JPH0426630B2 - - Google Patents
Info
- Publication number
- JPH0426630B2 JPH0426630B2 JP61118547A JP11854786A JPH0426630B2 JP H0426630 B2 JPH0426630 B2 JP H0426630B2 JP 61118547 A JP61118547 A JP 61118547A JP 11854786 A JP11854786 A JP 11854786A JP H0426630 B2 JPH0426630 B2 JP H0426630B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- coating
- film
- dimethyldiethoxysilane
- 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
- 238000000576 coating method Methods 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 239000008119 colloidal silica Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 33
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- -1 silicon alkoxide Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 229920005645 diorganopolysiloxane polymer Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101000856234 Clostridium acetobutylicum (strain ATCC 824 / DSM 792 / JCM 1419 / LMG 5710 / VKM B-1787) Butyrate-acetoacetate CoA-transferase subunit A Proteins 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Silicon Polymers (AREA)
Description
（技術分野）
本発明は、セメント基板や木材のように比較的
寸法変化の大きな基材に、深み感のある（厚膜化
できる）高硬度、高耐久なコーテイングを行いう
るコーテイング材の製法に関するものである。
（背景技術）
セメント基板や木材の上に、汚染防止等の目的
でコーテイングを施すこと行われている。その
際、一般に有機系のコーテイングを行うが、これ
は耐侯性がない。最近、フツ素樹脂系が高耐侯性
コーテイングとして使用されているが、塗膜硬度
が低い。また、無機系として水ガラス系、リン酸
塩系、シリカゾル系等があるが、エフロの発生、
透明性、密着性等で劣つている。また、ケイ素の
アルコキシド系でプラスチツク用ハードコートが
あるが、せいぜい数μｍ、厚くても5μｍまでが
限界である。（特開昭４−56230、48−81928等）
また、それらのコーテイング材は、セメント等へ
の基材には不適である。
更には、特開昭52−36800号公報では、柔軟性
を与えるために、分子鎖両端水酸基封鎖ジオルガ
ノポリシロキサンを添加しているが、テトラアル
コキシシランやアルキルトリアルコキシシランに
混合するジオルガノポリシロキサンの分子量で塗
膜物性が変わりやすく、安定した物性を得にく
く、また、ハジキや重ね塗り性の低下を招きやす
い。また、特開昭55−40631号公報には、低温硬
化の目的でジアルキルシアルコキシシランを添加
しているが、このような組成では、10μｍ以上の
膜厚でセメント基板のような寸法変化の比較的大
きなものにコーテイングするのは困難である。
（発明の目的）
本発明は上記の欠点を改善するために提案され
たもので、セメント基材や木材のように比較的寸
法変化の大きな基材に、透明性のある高硬度、高
耐久なコーテイングを１コートで、10μｍ以上厚
膜化できるコーテイング材の製法を提供すること
を目的とする。
（発明の開示）
本発明は、高硬度、高耐久でかつ１コートで
10μｍ以上の厚膜化が図れるコーテイング材の製
法に関するもので、セメント基材や木材のような
比較的寸法変化の大きな基材へ適用できるための
ものである。
以下詳細に記述する。すなわち本発明は、
(A) SiO2成分として、Si（OR′）4を用い、量
としては、30〜200重量部（ただし、R′は炭
素数１〜４のアルキル基である。）
(B) RSiO成分として、RSi（OR′）3を用い、量
としては、100重量部（ただし、Ｒはメチル
基あるいはエチル基、R′は炭素数１〜４の
アルキル基）
(C) RSiO成分として、R2Si（OR′）2を用い、量
としては、15〜50重量部（ただし、Ｒはメチ
ル基あるいはエチル基、R′は炭素数１〜４
のアルキル基）
以上、(A)、(B)、(C)成分を混合し、酸性触媒下
で、水−アルコール等の溶剤を混合し、反応さ
せ、コーテイング液を作り、基材にコーテイン
グ、200℃以下の温度で硬化させるものである。
ここに使用されるアルコキシシランとして
は、R′として炭素数１〜４のアルキル基、Ｒ
としてはメチル基あるいはエチル基である。
すなわち、Si（OR′）4としてのアルコキシ基
がメトキン、エトキン、プロポキシ、ブトキシ
などのテトラアルコキシシラン。RSi（OR′）3と
してのアルキル基としてはメチル、エチル基
と、アルコキシ基としてはメトキシ、エトキ
シ、プロポキシ、ブトキシなどのアルキルトリ
アルコキシシラン。また、R2Si（OR′）2として
のアルキル基としてはメチル、エチル基を、ア
ルコキシ基としてはメトキシ、エトキシ、プロ
ポキシ、ブトキシなどのジアルキルジアルコキ
シシランを用いる。
Ｒとしては、メチルあるいはエチルがよく、
