で表されるオルガノハロシランとして
は、具体的には下記の化学式：
ＣＨ３ ＳｉＣｌ３ 、（ ＣＨ３ ） ２ ＳｉＣｌ
２ 、ＰｈＳｉＣｌ３ 、ＰｈＭｅＳｉＣｌ２ （式中
、Ｐｈはフェニル基を表し、Ｍｅはメチル基を表す）で
表されるものなどが挙げられる。Examples include those represented by [Chemical formula 1]. Further, as the organohalosilane represented by the above general formula [4], specifically, the following chemical formula: CH3 SiCl3, (CH3) 2 SiCl
2, PhSiCl3, PhMeSiCl2 (in the formula, Ph represents a phenyl group and Me represents a methyl group), and the like.
【０００９】（ｂ） の有機溶剤
（ｂ）の有機溶剤は、 （ａ）成分のオルガノシラザン
共重合体を溶解することが可能なものであればいずれも
使用することができる。そのような有機溶剤としては、
フッ化炭化水素が好ましい。かかるフッ化炭化水素とし
ては、具体的には例えばトリクロロトリフルオロエタン
、テトラクロロジフルオロエタン、ジクロロモノフルオ
ロエタン、ジクロロトリフルオロエタン、ブロモクロロ
トリフルオロエタン、メタキシレンヘキサフロライドな
どが挙げられる。Organic solvent (b) Any organic solvent can be used as long as it can dissolve the organosilazane copolymer (a). Such organic solvents include:
Fluorinated hydrocarbons are preferred. Specific examples of such fluorinated hydrocarbons include trichlorotrifluoroethane, tetrachlorodifluoroethane, dichloromonofluoroethane, dichlorotrifluoroethane, bromochlorotrifluoroethane, metaxylene hexafluoride, and the like.
【００１０】（ｂ）の有機溶剤には、フッ化炭化水素以
外の有機溶剤を、（ａ）成分に対する溶解性が低下しな
い範囲でフッ化炭化水素と併用することができる。かか
るフッ化炭化水素以外の有機溶剤としては、例えばジク
ロロエタン、トリクロロエタン、メチレンクロライド、
などの塩化炭化水素、ベンゼン、トルエン、キシレンな
どの芳香族炭化水素、ジエチルエーテル、ジプロピルエ
ーテル、ジブチルエーテルなどのエーテル、ｎ−ペンタ
ン、ｎ−ヘキサン、ｎ−ヘプタン、シクロヘキサン、石
油エーテルなどの飽和炭化水素などが挙げられる。As the organic solvent (b), organic solvents other than fluorinated hydrocarbons can be used in combination with the fluorinated hydrocarbons as long as the solubility of component (a) is not reduced. Examples of organic solvents other than fluorinated hydrocarbons include dichloroethane, trichloroethane, methylene chloride,
Chlorinated hydrocarbons such as benzene, toluene, aromatic hydrocarbons such as xylene, ethers such as diethyl ether, dipropyl ether, dibutyl ether, saturated ethers such as n-pentane, n-hexane, n-heptane, cyclohexane, petroleum ether, etc. Examples include hydrocarbons.
【００１１】（ｂ）の有機溶剤は、 （ａ）のオルガノ
シラザン共重合体を合成する際の溶媒として使用するこ
とができ、 （ａ）成分のオルガノシラザン共重合体を
合成した後に （ｂ）成分を加えることにより目的とす
る皮膜形成剤組成物を得ることができる。The organic solvent (b) can be used as a solvent when synthesizing the organosilazane copolymer (a), and after synthesizing the organosilazane copolymer (a), (b) By adding the components, the desired film-forming agent composition can be obtained.
【００１２】用途
本発明の皮膜形成剤組成物による硬化皮膜は、良好な撥
水性を有する。そのため、本発明の皮膜形成剤組成物を
、例えば自動車、船舶、鉄道車両等の窓ガラス用の撥水
剤として利用することができる。Application: The cured film formed by the film-forming composition of the present invention has good water repellency. Therefore, the film-forming agent composition of the present invention can be used, for example, as a water repellent for window glass of automobiles, ships, railway vehicles, and the like.
