JPH0557308B2 - - Google Patents
Info
- Publication number
- JPH0557308B2 JPH0557308B2 JP58192159A JP19215983A JPH0557308B2 JP H0557308 B2 JPH0557308 B2 JP H0557308B2 JP 58192159 A JP58192159 A JP 58192159A JP 19215983 A JP19215983 A JP 19215983A JP H0557308 B2 JPH0557308 B2 JP H0557308B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- parts
- polysiloxane
- hours
- hydrolyzable
- 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.)
- Expired - Lifetime
Links
- -1 polysiloxane Polymers 0.000 claims description 39
- 239000011248 coating agent Substances 0.000 claims description 38
- 229920001296 polysiloxane Polymers 0.000 claims description 37
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 31
- 229920002554 vinyl polymer Polymers 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000005083 alkoxyalkoxy group Chemical group 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000006482 condensation reaction Methods 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 30
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 21
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 18
- 238000000576 coating method Methods 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 14
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229920006163 vinyl copolymer Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 3
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- DBGSRZSKGVSXRK-UHFFFAOYSA-N 1-[2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]acetyl]-3,6-dihydro-2H-pyridine-4-carboxylic acid Chemical group C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CCC(=CC1)C(=O)O DBGSRZSKGVSXRK-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Paints Or Removers (AREA)
Description
本発明は、ビニル系重合体とポリシロキサンと
を化学的に複合させた新規な静電防止用コーテイ
ング剤の製造方法に関する。
合成樹脂の静電防止法としては、練り込み型と
塗布型に大別される。塗布型は、施工が容易で透
明体に対しても美観を損うことなく静電防止でき
る等の利点を有し、化学物質的には、界面活性剤
型とシロキサン型に大別できる。シロキサン型
は、日本特許第231959号に開示されているよう
に、界面活性剤型のものよりも耐水性、耐摩擦
性、耐溶剤性、耐候性が格段に優れた静電防止性
被膜を与える。しかし、従来知られたシロキサン
型静電防止用コーテイング剤から得られる被膜は
完全無機質のシリカ膜であつて、もろく、可撓性
に乏しいものであり、樹脂によつては密着性に問
題を生じている。また、膜厚が0.1〜0.5μm程度の
薄膜でなければ剥離してしまい、この結果膜面で
の干渉作用により虹の発色を引き起こし、透明体
に適用して問題となる場合がある。
本発明者は、このような従来のシロキサン型静
電防止用コーテイング剤の欠点を解決することを
目的として鋭意研究を行つた結果、特定の有機樹
脂類の利用がきわめて効果的であることを見出し
た。
すなわち、本発明は、平均組成式：
（式中、Ｘは加水分解性基とヒドロキシル基か
ら選ばれる基であつて、１分子中に少なくとも１
個の加水分解性基またはヒドロキシル基が存在す
る。また、ａは、０＜ａ＜４である。）
で表わされるポリシロキサンと、末端または側鎖
に加水分解性基と結合したシリル基を１分子中に
少なくとも１個有するシリル基含有ビニル系重合
体とを縮合反応させて静電防止性コーテイング剤
を製造する方法を提供する。
本発明に係る静電防止用コーテイング剤は、樹
脂面への密着性に優れるとともに、得られる塗膜
は静電防止性、透明性、可撓性、耐水性、耐溶剤
性、耐候性、耐熱性、難燃性等も優れ、かつ適当
な表面硬度を有し、更に厚塗りした場合にも何ら
不都合がなく、塗膜の干渉作用による虹発色が防
止できる実用上極めて望ましいものである。
本発明において用いられるポリシロキサンは、
例えば次のように調製することができる。すなわ
ち、一般式
（式中、Ｒは炭素数１〜８のアルキル基、アル
コキシアルキル基、アラルキル基、アリール基を
表わし、それらは同一でも２以上の異なつたもの
でもよく、ｎは正の整数を表わす。）
で表わされる有機シリケートまたは一般式
（式中、ｍは０及び正の整数を表わす。）
で表わされる塩素化ポリシロキサンまたは、その
他の加水分解性基と結合したシロキサン化合物
を、通常アルコール溶媒中で水と反応させること
により前記式（）の物質を容易に調製できる。
例えば、前記一般式（）で表わされる有機シリ
ケート、すなわち、けい酸エステルは、水と接触
すると、そのアルコキシ基（OR）が加水分解し
てヒドロキシル基（OH）となり、加水分解反応
が進行した場合には、他アルコキシ基（OR）も
ヒドロキシル基に変換される。従つて、一般式
（）で表わされる有機シリケートから誘導され
る加水分解生成物は、一般に、分子内にけい素原
子に結合した加水分解性アルコキシ基及び／又は
ヒドロキシル基の多数を含有する。また、一般式
（）で表わされる塩素化ポリシロキサンは、け
い素原子に結合した多くの塩素原子を有し、この
加水分解性基は水と反応して容易にヒドロキシル
基に置換される。従つて、この塩素化ポリシロキ
サンの加水分解生成物は、加水分解性塩素原子及
び／又はヒドロキシル基の多数を含有する。
これらのすべての加水分解生成物は、有機基、
例えば、アルキル基やアリール基が、直接けい素
原子に結合した、所謂、オルガノポリシロキサン
ではなく、そのような有機基は、酸素原子Ｏを介
して結合している加水分解性基であつて、一般
に、けい酸エステル、あるいは有機シリケートと
呼ばれるポリシロキサン類である。本発明におい
て前記（）のポリシロキサンとは、かかるシロ
キサン化合物類を包含する。
調製されたポリシロキサン溶液と反応させる他
方のビニル系重合体は、例えば次のようにして調
製される。
一般式 CH2＝CHCOOR1 （）
（式中、R1は水素または炭素数１〜８のアル
キル基）で表わされるアクリル酸誘導体およびま
たは、一般式
（式中、R2は水素または炭素数１〜８のアル
キル基）で表わされるメタクリル酸誘導体および
またはこれらと共重合可能な他のビニル系単量体
の重合体または共重合体を、一般式
（式中、R3は炭素数１〜10のアルキル基、ア
ラルキル基、アリール基より選ばれる１価の炭化
水素基、X′はハロゲン原子、アルコキシ基、ア
ルコキシアルコキシ基、アシロキシ基、アミノ
基、アミノキシ基から選ばれる加水分解性基を表
わし、ｂは０、１または２である。）
で表わされるケイ素上に加水分解性基を少なくと
も１個有するヒドロシランでヒドロシリル化して
もよいし、また前記重合性ビニル系単量体と一般
式
（式中、R6は、炭素数１〜10までのアルキル
基、アラルキル基、アリール基より選ばれる１価
の炭化水素基、R7は、炭素−ケイ素結合により