それ以上のアルキル基やフエニル基等の導入は
耐侯性の低下を招く。
次に、(A)、(B)、(C)の混合比率について述べ
る。(A)、(B)、(C)の配合比率が非常に重要であ
り、この範囲を越えると、硬くなりすき、厚膜
化できなかつたり、基材の動きに追随できず、
クラツクがはいつたり、逆に軟らかくなりすぎ
る。特に、(B)の成分に対し(A)が30重量部以下で
は硬度がでず、200重量部以上では硬すぎて、
基材の動きに追随できない。また、ここに(C)成
分の添加が重要となる。(A)、(B)成分だけで、
(A)、(B)、(C)成分と同じ可撓性を出させるために
は、Ｒ基導入率がふえてしまう。それは、構造
的に、
(A)と(B)だけでは
(A)と(B)と(C)では
上のように同じＲ基導入率では、破線で囲む
ような領域の違いのためと思われる。しかしな
がら、(C)成分も15重量部以下では、可撓性のあ
る膜ができず、基材の動きに追随しにくく、50
重量部以上では、硬度の低下が大きくなる。
次にコーテイング液の調製について述べる。
ここでまず最も重要となるのは、(A)、(B)、(C)と
も、ほとんど加水分解、縮合がなされていない
か、まつたくされていない状態で均一に混合
し、その後、加水分解、縮合させる。(A)、(B)、
(C)のいずれか、あるいは、すべてを加水分解、
縮合反応が進んだものをコーテイング液として
使用するのと、単量体のもので行なうのとで
は、膜の状態がかなりかわる。すなわち、本発
明の同じ組成においても、加水分解、縮合反応
が進んだものを用いると、硬くなりすぎたり、
軟らかくなりすぎたりし、加水分解の程度でか
わり、コントロールしにくい。
また、塗膜にハジキやゆず肌を生じたり、重
ね塗り時のハジキや剥離の原因となる。すなわ
ち、(A)、(B)、(C)の各成分が均一に混合されてい
ることが膜の物性上重要となる。また、酸性触
媒としては、塩酸、リン酸、硫酸、酢酸等の水
溶液を用いる。
また加える水は、理論加水分解率（例えばSi
（OR′）4なら２モル、RSi（OR′）3なら1.5モル、
R2Si（OR′）2なら１モルを100％とする）の50％
以上500％以下とする。50％以下では、充分塗
膜性能がでず、500％以上では、反応がはやく
液の白化、コーテイング膜の白化しやすくな
る。
また、加水分解・縮合を行なうに当つて、種
種の溶剤を用いて行なうとよい。この溶剤とし
ては、メタノール、エタノール等の低級アルコ
ールや、エチレングリコール、モノメチルエー
テル、エチレングリコールモノエチルエーテル
などの単独あるいは混合溶剤を用いる。
また、加水分解、縮合反応は80℃以下の温度
で行なう。
塗装方法としては、特に限定しない。すなわ
ち、スプレー塗布、ロール塗布、浸漬塗布など
を用いる。
また、塗布後の加熱温度は、50℃以上200℃
以下で行なう。
前記の実施例においてSiO2成分として、
全SiO2量の10％以上80％以下をアルコール分
散性のコロイドシリカを用いる。
アルコール分散性のコロイドシリカを添加す
る効果としては、厚膜化の安定化および光沢付
与である。すなわち、の組成でもかなりの厚
膜化（１コートで10μｍ以上）がはかれるが、
それ以上の厚膜化は困難であり、また、冷却条
件をゆつくりとる必要がある。それに対し、ア
ルコール分散性のコロイドシリカを添加するこ
とにより、１コートで10μｍ以上の厚膜が冷却
条件を意識せずに行なえる。すなわち、加熱硬
化後すぐに常温に放置してもクラツク、剥離等
を発生しない。また、条件によつては15μｍ以
上の厚膜化が可能となる。
その添加量として、10％以下では効果がな
く、80％以上ではコーテイング液の時間的安定
性がなくなり、膜の白化を招きやすくなる。
（好ましくは10％以上70％以下がよい。）
前記の、あるいは及びの混合物に対
して、
(Technical Field) The present invention relates to a method for producing a coating material that can coat base materials with relatively large dimensional changes such as cement substrates and wood with a deep feeling (can be made into a thick film), high hardness, and high durability. It is something. (Background Art) Coatings are applied to cement substrates and wood for the purpose of preventing pollution. At that time, an organic coating is generally applied, but this is not weather resistant. Recently, fluororesin-based coatings have been used as highly weather-resistant coatings, but their coating film hardness is low. In addition, there are water glass-based, phosphate-based, silica sol-based, etc. as inorganic systems;
Poor transparency, adhesion, etc. Additionally, there are silicon alkoxide hard coats for plastics, but the maximum thickness is a few micrometers, and the maximum thickness is 5 micrometers. (Japanese Patent Publication No. 4-56230, 48-81928, etc.)