【００１３】[0013]
【実施例】実施例１
（ａ）成分のオルガノシラザン共重合体を合成するため
に、原料として下記の化学式で表される含フッ素トリク
ロロシラン
Ｃ ８ Ｆ １７ＣＨ２ ＣＨ２ ＳｉＣｌ３
５５．７ｇ （９．６×１０−２モル）および、
ジクロロジメチルシラン ４．１ｇ
（３．２×１０−２モル）
を、そして同時に、トリクロロトリフルオロエタン
２００ｍｌを反応容器に仕込んだ。この溶液を５℃に
冷却した後、液温を２０℃に保ちながら、溶液にアンモ
ニアガスを２時間吹き込んだ。その後加熱還流を３０分
間行って、溶液中に溶解していた過剰のアンモニアを除
去した。再び溶液を５℃に冷却した後、副生物である塩
化アンモニウムを溶液より濾別して、無色透明なオルガ
ノシラザン共重合体を得た。なお、前記の式［１］ で
表される単位と式［２］ で表される単位とのモル比は
、７４／２６であった。[Example] Example 1 In order to synthesize the organosilazane copolymer of component (a), fluorine-containing trichlorosilane C 8 F 17CH2 CH2 SiCl3 represented by the following chemical formula was used as a raw material.
55.7g (9.6 x 10-2 mol) and 4.1g dichlorodimethylsilane
(3.2 x 10-2 mol) and simultaneously trichlorotrifluoroethane
200 ml was charged into the reaction vessel. After cooling this solution to 5°C, ammonia gas was blown into the solution for 2 hours while maintaining the liquid temperature at 20°C. Thereafter, the solution was heated under reflux for 30 minutes to remove excess ammonia dissolved in the solution. After cooling the solution to 5° C. again, ammonium chloride as a by-product was filtered off from the solution to obtain a colorless and transparent organosilazane copolymer. The molar ratio of the units represented by the formula [1] and the units represented by the formula [2] was 74/26.
【００１４】次に、上記のオルガノシラザン共重合体を
トリクロロトリフルオロエタンで１重量％に希釈し、目
的とする皮膜形成剤組成物を得た。さらに、得られた皮
膜形成剤組成物を厚さが ０．５μｍ になるようにガ
ラス基板にコーティングし、 １０５℃で２時間硬化し
て硬化皮膜を形成した。Next, the above organosilazane copolymer was diluted to 1% by weight with trichlorotrifluoroethane to obtain the intended film-forming agent composition. Further, the obtained film-forming agent composition was coated on a glass substrate to a thickness of 0.5 μm, and cured at 105° C. for 2 hours to form a cured film.
【００１５】実施例２
（ａ）成分であるオルガノシラザン共重合体の原料とし
て、実施例１で使用した
含フッ素トリクロロシラン ５８．５ｇ
（１．０×１０−１モル） 、
ジクロロジメチルシラン １．５ｇ
（１．２×１０−２モル） 、
および、
トリクロロメチルシラン ０．１ｇ
（６．７×１０−４モル）
を使用した以外は実施例１と同様にして、上記重合体を
合成し、次いで、皮膜形成剤組成物を得た。なお、前記
の式［１］ で表される単位と式［２］ で表される単
位とのモル比は、８８／１２であった。さらに、得られ
た皮膜形成剤組成物を実施例１と同様に処理し、硬化し
て硬化皮膜を形成した。Example 2 58.5 g of the fluorine-containing trichlorosilane used in Example 1 was used as a raw material for the organosilazane copolymer as component (a).
(1.0 x 10-1 mol), dichlorodimethylsilane 1.5g
(1.2 x 10-2 mol), and trichloromethylsilane 0.1g
The above polymer was synthesized in the same manner as in Example 1 except that (6.7×10 −4 mol) was used, and then a film-forming agent composition was obtained. The molar ratio of the units represented by the formula [1] and the units represented by the formula [2] was 88/12. Furthermore, the obtained film-forming agent composition was treated in the same manner as in Example 1 and cured to form a cured film.
【００１６】実施例３
（ａ）成分であるオルガノシラザン共重合体の原料とし
て、実施例１で使用した
含フッ素トリクロロシラン ５２．０ｇ
（８．９×１０−２モル） 、
ジクロロジメチルシラン ７．８ｇ
（６．０×１０−２モル） 、
および
トリクロロメチルシラン ０．２３ｇ
（１．５×１０−３モル）
を使用した以外は実施例１と同様にして該共重合体を合
成し、次いで皮膜形成剤組成物を得た。なお、前記の式
［１］ で表される単位と式［２］ で表される単位と
のモル比は、５９／４１であった。さらに、得られた皮
膜形成剤組成物を実施例１と同様に処理し、硬化して硬
化皮膜を形成した。Example 3 52.0 g of the fluorine-containing trichlorosilane used in Example 1 was used as a raw material for the organosilazane copolymer as component (a).