ケイ素と結合した重合性二重結合を有する有機残
基、X″はハロゲン原子、アルコキシ基、アルコ
キシアルコキシ基、アシロキシ基、アミノ基、ア
ミノキシ基から選ばれる加水分解性基を表わし、
ｃは０、１または２である。）で表わされる加水
分解性基をケイ素上に少なくとも１個有する重合
性ケイ素化合物とを共重合して合成される末端あ
るいは側鎖に加水分解性基と結合したシリル基を
１分子中に少なくとも１個有するシリル基含有ビ
ニル系重合体を調製することもできる。このよう
に調製されたシリル基含有ビニル系重合体は、前
記ポリシロキサン溶液と混合し、ポリシロキサン
のヒドロキシル基とビニル系重合体に結合したシ
リル基に結合した加水分解性基との間で縮合反応
させることにより、ポリシロキサンとビニル系重
合体とが強固なシロキサン結合によつて化学的に
複合された新規かつ性能の優れた静電防止用コー
テイング剤を容易に得ることができる。
本発明になる静電防止用コーテイング剤の製造
方法は、上記したように次の３段階の反応で行わ
れる。
ポリシロキサン溶液の合成
シリル基含有ビニル系重合体の合成
シリル基含有ビニル系重合体をポリシロキサ
ンの複合
以下に格段階に分けて本発明を更に詳しく説明
する。
１） ポリシロキサン溶液の合成
前記式（）で表わされる有機シリケートまた
は、前記式（）で表わされる塩素化ポリシロキ
サンあるいは他の加水分解性基と結合したシロキ
サン化合物をアルコール中で水と反応させること
によつて合成することができる。
使用されるケイ素化合物としては例えば、
SiCl4、Si（OMe）4、Si（OC2H5）4、Si（OC3H7）4、
Si（OC4H9）4、（ACO）4Si、（
The present invention relates to a method for producing a novel antistatic coating agent, which is a chemical compound of a vinyl polymer and a polysiloxane. Antistatic methods for synthetic resins are broadly divided into kneading type and coating type. The coating type has the advantage of being easy to apply and can prevent static electricity even on transparent objects without impairing its appearance, and can be roughly divided into surfactant type and siloxane type in terms of chemical substances. The siloxane type, as disclosed in Japanese Patent No. 231959, provides an antistatic coating with much better water resistance, abrasion resistance, solvent resistance, and weather resistance than the surfactant type. . However, the film obtained from conventionally known siloxane-type antistatic coating agents is a completely inorganic silica film, which is brittle and has poor flexibility, and depending on the resin, there may be problems with adhesion. ing. Moreover, if the film is not thin enough to have a thickness of about 0.1 to 0.5 μm, it will peel off, resulting in rainbow coloring due to interference on the film surface, which may pose a problem when applied to transparent objects. As a result of intensive research aimed at solving the drawbacks of conventional siloxane-type antistatic coating agents, the present inventor discovered that the use of specific organic resins is extremely effective. Ta. That is, the present invention has an average compositional formula: (In the formula, X is a group selected from a hydrolyzable group and a hydroxyl group, and at least 1 group per molecule
There are several hydrolyzable groups or hydroxyl groups present. Further, a is 0<a<4. ) and a silyl group-containing vinyl polymer having at least one silyl group in one molecule bonded to a hydrolyzable group at the terminal or side chain to form an antistatic coating agent. Provides a method for manufacturing. The antistatic coating agent of the present invention has excellent adhesion to resin surfaces, and the resulting coating film has antistatic properties, transparency, flexibility, water resistance, solvent resistance, weather resistance, and heat resistance. It has excellent properties such as hardness and flame retardancy, and has an appropriate surface hardness.Furthermore, it causes no problems even when applied thickly, and is extremely desirable from a practical standpoint because it can prevent rainbow coloration due to the interference effect of the coating film. The polysiloxane used in the present invention is
For example, it can be prepared as follows. That is, the general formula (In the formula, R represents an alkyl group, an alkoxyalkyl group, an aralkyl group, or an aryl group having 1 to 8 carbon atoms, and they may be the same or 2 or more different groups, and n represents a positive integer.) Organosilicate represented or general formula (In the formula, m represents 0 or a positive integer.) By reacting a chlorinated polysiloxane represented by the formula or a siloxane compound bonded with other hydrolyzable groups with water in an alcohol solvent, the formula The substances in () can be easily prepared.