Furthermore, these coating materials are unsuitable for use as base materials for cement and the like. Furthermore, in JP-A-52-36800, a diorganopolysiloxane with hydroxyl groups blocked at both ends of the molecular chain is added to provide flexibility, but diorganopolysiloxane mixed with tetraalkoxysilane or alkyltrialkoxysilane is The physical properties of the coating film tend to change depending on the molecular weight of the siloxane, making it difficult to obtain stable physical properties, and also easily causing repellency and poor recoatability. Furthermore, in JP-A No. 55-40631, dialkylsialkoxysilane is added for the purpose of low-temperature curing, but with such a composition, it is difficult to compare the dimensional changes of a cement substrate with a film thickness of 10 μm or more. It is difficult to coat large objects. (Objective of the Invention) The present invention was proposed to improve the above-mentioned drawbacks. The purpose of the present invention is to provide a method for manufacturing a coating material that can thicken the coating by 10 μm or more in one coat. (Disclosure of the invention) The present invention provides high hardness, high durability, and one-coat
This relates to a method for manufacturing a coating material that can achieve a film thickness of 10 μm or more, and is applicable to base materials with relatively large dimensional changes, such as cement base materials and wood. It will be described in detail below. That is, in the present invention, Si(OR') 4 is used as the (A) SiO2 component, and the amount is 30 to 200 parts by weight (R' is an alkyl group having 1 to 4 carbon atoms.) B) RSi(OR') 3 was used as the RSiO component, and the amount was 100 parts by weight (R is a methyl group or ethyl group, R' is an alkyl group having 1 to 4 carbon atoms) (C) RSiO component , R2Si (OR') 2 is used, and the amount is 15 to 50 parts by weight (R is a methyl group or an ethyl group, and R' is a carbon number of 1 to 4.
Components (A), (B), and (C) are mixed together and reacted with water and a solvent such as alcohol under an acidic catalyst to create a coating solution, which is then coated on a substrate. It is cured at a temperature of 200℃ or less. The alkoxysilane used here includes an alkyl group having 1 to 4 carbon atoms as R', R
Examples include methyl group or ethyl group. That is, the alkoxy group as Si(OR′) 4 is tetraalkoxysilane such as methquine, ethquine, propoxy, butoxy. The alkyl group as RSi(OR′) 3 is methyl, ethyl group, and the alkoxy group is alkyltrialkoxysilane such as methoxy, ethoxy, propoxy, butoxy. Further, as the alkyl group as R 2 Si (OR') 2 , a methyl or ethyl group is used, and as the alkoxy group, a dialkyldialkoxysilane such as methoxy, ethoxy, propoxy, or butoxy is used. R is preferably methyl or ethyl;
Introduction of more alkyl groups, phenyl groups, etc. causes a decrease in weather resistance. Next, the mixing ratio of (A), (B), and (C) will be described. The blending ratio of (A), (B), and (C) is very important; if it exceeds this range, it will become hard and cannot be thickened, or it will not be able to follow the movement of the base material.
It gets cracky or becomes too soft. In particular, if (A) is less than 30 parts by weight of component (B), hardness will not be achieved, and if it is more than 200 parts by weight, it will be too hard.
Unable to follow the movement of the base material. Also, the addition of component (C) is important here. With only components (A) and (B),
In order to achieve the same flexibility as components (A), (B), and (C), the R group introduction rate must increase. Structurally, (A) and (B) alone are not enough. In (A), (B) and (C) This seems to be due to the difference in the region surrounded by the broken line at the same R group introduction rate as above. However, if component (C) is less than 15 parts by weight, a flexible film cannot be formed and it is difficult to follow the movement of the base material.
Above parts by weight, the hardness decreases significantly. Next, the preparation of the coating liquid will be described.
The most important thing to do here is to mix (A), (B), and (C) uniformly with almost no hydrolysis, condensation, or lashing, and then , to condense. (A), (B),
Hydrolyzing any or all of (C),
The state of the membrane is quite different depending on whether a coating solution that has undergone a condensation reaction is used or a monomer coating solution. That is, even if the composition of the present invention is the same, if a product that has undergone hydrolysis and condensation reactions is used, it may become too hard.