(8.9 x 10-2 mol), dichlorodimethylsilane 7.8g
(6.0 x 10-2 mol), and trichloromethylsilane 0.23g
The copolymer was synthesized in the same manner as in Example 1 except that (1.5×10 −3 mol) was used, and then a film-forming agent composition was obtained. The molar ratio of the units represented by the formula [1] and the units represented by the formula [2] was 59/41. Furthermore, the obtained film-forming agent composition was treated in the same manner as in Example 1 and cured to form a cured film.
【００１７】実施例４
（ａ）成分であるオルガノシラザン共重合体の原料とし
て、下記の化学式で表される含フッ素トリクロロシラン
Ｆ−［ＣＦ（ＣＦ３ ）ＣＦ ２ Ｏ］３ −ＣＦ（Ｃ
Ｆ３ ）ＣＨ ２ ＯＣＨ ２ ＣＨ２ ＣＨ２ Ｓｉ
Ｃｌ３
５５．９ｇ （６．８×１０−２モル） 、ジクロロ
ジメチルシラン ４．０ｇ （３．
１×１０−２モル） 、
および
トリクロロメチルシラン ０．１４ｇ
（１．０×１０−３モル）
を使用した以外は実施例１と同様にして該共重合体を合
成し、次いで、皮膜形成剤組成物を得た。なお、前記の
式［１］ で表される単位と式［２］ で表される単位
とのモル比は、６８／３２であった。さらに、得られた
皮膜形成剤組成物を実施例１と同様に処理し、硬化して
硬化皮膜を形成した。Example 4 Fluorine-containing trichlorosilane F-[CF(CF3)CF2O]3-CF(C
F3) CH2OCH2CH2CH2Si
Cl3 55.9g (6.8x10-2 mol), dichlorodimethylsilane 4.0g (3.
1x10-2 mol), and trichloromethylsilane 0.14g
The copolymer was synthesized in the same manner as in Example 1 except that (1.0×10 −3 mol) was used, and then a film-forming agent composition was obtained. The molar ratio of the units represented by the formula [1] and the units represented by the formula [2] was 68/32. Furthermore, the obtained film-forming agent composition was treated in the same manner as in Example 1 and cured to form a cured film.
【００１８】比較例１
オルガノシラザン共重合体の原料として、実施例１で使
用した含フッ素トリクロロシラン ６０．０ｇ（１．
０×１０−１モル） のみを使用した以外は実施例１と
同様にして合成し、次いで同様にして皮膜形成剤組成物
を得た。なお、前記の式［１］ で表される単位と式［
２］ で表される単位とのモル比は、 １００／０ で
あった。さらに、得られた皮膜形成剤組成物を実施例１
と同様に処理し、硬化して硬化皮膜を形成した。Comparative Example 1 As a raw material for the organosilazane copolymer, 60.0 g (1.
Synthesis was carried out in the same manner as in Example 1 except that only 0x10-1 mol) was used, and then a film-forming agent composition was obtained in the same manner. In addition, the unit expressed by the above formula [1] and the formula [
The molar ratio with the unit represented by 2] was 100/0. Furthermore, the obtained film forming agent composition was prepared in Example 1.
It was treated in the same manner as above and cured to form a cured film.
【００１９】比較例２
オルガノシラザン共重合体の原料として、トリクロロメ
チルシラン ５１．０ｇ（３．４×１０−１モル）
および、ジクロロジメチルシラン ９．０ｇ（７．０×
１０−２モル） を使用した以外は実施例１と同様にし
て合成し、次いで皮膜形成剤組成物を得た。なお、前記
の式［１］ で表される単位と式［２］ で表される単
位とのモル比は、０／１００であった。さらに、得られ
た皮膜形成剤組成物を実施例１と同様に処理し、硬化し
て硬化皮膜を形成した。Comparative Example 2 51.0 g (3.4×10 −1 mol) of trichloromethylsilane was used as a raw material for organosilazane copolymer.
and 9.0 g of dichlorodimethylsilane (7.0×
Synthesis was carried out in the same manner as in Example 1 except that 10-2 mol) was used, and then a film-forming agent composition was obtained. The molar ratio of the unit represented by the formula [1] and the unit represented by the formula [2] was 0/100. Furthermore, the obtained film-forming agent composition was treated in the same manner as in Example 1 and cured to form a cured film.