For example, when an organic silicate represented by the above general formula (), that is, a silicate ester, comes into contact with water, its alkoxy group (OR) is hydrolyzed to become a hydroxyl group (OH), and the hydrolysis reaction progresses. In addition, other alkoxy groups (OR) are also converted to hydroxyl groups. Therefore, hydrolysis products derived from organosilicates of the general formula () generally contain in the molecule a large number of hydrolyzable alkoxy groups and/or hydroxyl groups bonded to silicon atoms. Further, the chlorinated polysiloxane represented by the general formula () has many chlorine atoms bonded to silicon atoms, and these hydrolyzable groups react with water and are easily substituted with hydroxyl groups. The hydrolysis product of this chlorinated polysiloxane therefore contains a large number of hydrolyzable chlorine atoms and/or hydroxyl groups. All these hydrolysis products contain organic groups,
For example, instead of a so-called organopolysiloxane in which an alkyl group or an aryl group is directly bonded to a silicon atom, such an organic group is a hydrolyzable group in which the alkyl group or aryl group is bonded via an oxygen atom O. Generally, they are polysiloxanes called silicate esters or organic silicates. In the present invention, the above-mentioned polysiloxane () includes such siloxane compounds. The other vinyl polymer to be reacted with the prepared polysiloxane solution is prepared, for example, as follows. Acrylic acid derivatives represented by the general formula CH 2 =CHCOOR 1 () (in the formula, R 1 is hydrogen or an alkyl group having 1 to 8 carbon atoms) and/or the general formula (In the formula, R 2 is hydrogen or an alkyl group having 1 to 8 carbon atoms) A polymer or copolymer of a methacrylic acid derivative represented by the formula (In the formula, R 3 is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aralkyl group, and an aryl group, and X' is a halogen atom, an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an amino group, It represents a hydrolyzable group selected from aminoxy groups, and b is 0, 1 or 2.) Hydrosilane having at least one hydrolyzable group on silicon represented by Polyvinyl monomer and general formula (In the formula, R 6 is a monovalent hydrocarbon group selected from an alkyl group, an aralkyl group, and an aryl group having 1 to 10 carbon atoms, and R 7 is a polymerizable double bonded to silicon through a carbon-silicon bond. The organic residue having a bond, X'' represents a hydrolyzable group selected from a halogen atom, an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an amino group, and an aminoxy group,
c is 0, 1 or 2. ) Synthesized by copolymerizing with a polymerizable silicon compound having at least one hydrolyzable group on silicon, at least one silyl group in one molecule is synthesized by copolymerizing with a polymerizable silicon compound having at least one hydrolyzable group on silicon. It is also possible to prepare vinyl polymers containing silyl groups. The silyl group-containing vinyl polymer thus prepared is mixed with the polysiloxane solution, and condensation occurs between the hydroxyl group of the polysiloxane and the hydrolyzable group bonded to the silyl group bonded to the vinyl polymer. By reacting, it is possible to easily obtain a novel antistatic coating agent with excellent performance, in which polysiloxane and vinyl polymer are chemically composited by strong siloxane bonds. The method for producing the antistatic coating agent of the present invention is carried out in the following three steps as described above. Synthesis of polysiloxane solution Synthesis of silyl group-containing vinyl polymer Composite of silyl group-containing vinyl polymer with polysiloxane The present invention will be explained in more detail below by dividing it into specific stages. 1) Synthesis of polysiloxane solution Reacting an organic silicate represented by the above formula (), a chlorinated polysiloxane represented by the above formula (), or a siloxane compound bonded to another hydrolyzable group with water in alcohol. It can be synthesized by Examples of the silicon compounds used include:
SiCl 4 , Si(OMe) 4 , Si(OC 2 H 5 ) 4 , Si(OC 3 H 7 ) 4 ,
Si ( OC4H9 ) 4 ,(ACO) 4Si ,(
参考例 １
100℃に加熱した90部のトルエン中にMMA100
部、AIBN3部、ｎ−ドデシルメルカプタン２部
を溶かした溶液を６時間で滴下し、後２時間反応
させて分子量８，000のMMA重合体を得た。
得られたMMA重合体30部にメチルジメトキシ
シラン2.5部、塩化白金酸0.0005部をイソプロパ
ノールに溶解した液を加え、90℃の温度で密封
し、８時間反応させてシリル基含有MMA重合体
を得た。
参考例 ２
100℃に加熱した90部のトルエン中にメタクリ
ル酸ブチル（以下BMA）100部、AIBN3部、ｎ
−ドデシルメルカプタン２部を溶かした溶液を６
時間で滴下し、後２時間反応させ、分子量5000の
BMA重合体を得た。
次いで得られたBMA重合体30部にメチルジメ
トキシシラン2.5部、塩化白金酸0.0005部をイソ
プロパノールに溶解した液を加え、90℃の温度で
密封し、８時間反応させてシリル基含有BMA重
合体を得た。
参考例 ３
100℃に加熱した90部のトルエン中にスチレン
（以下ST）15部、MMA25部、BMA60部、
AIBN3部、ｎ−ドデシルメルカプタン２部を溶
かした溶液を６時間で滴下し、後２時間反応させ
分子量8000のビニル系共重合体を得た。
得られた共重合体30部にメチルジメトキシシラ
ン2.5部、塩化白金酸0.0005部をイソプロパノー
ルに溶解した溶液を加え、90℃の温度で密封し８
時間反応させてシリル基含有ビニル系共重合体を
得た。
参考例 ４
100℃に加熱した45部のキシレン中にMMA150
部、γ−メタクリルオキシプロピルトリメトキシ
シラン（以下TSMA）45部、AIBN10部の混合
液を５時間にわたつて滴下し、その後２時間反応
させて、分子量8000ののシリル基含有ビニル系重
合体を得た。
参考例 ５
100℃に加熱した45部のキシレン中にBMA150
部、TSMA45部、AIBN10部の混合液を５時間
かけて滴下し、その後２時間反応させて、分子量
5000のシリル基含有ビニル系共重合体を得た。
参考例 ６
100℃に加熱した45部のキシレン中にST15部、
MMA25部、BMA40部、TSMA25部、AIBN5部
の混合液を５時間かけて滴下し、その後２時間反
応させて、分子量5000のシリル基含有ビニル系共
重合体を得た。
〔ポリシロキサンの製造〕
参考例 ７
イソプロパノール100部に、水25部、オルトエ
チルシリケート35部、濃塩酸0.5部を混合し、60
℃の温度で５時間反応させてポリシロキサン溶液
を得た。
実施例 １
参考例１で製造したシリル基含有MMA重合体
10部に参考例７で得たポリシロキサン溶液50部を
加え、室温で30分間撹拌しながら反応させた。こ
れに酢酸エチル30部、ｎ−ブタノール10部を加え
たのち、24時間放置して静電防止用コーテイング
剤を得た。
実施例 ２
参考例２で得られたシリル基含有BMA重合体
10部に参考例７で調製されたポリシロキサン溶液
50部を加え室温で30分間撹拌し反応させた。これ
に酢酸エチル20部、ｎ−ブタノール10部、シクロ
ヘキサノン10部を加えたのち、24時間放置して静
電防止用コーテイング剤を得た。
実施例 ３
参考例３で調製したシリル基含有ビニル系共重
合体10部に参考例７で得られたポリシロキサン溶
液50部を加え室温で30分間撹拌下に反応させた。
次いで、これに酢酸エチル20部、ｎ−ブタール10
部、シクロヘキサン10部を加え、24時間そのまゝ
放置して静電防止用コーテイング剤を得た。
実施例 ４
参考例４で得たシリル基含有ビニル系重合体10
部に参考例７で得られたポリシロキサン溶液50部
を加え室温で30分間撹拌下に反応させた。これに
酢酸エチル30部ｎ−ブタノール10部を加え、24時
間そのまゝ放置して静電防止用コーテイング剤を
得た。
実施例 ５
参考例５で調製したシリル基含有ビニル系共重
合体10部に参考例７で得られたポリシロキサン溶
液50部を加え室温で30分間撹拌しながら反応させ
た。これに酢酸エチル20部、ｎ−ブタノール10
部、シクロヘキサン10部を加え24時間放置して、
静電防止用コーテイング剤を得た。
比較例 １
参考例１の工程中で調製された分子量約8000の
MMA重合体10部に参考例７で得たポリシロキサ
ン溶液50部を加え室温で30分間撹拌した。これに
酢酸エチル30部、ｎ−ブタノール10部を加え24時
間放置して比較用の液を得た。
比較例 ２
参考例２の工程中で調製されたBMA重合体10
部に参考例７で調製されたポリシロキサン溶液50
部を加え、室温で30分間撹拌したのち、これに酢
酸エチル20部、ｎ−ブタノール10部、シクロヘキ
サノン10部を加え、そのまま24時間放置して比較
用液を得た。
比較例 ３
参考例３で調製されたシリル基含有ビニル系重
合体10部にイソプロパノール50部を加え室温で30
分間撹拌した。これに酢酸エチル20部、ｎ−ブタ
ノール10部、シクロヘキサノン10部を加え、24時
間放置して比較用液を得た。
比較例 ４
参考例４で調製したシリル基含有ビニル系共重
合体10部にイソプロパノール50部を加え室温で30
分間撹拌した。これに酢酸エチル30部、ｎ−ブタ
ノール10部を加え、24時間放置して比較用液を得
た。
比較例 ５
参考例５で調製したシリル基含有のビル系重合
体10部にイソプロパノール50部を加え、室温で30
分間撹拌したのち、これに酢酸エチル30部、ｎ−
ブタノール10部を加えて24時間放置し比較用液を
得た。
比較例 ６
参考例６で調製したシリル基含有ビニル系共重
合体10部にイソプロパノール50部を加え、室温で
30分間撹拌した。これに酢酸エチル20部、ｎ−ブ
タノール10部、シクロヘキサノン10部を加えて24
時間放置し、比較用液を得た。
比較例 ７
参考例７で調製したポリシロキサン溶液50部に
酢酸エチル30部、ｎ−ブタノール20部、シクロヘ
キサノン10部を混合し、24時間放置して比較用液
を得た。
上記実施例および比較例で得られた各静電防止
用コーテイング液を用いて、ポリメチルメタクリ
レートのキヤステイング板およびポリ塩化ビニル
の押出成型板に浸漬塗布し、24時間放置して形成
された塗膜の性能と静電防止効果をしらべた。そ
れらの測定結果を第１表にまとめて示した。
なお、塗膜の硬度、密着性および表面抵抗の測
定はそれぞれ次の方法によつた。
(イ) 鉛筆硬度
JIS K5400に準じて行つた。また装置は、Ｕ
−Ｆひつかき式鉛筆硬度計（上島製作所製）を
用いた。
(ロ) 密着性
セロハンテープ（商品名 セロテープ ニチ
バン株式会社製）を強くはりつけ、90度方向に
急激にはがして塗膜の剥離の有無を調べた。そ
の際、全く剥離がなかつたものを〇、剥離がみ
られたものを×で表示した。
(ハ) 表面抵抗値
高−抵抗計、スタツクTR−３型（東京電子
株式会社製）を用いて測定した。静電防止効果
は１×1012Ω（測定機の上限）を目安とし、こ
れ以上では静電防止効果はないと判定される。
Reference example 1 MMA100 in 90 parts of toluene heated to 100℃