It may become too soft and change depending on the degree of hydrolysis, making it difficult to control. It may also cause repellency or peeling on the paint film, or repellency or peeling during overcoating. That is, it is important for the physical properties of the film that the components (A), (B), and (C) are uniformly mixed. Further, as the acidic catalyst, an aqueous solution of hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, etc. is used. In addition, the amount of water added is determined by the theoretical hydrolysis rate (e.g. Si
(OR') 4 means 2 moles, RSi(OR') 3 means 1.5 moles,
R 2 Si (OR') 50% of 2 (1 mole is 100%)
500% or less. If it is less than 50%, the coating film performance will not be sufficient, and if it is more than 500%, the reaction will be rapid and the whitening of the liquid and coating film will easily occur. Further, in carrying out the hydrolysis and condensation, it is preferable to use various kinds of solvents. As this solvent, lower alcohols such as methanol and ethanol, and single or mixed solvents such as ethylene glycol, monomethyl ether, and ethylene glycol monoethyl ether are used. Further, hydrolysis and condensation reactions are carried out at a temperature of 80°C or lower. The coating method is not particularly limited. That is, spray coating, roll coating, dip coating, etc. are used. In addition, the heating temperature after application is 50℃ or higher and 200℃.
Do it below. In the above examples, as the SiO 2 component,
Alcohol-dispersible colloidal silica is used for 10% or more and 80% or less of the total amount of SiO2. The effects of adding alcohol-dispersible colloidal silica include stabilizing thickening and imparting gloss. In other words, even with the composition of
It is difficult to make the film thicker than that, and cooling conditions must be relaxed. On the other hand, by adding alcohol-dispersible colloidal silica, a thick film of 10 μm or more can be formed in one coat without worrying about cooling conditions. That is, even if it is left at room temperature immediately after being heated and cured, cracks, peeling, etc. will not occur. Furthermore, depending on the conditions, it is possible to increase the thickness of the film to 15 μm or more. If the amount added is less than 10%, it will not be effective, and if it is more than 80%, the coating liquid will lose its temporal stability and will easily cause whitening of the film.
(Preferably 10% or more and 70% or less.) For the above or a mixture of and,
【式】H2N
−R2−Si（OR′）3、あるいは
[Formula] H 2 N −R 2 −Si(OR′) 3 or
【式】の単独
あるいは複数を固形分に対して、0.1重量部以
上３重量部以下添加する。
（R2、R2′はCo′H2o′でｎ＝１〜３、R3 oはＣ
＝１〜４のアルキル基、ｎ＝0or1、R′はＣ＝
１〜４のアルキル基）
（）の添加の目的は、コーテイング膜相互
の密着性の向上と、１コートで厚膜化させたと
きの反応を均一に行なわせるためのものであ
る。すなわち、基材に何層か重ね塗りをして塗
膜を仕上げるが、そのときの相互の密着性をあ
げるためであり、更に一度に10μｍ以上の膜を
形成するに際しどうしても厚さ方向に反応のム
ラができ、塗膜物性が低下するのを防ぐためで
ある。
添加剤は固形分に対して、0.1重量部以上３
重量部以下添加する。0.1重量部では効果がな
く、３重量部以上では膜の白化やゆず肌を招
く。また、耐侯性の低下を招く。（好ましくは
0.1重量部以上１重量部以下がよい。）
、、のそれぞれあるいは、、の
複数の組合せに対して、最大径5μｍ以下の無
定形の微粉シリカを0.1重量部以上10重量部以
下添加することを特徴とする（固形分に対し
て）。その目的は、厚膜化および硬度の向上、
すなわち、フイラー効果を示すものであるが、
シリカとして無定形に限定するのは、透明性の
ためであり、加熱、冷却時の熱膨張、収縮に伴
なう影響を少なくするためである。また、粒径
として5μｍ以上のものが含まれると、コーテ
イング膜の平滑性や物性低下を招く。また添加
量としては、0.1重量部未満では効果がなく、
10重量部超過では光沢、透明性の低下を招く。
好ましくは、0.1重量部以上５重量部以下が好
ましい。
以上のようなコーテイング材に、増粘剤、界面
活性剤、紫外線吸収剤、着色剤など、目的に応じ
て加えることができる。
また、基材へのプライマーも用いてよく、上述
のコーテイング液のプライマーとしては、アクリ
ル、ウレタン、エポキシ樹脂とシリコンとの複合
系がよい。
次に実施例について説明する。
実施にあたり、基材がJIS A5403の石綿スレー
ト系のフレキシブル板６mm厚を12cm×18cmの大き
さに切断し用いた。またプライマーとして、東芝
シリコーン社製のシリコーン変性ウレタン系を膜
厚で3μｍになるよう塗布して使用した。
の場合の実施例
比較例 １
メチルトリメトキシシラン100重量部にテトラ
エトキシシラン150重量部、ジメチルジエトキシ
シラン５重量部、イソプロピルアルコール100重
量部を混合、更に、0.1NのHCll0重部とH2O80重
量部を添加し、撹拌する。それを室温で６時間熟
成させ、コーテイング材とする。
比較例 ２
テトラエトキシシラン100重量部にイソプロピ
ルアルコール50重量部を加え、混合、更に0.1N
のHCl5重量部とH2O30重量部を加えて、撹拌、
それを室温で６時間熟成した。
上述のコーテイング液のテトラエトキシシラン
成分150重量部に対して、メチルトリメトキシシ
ラン100重量部とジメチルジエトキシシラン30重
量部とH2O18重量部を添加し撹拌。それを室温
で６時間熟成してコーテイング液を得た。
比較例 ３
ジメチルジエトキシシラン100重量部にイソプ
ロピルアルコール50重量部を加え、混合、更に
0.1NのHCl5重量部とH2O20重量部を加えて撹
拌、それを室温で６時間熟成した。
上述のコーテイング液を（）とすると、メチ
ルトリメトキシシラン100重量部に対し、テトラ
エトキシシラン150重量部とイソプロピルアルコ
ール50重量部と（）を50重量部加えて撹拌。そ
れを室温で６時間熟成してコーテイング液を得
た。
実施例 １
メチルトリメトキシシラン100重量部とテトラ
エトキシシラン150重量部とジメチルジエトキシ
シラン30重量部とイソプロピルアルコール150重
量部を混合、さらに0.1NのHCl15重量部と
H2O85重量部を添加し、撹拌。それを室温で６
時間熟成させ、コーテイング液を得た。
実施例 ２
実施例１のテトラエトキシシランを200重量部
とし、他は１と同様。
実施例 ３
実施例１のジメチルジエトキシシランを15重量
部とし、他は１と同様。
実施例 ４
実施例１のテトラエトキシシランを100重量部
とし、ジメチルジエトキシシランを15重量部と
し、他は１と同じ。
実施例 ５
実施例１のテトラエトキシシランを200重量部
とし、ジメチルジエトキシシランを15重量部と