【００２０】以上の実施例１〜４及び比較例１〜２で得
られた硬化皮膜の撥水性および撥油性を調べるため、水
に対する接触角および落下角、並びにｎ−ヘキサデカン
に対する接触角および落下角を測定した。接触角の測定
においては、コンタクトアングルメーター（協和科学（
株）社製、商品名ＣＡ−Ａ）を用い、温度２５℃の条件
下で試料板上に、約６μｌ の水滴もしくはｎ−ヘキサ
デカン滴を滴下し、水滴もしくは油滴の２接点と試料板
との角度を測定した。また、落下角の測定においては、
静摩擦係数測定器（新東科学（株）社製）を用い、温度
２５℃の条件下、１６ｍｍ／ｓｅｃ． の速度で試料板
を上昇させ、水滴またはｎ−ヘキサデカン滴が落下開始
する角度を測定した。接触角がより大きな値を示し、か
つ落下角がより小さな値を示すほど、皮膜の撥水性は良
好であるといえる。測定した結果を表１に示す。[0020] In order to examine the water repellency and oil repellency of the cured films obtained in Examples 1 to 4 and Comparative Examples 1 to 2, the contact angle and fall angle with respect to water, and the contact angle and fall angle with respect to n-hexadecane were measured. was measured. When measuring the contact angle, a contact angle meter (Kyowa Scientific Co., Ltd.) is used.
Using a water droplet or n-hexadecane droplet of approximately 6 μl on the sample plate at a temperature of 25°C, the two contact points of the water droplet or oil droplet and the sample plate are connected. The angle was measured. In addition, when measuring the falling angle,
Using a static friction coefficient measuring device (manufactured by Shinto Kagaku Co., Ltd.), at a temperature of 25° C., at a rate of 16 mm/sec. The sample plate was raised at a speed of , and the angle at which a water droplet or n-hexadecane droplet started falling was measured. It can be said that the larger the contact angle and the smaller the falling angle, the better the water repellency of the film. The measured results are shown in Table 1.
【００２１】[0021]
【００２２】実施例１〜４においては、水滴および油滴
での接触角および落下角がともに良好な値であり、実施
例１〜４で得られた硬化皮膜が有する撥水性および撥油
性は満足できるレベルのものであることがわかる。比較
例１においては、水滴および油滴での落下角が大きな値
であった。また、比較例２においては、水滴および油滴
での接触角が小さな値であった。これらのことから、比
較例１〜２において得られた硬化皮膜が有する撥水性及
び撥油性は、バランスを欠いた、劣ったものであること
がわかる。In Examples 1 to 4, the contact angle and falling angle of water droplets and oil droplets were both good values, and the water repellency and oil repellency of the cured films obtained in Examples 1 to 4 were satisfactory. You can see that it is at a level that is possible. In Comparative Example 1, the falling angles of water droplets and oil droplets were large values. Furthermore, in Comparative Example 2, the contact angles with water droplets and oil droplets were small values. From these results, it can be seen that the water repellency and oil repellency of the cured films obtained in Comparative Examples 1 and 2 are unbalanced and inferior.
【００２３】[0023]
【発明の効果】本発明の皮膜形成剤組成物は、硬化して
得られる硬化物が良好な撥水性および撥油性を有するも
のである。Effects of the Invention The film-forming agent composition of the present invention is such that the cured product obtained by curing has good water and oil repellency.