A solution containing 1 part of AIBN, 3 parts of AIBN, and 2 parts of n-dodecylmercaptan was added dropwise over 6 hours, and the reaction was continued for another 2 hours to obtain an MMA polymer with a molecular weight of 8,000. A solution of 2.5 parts of methyldimethoxysilane and 0.0005 parts of chloroplatinic acid dissolved in isopropanol was added to 30 parts of the obtained MMA polymer, sealed at a temperature of 90°C, and reacted for 8 hours to obtain a silyl group-containing MMA polymer. Ta. Reference example 2 100 parts of butyl methacrylate (BMA), 3 parts of AIBN, n
- 6 parts of a solution of 2 parts of dodecyl mercaptan
After 2 hours of reaction, the molecular weight was 5000.
A BMA polymer was obtained. Next, a solution of 2.5 parts of methyldimethoxysilane and 0.0005 parts of chloroplatinic acid dissolved in isopropanol was added to 30 parts of the obtained BMA polymer, sealed at a temperature of 90°C, and reacted for 8 hours to form a silyl group-containing BMA polymer. Obtained. Reference example 3 In 90 parts of toluene heated to 100℃, 15 parts of styrene (ST), 25 parts of MMA, 60 parts of BMA,
A solution containing 3 parts of AIBN and 2 parts of n-dodecylmercaptan was added dropwise over 6 hours, and the reaction was allowed to continue for another 2 hours to obtain a vinyl copolymer with a molecular weight of 8,000. A solution of 2.5 parts of methyldimethoxysilane and 0.0005 parts of chloroplatinic acid dissolved in isopropanol was added to 30 parts of the obtained copolymer, and the mixture was sealed at 90°C.
A silyl group-containing vinyl copolymer was obtained by reacting for a period of time. Reference example 4 MMA150 in 45 parts of xylene heated to 100℃
A mixture of 45 parts of γ-methacryloxypropyltrimethoxysilane (TSMA) and 10 parts of AIBN was added dropwise over 5 hours, and then reacted for 2 hours to form a silyl group-containing vinyl polymer with a molecular weight of 8000. Obtained. Reference example 5 BMA150 in 45 parts of xylene heated to 100℃
A mixture of 10 parts of TSMA, 45 parts of TSMA, and 10 parts of AIBN was added dropwise over 5 hours, and then reacted for 2 hours to determine the molecular weight.
A vinyl copolymer containing 5000 silyl groups was obtained. Reference example 6 15 parts of ST in 45 parts of xylene heated to 100℃,
A mixed solution of 25 parts of MMA, 40 parts of BMA, 25 parts of TSMA, and 5 parts of AIBN was added dropwise over a period of 5 hours, and then reacted for 2 hours to obtain a silyl group-containing vinyl copolymer having a molecular weight of 5000. [Manufacture of polysiloxane] Reference example 7 100 parts of isopropanol, 25 parts of water, 35 parts of orthoethyl silicate, and 0.5 part of concentrated hydrochloric acid were mixed, and 60 parts of
A polysiloxane solution was obtained by reacting at a temperature of .degree. C. for 5 hours. Example 1 Silyl group-containing MMA polymer produced in Reference Example 1
50 parts of the polysiloxane solution obtained in Reference Example 7 was added to 10 parts, and the mixture was reacted with stirring at room temperature for 30 minutes. After adding 30 parts of ethyl acetate and 10 parts of n-butanol, the mixture was left to stand for 24 hours to obtain an antistatic coating agent. Example 2 Silyl group-containing BMA polymer obtained in Reference Example 2
10 parts of the polysiloxane solution prepared in Reference Example 7
50 parts were added and stirred at room temperature for 30 minutes to react. After adding 20 parts of ethyl acetate, 10 parts of n-butanol, and 10 parts of cyclohexanone, the mixture was left to stand for 24 hours to obtain an antistatic coating agent. Example 3 50 parts of the polysiloxane solution obtained in Reference Example 7 was added to 10 parts of the silyl group-containing vinyl copolymer prepared in Reference Example 3, and reacted with stirring at room temperature for 30 minutes.
Next, 20 parts of ethyl acetate and 10 parts of n-butal were added to this.