し、他は１と同じ。
以上の組成のものを用意した基板にスプレーで
塗布し、常温で１分おいたのち、150℃で30分加
熱した。[Formula] alone or in combination is added from 0.1 parts by weight to 3 parts by weight based on the solid content. (R 2 , R 2 ′ are C o ′ H 2o ′, n = 1 to 3, R 3 o is C
=1-4 alkyl group, n=0or1, R' is C=
(1 to 4 alkyl groups) The purpose of adding () is to improve the adhesion between the coating films and to uniformly react when the film is thickened with one coat. In other words, the coating film is finished by applying several layers to the base material, but this is done to improve mutual adhesion.Furthermore, when forming a film of 10 μm or more at a time, it is inevitable that reactions occur in the thickness direction. This is to prevent unevenness from occurring and deterioration of the physical properties of the coating film. Additives are 0.1 parts by weight or more based on the solid content3
Add less than part by weight. 0.1 part by weight has no effect, and 3 parts by weight or more causes whitening of the membrane and orange skin. Moreover, it causes a decrease in weather resistance. (Preferably
It is preferably 0.1 part by weight or more and 1 part by weight or less. ) , , or a plurality of combinations of , 0.1 part by weight or more and 10 parts by weight or less of amorphous fine powder silica having a maximum diameter of 5 μm or less is added (based on solid content). The purpose is to thicken the film and improve hardness.
In other words, it shows a filler effect, but
The reason why silica is limited to amorphous is to ensure transparency and to reduce the effects of thermal expansion and contraction during heating and cooling. Furthermore, if particles with a particle size of 5 μm or more are included, the smoothness and physical properties of the coating film will be deteriorated. Also, if the amount added is less than 0.1 part by weight, it will not be effective.
If it exceeds 10 parts by weight, gloss and transparency will decrease.
Preferably, the amount is 0.1 parts by weight or more and 5 parts by weight or less. Thickeners, surfactants, ultraviolet absorbers, colorants, and the like can be added to the above-mentioned coating materials depending on the purpose. Further, a primer for the base material may also be used, and a composite system of acrylic, urethane, or epoxy resin and silicone is preferable as the primer for the above-mentioned coating liquid. Next, an example will be described. In carrying out the experiment, a JIS A5403 asbestos slate flexible board with a thickness of 6 mm was cut into a size of 12 cm x 18 cm. As a primer, a silicone-modified urethane system manufactured by Toshiba Silicone Co., Ltd. was applied to a film thickness of 3 μm. Example Comparative Example 1 100 parts by weight of methyltrimethoxysilane, 150 parts by weight of tetraethoxysilane, 5 parts by weight of dimethyldiethoxysilane, and 100 parts by weight of isopropyl alcohol were mixed, and further, 0 parts by weight of 0.1N HCCl and H 2 Add 80 parts by weight of O and stir. It is aged at room temperature for 6 hours and used as a coating material. Comparative Example 2 Add 50 parts by weight of isopropyl alcohol to 100 parts by weight of tetraethoxysilane, mix, and then add 0.1N
Add 5 parts by weight of HCl and 30 parts by weight of H 2 O, stir,
It was aged for 6 hours at room temperature. To 150 parts by weight of the tetraethoxysilane component of the above coating liquid, 100 parts by weight of methyltrimethoxysilane, 30 parts by weight of dimethyldiethoxysilane, and 18 parts by weight of H 2 O were added and stirred. It was aged for 6 hours at room temperature to obtain a coating liquid. Comparative Example 3 50 parts by weight of isopropyl alcohol was added to 100 parts by weight of dimethyldiethoxysilane, mixed, and then
5 parts by weight of 0.1N HCl and 20 parts by weight of H 2 O were added and stirred, and the mixture was aged at room temperature for 6 hours. Assuming that the above coating liquid is (), 150 parts by weight of tetraethoxysilane, 50 parts by weight of isopropyl alcohol, and 50 parts by weight of () are added to 100 parts by weight of methyltrimethoxysilane and stirred. It was aged for 6 hours at room temperature to obtain a coating liquid. Example 1 100 parts by weight of methyltrimethoxysilane, 150 parts by weight of tetraethoxysilane, 30 parts by weight of dimethyldiethoxysilane and 150 parts by weight of isopropyl alcohol were mixed, and further 15 parts by weight of 0.1N HCl were mixed.