Claims (2)
１ Ｑ）ａ Ｒ ２ ｂ Ｓｉ（ＮＲ ３ ） （４−
ａ−ｂ）／２ ［１］（式中、 Ｒ１ は同じ
でも異なってもよく、パーフロオロアルキル基もしくは
パーフルオロアルキルエーテル基を表し、 Ｒ２ およ
び Ｒ３ は同じでも異なってもよく、水素原子または
置換もしくは非置換の１価の炭化水素基を表し、Ｑは同
じでも異なってもよく、２価の有機基を表し、ａは１〜
３の整数を表し、ｂは０〜２の整数を表す。ただし、ａ
＋ｂは１〜３の整数である。）で表される単位、および
下記の一般単位式［２］：Ｒ ２ ｃ Ｓｉ（ＮＲ ３
） （４−ｃ）／２ ［２］（式中、 Ｒ２ およ
び Ｒ３ は前記のとおりであり、ｃは１〜３の整数を
表す。）で表される単位からなり、単位式［１］ と［
２］ のモル比が ［１］／［２］ ＝９５／５ 〜５
０／５０であるオルガノシラザン共重合体、（ｂ） 上
記 （ａ）成分のオルガノシラザン共重合体を溶解する
ことが可能な有機溶剤、以上の （ａ）および （ｂ）
成分を必須の構成成分として含む硬化性皮膜形成剤組成
物。[Claim 1] (a) The following general unit formula [1]: (R
1 Q) a R 2 b Si(NR 3 ) (4-
a-b)/2 [1] (wherein R1 may be the same or different and represent a perfluoroalkyl group or a perfluoroalkyl ether group, R2 and R3 may be the same or different and represent a hydrogen atom or a substituted or represents an unsubstituted monovalent hydrocarbon group, Q may be the same or different and represents a divalent organic group, and a is 1 to
represents an integer of 3, and b represents an integer of 0 to 2. However, a
+b is an integer from 1 to 3. ), and the following general unit formula [2]: R 2 c Si (NR 3
) (4-c)/2 [2] (In the formula, R2 and R3 are as described above, and c represents an integer of 1 to 3.) Consisting of a unit represented by the unit formula [1] and [
2] molar ratio of [1]/[2] =95/5 ~5
(b) an organic solvent capable of dissolving the organosilazane copolymer of component (a); (a) and (b) above;
A curable film-forming agent composition comprising the following as an essential component.
て得られる硬化皮膜。2. A cured film obtained by curing the curable film-forming composition according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10860091A JPH0686584B2 (en) | 1991-04-12 | 1991-04-12 | Film-forming agent composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10860091A JPH0686584B2 (en) | 1991-04-12 | 1991-04-12 | Film-forming agent composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04314771A true JPH04314771A (en) | 1992-11-05 |
| JPH0686584B2 JPH0686584B2 (en) | 1994-11-02 |
Family
ID=14488914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10860091A Expired - Lifetime JPH0686584B2 (en) | 1991-04-12 | 1991-04-12 | Film-forming agent composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0686584B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2766198A1 (en) * | 1997-07-15 | 1999-01-22 | Saint Gobain Vitrage | PLASTIC GLAZING, PARTICULARLY FOR THE AUTOMOTIVE AND METHOD FOR THE PRODUCTION THEREOF |
| EP1393874A1 (en) * | 2002-08-26 | 2004-03-03 | Shin-Etsu Chemical Co., Ltd. | Release agent for silicone rubber molding molds and molding method using said release agent |
| JP2012532207A (en) * | 2009-06-30 | 2012-12-13 | スリーエム イノベイティブ プロパティズ カンパニー | Compositions and methods for preparing curable organofluorine-modified polysilazanes, and polysilazanes prepared thereby |
-
1991
- 1991-04-12 JP JP10860091A patent/JPH0686584B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2766198A1 (en) * | 1997-07-15 | 1999-01-22 | Saint Gobain Vitrage | PLASTIC GLAZING, PARTICULARLY FOR THE AUTOMOTIVE AND METHOD FOR THE PRODUCTION THEREOF |
| WO1999003678A1 (en) * | 1997-07-15 | 1999-01-28 | Saint-Gobain Vitrage | Plastic glazing, in particular for motor car and method for making same |
| CZ297388B6 (en) * | 1997-07-15 | 2006-11-15 | Saint-Gobain Vitrage | Plastic windows, particularly for motor vehicles and process for producing thereof |
| EP1393874A1 (en) * | 2002-08-26 | 2004-03-03 | Shin-Etsu Chemical Co., Ltd. | Release agent for silicone rubber molding molds and molding method using said release agent |
| US6841596B2 (en) | 2002-08-26 | 2005-01-11 | Shin-Etsu Chemical Co., Ltd. | Release agent for silicone rubber molding molds and molding method |
| JP2012532207A (en) * | 2009-06-30 | 2012-12-13 | スリーエム イノベイティブ プロパティズ カンパニー | Compositions and methods for preparing curable organofluorine-modified polysilazanes, and polysilazanes prepared thereby |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0686584B2 (en) | 1994-11-02 |
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