10 parts of cyclohexane were added thereto, and the mixture was left to stand for 24 hours to obtain an antistatic coating agent. Example 4 Silyl group-containing vinyl polymer 10 obtained in Reference Example 4
50 parts of the polysiloxane solution obtained in Reference Example 7 was added to the mixture, and the mixture was allowed to react at room temperature for 30 minutes with stirring. To this was added 30 parts of ethyl acetate and 10 parts of n-butanol, and the mixture was left to stand for 24 hours to obtain an antistatic coating agent. Example 5 50 parts of the polysiloxane solution obtained in Reference Example 7 was added to 10 parts of the silyl group-containing vinyl copolymer prepared in Reference Example 5, and reacted with stirring at room temperature for 30 minutes. To this, 20 parts of ethyl acetate, 10 parts of n-butanol
1 part and 10 parts of cyclohexane were added and left to stand for 24 hours.
An antistatic coating agent was obtained. Comparative Example 1 A sample with a molecular weight of about 8000 prepared during the process of Reference Example 1
50 parts of the polysiloxane solution obtained in Reference Example 7 was added to 10 parts of the MMA polymer, and the mixture was stirred at room temperature for 30 minutes. To this, 30 parts of ethyl acetate and 10 parts of n-butanol were added and left to stand for 24 hours to obtain a comparative solution. Comparative Example 2 BMA polymer 10 prepared during the process of Reference Example 2
Part 50 of the polysiloxane solution prepared in Reference Example 7
After stirring at room temperature for 30 minutes, 20 parts of ethyl acetate, 10 parts of n-butanol, and 10 parts of cyclohexanone were added thereto, and the mixture was left to stand for 24 hours to obtain a comparative solution. Comparative Example 3 50 parts of isopropanol was added to 10 parts of the silyl group-containing vinyl polymer prepared in Reference Example 3, and the mixture was heated for 30 minutes at room temperature.
Stir for a minute. To this were added 20 parts of ethyl acetate, 10 parts of n-butanol, and 10 parts of cyclohexanone, and the mixture was left to stand for 24 hours to obtain a comparative solution. Comparative Example 4 50 parts of isopropanol was added to 10 parts of the silyl group-containing vinyl copolymer prepared in Reference Example 4, and the mixture was heated for 30 minutes at room temperature.
Stir for a minute. To this, 30 parts of ethyl acetate and 10 parts of n-butanol were added and left to stand for 24 hours to obtain a comparative solution. Comparative Example 5 50 parts of isopropanol was added to 10 parts of the silyl group-containing building polymer prepared in Reference Example 5, and 30 parts of isopropanol was added at room temperature.
After stirring for a minute, 30 parts of ethyl acetate and n-
10 parts of butanol was added and left to stand for 24 hours to obtain a comparative solution. Comparative Example 6 50 parts of isopropanol was added to 10 parts of the silyl group-containing vinyl copolymer prepared in Reference Example 6, and the mixture was heated at room temperature.
Stir for 30 minutes. Add 20 parts of ethyl acetate, 10 parts of n-butanol, and 10 parts of cyclohexanone to 24
A comparison solution was obtained by standing for a period of time. Comparative Example 7 30 parts of ethyl acetate, 20 parts of n-butanol, and 10 parts of cyclohexanone were mixed with 50 parts of the polysiloxane solution prepared in Reference Example 7, and the mixture was left to stand for 24 hours to obtain a comparative solution. The antistatic coating liquids obtained in the above Examples and Comparative Examples were applied by dip coating to a polymethyl methacrylate casting board and a polyvinyl chloride extrusion molded board, and the resulting coating was left to stand for 24 hours. The membrane's performance and antistatic effect were investigated. The measurement results are summarized in Table 1. The hardness, adhesion, and surface resistance of the coating film were measured by the following methods. (a) Pencil hardness: Conformed to JIS K5400. Also, the device is
-F hit type pencil hardness tester (manufactured by Uejima Seisakusho) was used. (B) Adhesion Cellophane tape (trade name: Cellotape, manufactured by Nichiban Co., Ltd.) was strongly applied and peeled off rapidly in a 90-degree direction to check for peeling of the paint film. At that time, cases in which there was no peeling at all were marked as ○, and cases in which peeling was observed were marked as ×. (c) Surface resistance value Measured using a high-resistance meter, Stack TR-3 model (manufactured by Tokyo Electronics Co., Ltd.). The antistatic effect is set at 1×10 12 Ω (the upper limit of the measuring device), and it is determined that there is no antistatic effect above this value.
【表】
上表より、実施例１〜３、比較例１〜３はヒド
ロシリル化法により合成されたシリル基含有ビニ
ル系重合体を用いた実施例およびその比較例であ
つて、実施例１〜３は表面抵抗値が低く、良好な
静電防止性を有するとともに、ポリ塩化ビニル板
に対しても密着性に優れ、鉛筆硬度も十分の値を
有することがわかる。これに対し、本発明外のコ
ーテイング剤、すなわち、ヒドロシリル化により
シリル基が導入されていないビニル系重合体とポ
リシロキサン溶液を混合した比較例１、２では、
ビニル系重合体とポリシロキサンとが化学的に結
合されず、単なる物理混合のみであるため、実施
例の如き効果が発揮されていない。また、シリル
基含有ビニル系重合体だけで、ポリシロキサン溶
液を混合していない比較例３では、密着性には優
れるものの、静電防止効果はまつたく現われてい
ない。
実施例４〜６及び比較例４〜６は、共重合法に
よつて合成されたシリル基含有ビニル系重合体を
用いた具体例であつて、ポリシロキサンの混用の
有無に基く実施例および比較例である。実施例４
〜６のコーテイング剤から得られる塗膜は、実施
例１〜３とほゞ同様の効果を発揮しているのに対
し、ポリシロキサンを配合していない比較例４〜
６は、静電防止性を持つていないことがわかる。
比較例７は、ポリシロキサン溶液のみからな
り、シリル基含有ビル系重合体を混合していない
もので、静電防止性には優れるポリ塩化ビニル板
への密着性は著るしく劣つている。
以上の如く、シリル基含有ビニル系重合体とポ
リシロキサン溶液とを混合し、縮合反応によつて
化学的に両者が複合されることにより、目的とす
る物性が始めて具現されることは明白である。
添付図面第１図は、前記実施例３および５のコ
ーテイング剤について、調製後の放置時間とその
塗布膜の表面抵抗値との関係を示すグラフであ
る。なお、測定は所定時間放置したコーテイング
剤を塩化ビニル樹脂板に塗布し、24時間経過後に
行つたもので、実線が実施例３、点線が実施例５
である。グラフよりシリカ基含有ビニル系重合体
とポリシロキサンとが時間の経過とともに確実に
化学結合によつて複合して静電防止効果が発揮さ
れることがわかる。両実施例の場合の触媒量で
は、いずれも室温での反応時間は５時間以上好ま
しくは10時間以上を要することがグラフより理解
できる。
本発明になる静電防止用コーテイング剤は、従
来行なわれている、浸漬塗布、刷毛塗り、スピン
ナー塗布、スプレー塗布等いずれの方法を用いて
塗布することもできる。通常要求される表面抵抗
値の範囲は、1010Ωオーダー以下望ましくは109
〜107Ωオーダー以下であるが、本発明に係る静
電防止用コーテイング剤より得られる膜の表面抵
抗値は、108〜109Ωオーダーであり、十分な静電
防止性を有していることがわかる。樹脂面への密
着性は通常実施されているセロテープ試験法で評
価したが、従来のシロキサンタイプでは、簡単に
剥離してしまう塩化ビニール樹脂表面へも極めて
強固な被膜が形成されている。これらの性質の発
現は、化学的に複合されたビニル系ポリマーとポ
リシロキサンとが、ある種の高分子界面活性剤の
如く作用し、樹脂面に対しては親油性のビニル系
重合体が、また湿分を含んだ大気側には親水性の
ポリシロキサンがそれぞれ向するためと考えられ
る。この被膜は高分子のみで構成されているた
め、耐水性、耐溶剤性に優れるとともにメタアク
リル酸メチルの様な耐候性に優れたモノマーを主
体としたビニル系重合体を有機骨格とすれば耐候
性にも優れた塗膜が得られる。シリカ成分の表面
配向により、表面硬度も4H〜2Hと高く、難燃性
も付与される。更に、本発明に係るコーテイング
剤は厚塗りも出来、干渉作用による虹発色を生ぜ
ず、透明品に対しても外観を損うことなく処理で
きるなど種々の利点を有している。[Table] From the above table, Examples 1 to 3 and Comparative Examples 1 to 3 are examples and comparative examples using a silyl group-containing vinyl polymer synthesized by a hydrosilylation method. It can be seen that Sample No. 3 has a low surface resistance value, good antistatic properties, excellent adhesion to polyvinyl chloride plates, and sufficient pencil hardness. On the other hand, in Comparative Examples 1 and 2, in which a coating agent other than the present invention, that is, a vinyl polymer in which no silyl group has been introduced by hydrosilylation, and a polysiloxane solution were mixed,
Since the vinyl polymer and polysiloxane are not chemically bonded and are merely physically mixed, the effects as in the examples are not exhibited. Further, in Comparative Example 3, which contained only a silyl group-containing vinyl polymer and did not mix a polysiloxane solution, although the adhesion was excellent, the antistatic effect was not clearly exhibited. Examples 4 to 6 and Comparative Examples 4 to 6 are specific examples using a silyl group-containing vinyl polymer synthesized by a copolymerization method, and are examples and comparisons based on the presence or absence of mixed use of polysiloxane. This is an example. Example 4
The coating films obtained from the coating agents of Examples 1 to 6 exhibited almost the same effects as those of Examples 1 to 3, whereas Comparative Examples 4 to 6, which did not contain polysiloxane,
It can be seen that No. 6 does not have antistatic properties. Comparative Example 7 consisted of only a polysiloxane solution without mixing a silyl group-containing building polymer, and its adhesion to a polyvinyl chloride plate, which has excellent antistatic properties, was significantly poor. As described above, it is clear that the desired physical properties can only be realized by mixing a silyl group-containing vinyl polymer and a polysiloxane solution and chemically combining them through a condensation reaction. . FIG. 1 of the accompanying drawings is a graph showing the relationship between the standing time after preparation and the surface resistance value of the coating film for the coating agents of Examples 3 and 5. The measurements were made after 24 hours had elapsed after applying the coating agent to a vinyl chloride resin plate after leaving it for a predetermined period of time.The solid line indicates Example 3, and the dotted line indicates Example 5.
It is. From the graph, it can be seen that the silica group-containing vinyl polymer and polysiloxane are reliably combined through chemical bonds over time, and the antistatic effect is exhibited. It can be seen from the graph that with the amount of catalyst used in both Examples, the reaction time at room temperature is 5 hours or more, preferably 10 hours or more. The antistatic coating agent of the present invention can be applied using any of the conventional methods such as dip coating, brush coating, spinner coating, and spray coating. The normally required range of surface resistance is on the order of 10 10 Ω or less, preferably 10 9
However, the surface resistance value of the film obtained from the antistatic coating agent according to the present invention is on the order of 10 8 to 10 9 Ω, indicating that it has sufficient antistatic properties. I know that there is. Adhesion to resin surfaces was evaluated using the commonly used Cellotape test method, and conventional siloxane types form an extremely strong film even on vinyl chloride resin surfaces, which are easily peeled off. The manifestation of these properties is that the chemically composited vinyl polymer and polysiloxane act like a kind of polymeric surfactant, and the lipophilic vinyl polymer acts on the resin surface. It is also believed that this is because the hydrophilic polysiloxane is directed toward the atmosphere containing moisture. Since this coating is composed only of polymers, it has excellent water resistance and solvent resistance, and if the organic skeleton is a vinyl polymer based on a monomer with excellent weather resistance such as methyl methacrylate, it is weather resistant. A coating film with excellent properties can be obtained. Due to the surface orientation of the silica component, the surface hardness is as high as 4H to 2H, and flame retardancy is also imparted. Furthermore, the coating agent according to the present invention has various advantages, such as being able to be applied thickly, not causing iridescence due to interference, and being able to treat transparent items without impairing their appearance.
第１図は、本発明に係る静電防止用コーテイン
グ剤の調製後の放置時間と塗膜の抵抗値の関係を
示すグラフである。実線は実施例３、点線は実施
例５のコーテイング剤についてのものである。
FIG. 1 is a graph showing the relationship between the standing time after preparation of the antistatic coating agent according to the present invention and the resistance value of the coating film. The solid line is for the coating agent of Example 3, and the dotted line is for the coating agent of Example 5.
Claims (1)
リル基を１分子中に少なくとも１個有するシリル
基含有ビニル系重合体と、 平均組成比： （式中、Ｘは加水分解性基とヒドロキシル基か
ら選ばれる基であつて、１分子中に少なくとも１
個の加水分解性基またはヒドロキシル基が存在す
る。また、ａは、０＜ａ＜４である。） で表わされるポリシロキサンとを縮合反応させる
ことを特徴とする静電防止性コーテイング剤の製
造方法。 ２ 加水分解性基が、ハロゲン原子，アルコキシ
基，アルコキシアルコキシ基，アシロキシ基，ア
ミノ基またはアミノキシ基である特許請求の範囲
第１項に記載の方法。[Scope of Claims] 1. A silyl group-containing vinyl polymer having at least one silyl group in one molecule bonded to a hydrolyzable group at the terminal or side chain, and the average composition ratio: (In the formula, X is a group selected from a hydrolyzable group and a hydroxyl group, and at least 1 group per molecule
There are several hydrolyzable groups or hydroxyl groups present. Further, a is 0<a<4. ) A method for producing an antistatic coating agent, characterized by carrying out a condensation reaction with a polysiloxane represented by: 2. The method according to claim 1, wherein the hydrolyzable group is a halogen atom, an alkoxy group, an alkoxyalkoxy group, an acyloxy group, an amino group, or an aminoxy group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19215983A JPS6084366A (en) | 1983-10-14 | 1983-10-14 | Antistatic coating agent and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19215983A JPS6084366A (en) | 1983-10-14 | 1983-10-14 | Antistatic coating agent and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6084366A JPS6084366A (en) | 1985-05-13 |
| JPH0557308B2 true JPH0557308B2 (en) | 1993-08-23 |
Family
ID=16286672
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19215983A Granted JPS6084366A (en) | 1983-10-14 | 1983-10-14 | Antistatic coating agent and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6084366A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2570574C2 (en) * | 2010-04-23 | 2015-12-10 | ХЕНКЕЛЬ АйПи ЭНД ХОЛДИНГ ГМБХ | Silicone-acrylic copolymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5019900A (en) * | 1973-06-21 | 1975-03-03 | ||
| JPS5592737A (en) * | 1978-12-30 | 1980-07-14 | Bayer Ag | Graft polymer containing silicon and its manufacture |
| JPS59202225A (en) * | 1983-04-29 | 1984-11-16 | Kuraray Co Ltd | Production of polyvinyl alcohol block copolymer |
| JPS59202224A (en) * | 1983-04-29 | 1984-11-16 | Kuraray Co Ltd | Production of block copolymer |
-
1983
- 1983-10-14 JP JP19215983A patent/JPS6084366A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5019900A (en) * | 1973-06-21 | 1975-03-03 | ||
| JPS5592737A (en) * | 1978-12-30 | 1980-07-14 | Bayer Ag | Graft polymer containing silicon and its manufacture |
| JPS59202225A (en) * | 1983-04-29 | 1984-11-16 | Kuraray Co Ltd | Production of polyvinyl alcohol block copolymer |
| JPS59202224A (en) * | 1983-04-29 | 1984-11-16 | Kuraray Co Ltd | Production of block copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6084366A (en) | 1985-05-13 |
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