Add 85 parts by weight of H 2 O and stir. 6 at room temperature
A coating liquid was obtained by aging for a period of time. Example 2 Same as in Example 1 except that the tetraethoxysilane used in Example 1 was used in an amount of 200 parts by weight. Example 3 Same as in Example 1 except that the dimethyldiethoxysilane used in Example 1 was used in an amount of 15 parts by weight. Example 4 The same as in Example 1 except that the tetraethoxysilane of Example 1 was used as 100 parts by weight, and the dimethyldiethoxysilane was used as 15 parts by weight. Example 5 The tetraethoxysilane of Example 1 was changed to 200 parts by weight, the dimethyldiethoxysilane was changed to 15 parts by weight, and the other conditions were the same as in Example 1. The above composition was applied by spray to the prepared substrate, left at room temperature for 1 minute, and then heated at 150°C for 30 minutes.
【表】
の場合の実施例
実施例 ６
メチルトリメトキシシラン100重量部とテトラ
エトキシシラン75重量部とIPAオルガノゾル
（OSCAL−1432 SO2 30％）72重量部とジメチル
ジエトキシシラン30重量部と、イソプロピルアル
コール100重量部を混合、さらに0.1NのHCl10重
量部とH2O70重量部を添加、撹拌。
熟成は同じ（IPAとはイソプロピルアルコー
ル）
実施例 ７
メチルトリメトキシシラン100重量部、テトラ
エトキシシラン100重量部とIPAオルガノゾル
（OSCAL−1432）100重量部とジメチルジエトキ
シシラン30重量部とイソプロピルアルコール100
重量部。他は実施例６と同じ。
実施例 ８
実施例６のジメチルジエトキシシランを15重量
部とした。他は実施例６と同じ。
実施例 ９
メチルトリメトキシシラン100重量部とテトラ
エトキシシラン50重量部とIPオルガノゾル
（OSCAL−1432）50重量部とジメチルジエトキ
シシラン15重量部とイソプロピルアルコール100
重量部。他は実施例６と同じ。
実施例 10
実施例７のジメチルジエトキシシランを15重量
部とした。他は実施例７と同じ。
比較例 ４
メチルトリメトキシシラン100重量部とテトラ
エトキシシラン140重量部とIPAオルガノゾル
（OSCAL−1432）10重量部とジメチルジエトキ
シシラン530重量部とイソプロピルアルコール100
重量部を混合、更に0.1NのHCl1重量部H2O80重
量部を添加。後は実施例６と同じ。
比較例 ５
メチルトリメトキシシラン100重量部とIPAオ
ルガノゾル（OSCAL−1432）150重量部とジメ
チルジエトキシシラン30重量部とイソプロピルア
ルコール100重量部を混合、更に0.1NのHCl10重
量部H2O35重量部添加。後は実施例６と同じ。[Table] Example 6 100 parts by weight of methyltrimethoxysilane, 75 parts by weight of tetraethoxysilane, 72 parts by weight of IPA organosol (OSCAL-1432 SO 2 30%) and 30 parts by weight of dimethyldiethoxysilane, Mix 100 parts by weight of isopropyl alcohol, then add 10 parts by weight of 0.1N HCl and 70 parts by weight of H 2 O, and stir. Aging is the same (IPA is isopropyl alcohol) Example 7 100 parts by weight of methyltrimethoxysilane, 100 parts by weight of tetraethoxysilane, 100 parts by weight of IPA organosol (OSCAL-1432), 30 parts by weight of dimethyldiethoxysilane, and 100 parts by weight of isopropyl alcohol.
Weight part. Others are the same as in Example 6. Example 8 The amount of dimethyldiethoxysilane used in Example 6 was 15 parts by weight. Others are the same as in Example 6. Example 9 100 parts by weight of methyltrimethoxysilane, 50 parts by weight of tetraethoxysilane, 50 parts by weight of IP organosol (OSCAL-1432), 15 parts by weight of dimethyldiethoxysilane, and 100 parts by weight of isopropyl alcohol
Weight part. Others are the same as in Example 6. Example 10 The amount of dimethyldiethoxysilane used in Example 7 was 15 parts by weight. The rest is the same as in Example 7. Comparative Example 4 100 parts by weight of methyltrimethoxysilane, 140 parts by weight of tetraethoxysilane, 10 parts by weight of IPA organosol (OSCAL-1432), 530 parts by weight of dimethyldiethoxysilane, and 100 parts by weight of isopropyl alcohol.
Mix parts by weight and further add 1 part by weight of 0.1N HCl and 80 parts by weight of H 2 O. The rest is the same as in Example 6. Comparative Example 5 100 parts by weight of methyltrimethoxysilane, 150 parts by weight of IPA organosol (OSCAL-1432), 30 parts by weight of dimethyldiethoxysilane and 100 parts by weight of isopropyl alcohol were mixed, and further 10 parts by weight of 0.1N HCl 35 parts by weight of H 2 O Addition. The rest is the same as in Example 6.
【表】【table】
【表】【table】
【表】
の場合の実施例
〓実施例６の組成を基準に添加剤を加えていつ
た。
〓塗装条件および加熱条件は同じ、また１コート
20μｍの膜厚について検討した。[Table] Example: Based on the composition of Example 6, additives were added. 〓Painting conditions and heating conditions are the same, and 1 coat
A film thickness of 20 μm was investigated.
【表】
の場合の実施例
添加する微粉末シリカは日本アエロジル社製の
比表面積110±20m2／ｇのもの（R972）および日
本シリカ社Nipsil SS−50（75m2／ｇ）を使用し
た。
実施例16〜18と20は実施例１の配合に添加。
実施例19は実施例11の配合に添加。
塗装条件および加熱条件は同じ。Examples for [Table] The fine powder silica to be added was Nippon Aerosil Co., Ltd. with a specific surface area of 110±20 m 2 /g (R972) and Nippon Silica Co., Ltd. Nipsil SS-50 (75 m 2 /g). Examples 16-18 and 20 were added to the formulation of Example 1. Example 19 was added to the formulation of Example 11. Painting and heating conditions are the same.
【表】【table】
【表】
（発明の効果）
叙上のように本発明によれば、コロイドシリカ
にテトラアルコキシシラン（一般にはR2Si
（OR′）2）を適当な範囲で併用することにより、
皮膜の厚膜化が可能であり、かつ対クラツク性の
向上を図り、さらに液の経時による塗膜の光沢の
低下を防ぐことができる効果を有するものであ
る。[Table] (Effects of the Invention) As described above, according to the present invention, colloidal silica is mixed with tetraalkoxysilane (generally R 2 Si
By using (OR′) 2 ) in an appropriate range,
It has the effect of making it possible to thicken the coating, improving crack resistance, and preventing a decrease in the gloss of the coating as the liquid ages.
Claims (1)
は炭素数１〜４のアルキル基を示し Ａ：SiO2成分としてSi（OR′）4を用い、50〜200重
量部 Ｂ：RSiO3/2成分としてRSi（OR′）3を用い、100
重量部 Ｃ：R2SiO成分としてR2Si（OR′）2を用い、13〜
50重量部 かつSiO2成分として、全重量の10％以上80％
以下をアルコール分散性のコロイドシリカを用
い、前記Ａ、Ｂ、Ｃを混合し、酸性触媒下で加水
分解することを特徴とするコーテイング材の製
法。[Claims] 1 R represents a methyl group or an ethyl group; R' represents an alkyl group having 1 to 4 carbon atoms; A: Si(OR') 4 is used as the second SiO component; 50 to 200 parts by weight; B: Using RSi(OR') 3 as the RSiO3/2 component, 100
Weight part C: R2Si (OR') 2 is used as the R2SiO component, 13~
50 parts by weight and 10% or more 80% of the total weight as two SiO components
A method for producing a coating material, which comprises using alcohol-dispersible colloidal silica, mixing A, B, and C, and hydrolyzing the mixture under an acidic catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11854786A JPS62275170A (en) | 1986-05-23 | 1986-05-23 | Production of coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11854786A JPS62275170A (en) | 1986-05-23 | 1986-05-23 | Production of coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62275170A JPS62275170A (en) | 1987-11-30 |
| JPH0426630B2 true JPH0426630B2 (en) | 1992-05-07 |
Family
ID=14739287
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11854786A Granted JPS62275170A (en) | 1986-05-23 | 1986-05-23 | Production of coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62275170A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0269374A (en) * | 1988-09-05 | 1990-03-08 | Aoki Corp | Concrete coloring material and coloring method |
| JPH0269375A (en) * | 1988-09-05 | 1990-03-08 | Aoki Corp | Concrete covering material and covering method |
| JP2005314616A (en) * | 2004-04-30 | 2005-11-10 | Shin Etsu Chem Co Ltd | Silicone coating composition and article to be coated |
| JP2011002644A (en) * | 2009-06-18 | 2011-01-06 | Konica Minolta Business Technologies Inc | Display particle for image display and image display |
| EP3290487B1 (en) * | 2015-04-30 | 2022-08-31 | Lintec Corporation | Antifouling composition, antifouling sheet and method for producing antifouling sheet |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50116600A (en) * | 1974-02-28 | 1975-09-11 | ||
| JPS50126033A (en) * | 1974-03-25 | 1975-10-03 | ||
| JPS512736A (en) * | 1974-06-25 | 1976-01-10 | Dow Corning | |
| JPS53130732A (en) * | 1977-03-18 | 1978-11-15 | Rohm & Haas | Weatherproof and wearrresistant coating composition and method of bonding same |
| JPS54116099A (en) * | 1978-03-01 | 1979-09-10 | Japan Atom Energy Res Inst | Thermosetting resin composition |
| JPS5540631A (en) * | 1978-09-18 | 1980-03-22 | Nippon Chemiphar Co Ltd | Novel beta-lactam compound and its preparation |
| JPS55116765A (en) * | 1979-03-02 | 1980-09-08 | Toray Ind Inc | Coating composition |
| JPS5699263A (en) * | 1980-01-10 | 1981-08-10 | Nippon Sheet Glass Co Ltd | Coating composition |
-
1986
- 1986-05-23 JP JP11854786A patent/JPS62275170A/en active Granted
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS50116600A (en) * | 1974-02-28 | 1975-09-11 | ||
| JPS50126033A (en) * | 1974-03-25 | 1975-10-03 | ||
| JPS512736A (en) * | 1974-06-25 | 1976-01-10 | Dow Corning | |
| JPS53130732A (en) * | 1977-03-18 | 1978-11-15 | Rohm & Haas | Weatherproof and wearrresistant coating composition and method of bonding same |
| JPS54116099A (en) * | 1978-03-01 | 1979-09-10 | Japan Atom Energy Res Inst | Thermosetting resin composition |
| JPS5540631A (en) * | 1978-09-18 | 1980-03-22 | Nippon Chemiphar Co Ltd | Novel beta-lactam compound and its preparation |
| JPS55116765A (en) * | 1979-03-02 | 1980-09-08 | Toray Ind Inc | Coating composition |
| JPS5699263A (en) * | 1980-01-10 | 1981-08-10 | Nippon Sheet Glass Co Ltd | Coating composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62275170A (en) | 1987-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2003225538B2 (en) | Elastomer-modified epoxy siloxane compositions | |
| JP4017477B2 (en) | Silica-based coating liquid, silica-based coating film using the same, and silica-based coating film-coated substrate | |
| JP2914710B2 (en) | Solvent-free silicone coating composition | |
| US20050148752A1 (en) | Amino-functional polysiloxanes and their use in coatings | |
| US5599893A (en) | Water repellent composition | |
| CA1159991A (en) | Silicone resin coating composition | |
| JPH0426630B2 (en) | ||
| JP6939142B2 (en) | Paint for metal plate and manufacturing method of painted metal plate using it | |
| JPH08209118A (en) | Water repellency agent | |
| US4302512A (en) | Preparation for the abhesive coating of baking tins, cake tins, frying pans, metal pots, and the like | |
| JPS63156867A (en) | Coating material composition | |
| JPS6348363A (en) | Coating composition | |
| JPS63137972A (en) | Coating composition | |
| JP3245521B2 (en) | Paint composition | |
| JPH028273A (en) | Silicon alkoxide-based coating material | |
| JPH0485380A (en) | Inorganic coating material | |
| JP4352568B2 (en) | Inorganic paint | |
| JP2695113B2 (en) | Method for repairing inorganic hardened body or metal surface having silicon-based coating layer | |
| JPH0236282A (en) | Silicon alkoxide-based coating material and production thereof | |
| JPH0940910A (en) | Water repellent | |
| JP3761747B2 (en) | Paint structure | |
| JPH08283661A (en) | Composition for coating layer | |
| JPS59126470A (en) | Material for forming dust-proofing coating film | |
| JP3976417B2 (en) | Composition for forming water-repellent coating | |
| JP2002186900A (en) | Antifoulancy coating film and its production method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |