JPH03258878A - Coating composition - Google Patents
Coating compositionInfo
- Publication number
- JPH03258878A JPH03258878A JP5550790A JP5550790A JPH03258878A JP H03258878 A JPH03258878 A JP H03258878A JP 5550790 A JP5550790 A JP 5550790A JP 5550790 A JP5550790 A JP 5550790A JP H03258878 A JPH03258878 A JP H03258878A
- Authority
- JP
- Japan
- Prior art keywords
- coating
- silica sol
- coating film
- alkoxysilane
- silica
- 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.)
- Pending
Links
- 239000008199 coating composition Substances 0.000 title claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 125000002252 acyl group Chemical group 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012736 aqueous medium Substances 0.000 claims description 4
- 238000001238 wet grinding Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 3
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 67
- 238000000576 coating method Methods 0.000 abstract description 62
- 239000000203 mixture Substances 0.000 abstract description 19
- 239000002253 acid Substances 0.000 abstract description 11
- 239000012776 electronic material Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000006460 hydrolysis reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000010298 pulverizing process Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 239000002612 dispersion medium Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000006482 condensation reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- -1 glycol ethers Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 235000012970 cakes Nutrition 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000005459 Digitaria exilis Nutrition 0.000 description 1
- 240000008570 Digitaria exilis Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 235000010575 Pueraria lobata Nutrition 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 235000021463 dry cake Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000008206 lipophilic material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000010023 transfer printing Methods 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野１
本発明は、コロイダルシリカの共存下にアルコキシシラ
ンを加水分解及び縮合する事により得られるコーティン
グ用組成物の改良に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to an improvement in a coating composition obtained by hydrolyzing and condensing an alkoxysilane in the coexistence of colloidal silica.
本発明のコーティング剤は、これを用いてガラス、セラ
ミックス、金属、プラスチック等の各種基材上に厚い塗
膜を形成させても、クラックの入らない塗膜が得られ、
この塗膜は密着強度と機械的強度に優れた、化学的及び
物理的保護コートとして機能する。Even if the coating agent of the present invention is used to form a thick coating film on various substrates such as glass, ceramics, metals, and plastics, a crack-free coating film can be obtained.
This coating functions as a chemical and physical protective coat with excellent adhesion and mechanical strength.
〔従来の技術］
アルコキシシランを水及び触媒の存在下で加水分解する
事によってコーティング用組成物が得られる事は既に知
られ、ガラス基板からのアルカリ成分溶出防止等に実用
されている。又、特開昭６１−２９１６６５号公報には
、コロイタルシリ力の共存下にアルコキシシランを加水
分解及び縮合させてなる組成物が、耐クラツク性に優れ
た厚塗り用コーティング剤として用いられることが開示
されている。[Prior Art] It is already known that a coating composition can be obtained by hydrolyzing an alkoxysilane in the presence of water and a catalyst, and it has been put into practical use for preventing the elution of alkaline components from glass substrates. Furthermore, JP-A No. 61-291665 discloses that a composition obtained by hydrolyzing and condensing alkoxysilane in the presence of colloidal silica can be used as a thick coating agent with excellent crack resistance. has been done.
一方、アルコキシシランの加水分解物を結合剤として、
これにアルミナ、ムライト、石英等の無機耐火物粉末や
湿式法又は乾式法で得られたシリカ微粉を分散させた塗
料が提案されている。On the other hand, using an alkoxysilane hydrolyzate as a binder,
Paints have been proposed in which powders of inorganic refractories such as alumina, mullite, and quartz or fine silica powder obtained by wet or dry methods are dispersed.
［発明が解決しようとする課題１
上記アルコキシシランの加水分解によって得られるコー
ティング剤を基材に塗布すると、基材との熱膨張率の差
や塗膜の硬化時の体積収縮による内部応力により ０．
３μ以上の塗膜を形成した場合、クラックが発生する。[Problem to be Solved by the Invention 1] When the coating agent obtained by hydrolyzing the alkoxysilane is applied to a base material, internal stress due to the difference in coefficient of thermal expansion with the base material and volume shrinkage during curing of the coating film causes 0 ．．
If a coating film with a thickness of 3μ or more is formed, cracks will occur.
上記特開昭６１−２９１６６５号公報に記載のアルコキ
シシランとコロイグルシリ力の反応物からなるコーティ
ング剤を用いても１回の塗布で形成しつる塗膜の厚みは
１．５ｕが限界であり、それ以上の厚みを有する塗膜を
形成させると、塗膜のクラック、剥離等が発生する。Even if a coating agent made of a reaction product of alkoxysilane and colloidal silicate described in JP-A No. 61-291665 is used, the maximum thickness of the vine coating film that can be formed in one application is 1.5 μ; If a coating film having a thickness greater than that is formed, cracks, peeling, etc. of the coating film will occur.
上記アルコキシシランの加水分解物を結合剤として、こ
れにアルミナ、ムライト、石英等の無機耐火物粉末や湿
式シリカ微粉を分散させたコーティング剤は、分散後比
較的早い時間に粉末成分の沈降固結が起こり、再分散が
困難となり塗膜形成は不可能となる。一方、湿式シリカ
微粉、例えば、アエロジルは分散性が良く沈降固結の問
題はないものの、コーティング剤の粘度が増加し、塗布
性が良好でないばかりでなく貯蔵安定性にも欠ける。又
、得られた塗膜はアエロジルの結合力が弱いため基材に
対する密着力が低く、耐クラツク性にも劣る。Coating agents in which inorganic refractory powder such as alumina, mullite, quartz, or wet silica fine powder is dispersed in the alkoxysilane hydrolyzate as a binder, cause the powder components to settle and solidify relatively quickly after dispersion. occurs, making redispersion difficult and making it impossible to form a coating. On the other hand, wet silica fine powder, such as Aerosil, has good dispersibility and does not cause the problem of sedimentation and caking, but it increases the viscosity of the coating agent and not only does not have good applicability but also lacks storage stability. Furthermore, the resulting coating film has low adhesion to the substrate due to the weak binding force of Aerosil, and is also poor in crack resistance.
本発明は、上記従来技術における問題点を解決したもの
であって、−回の塗布により３ＬＬ以上の膜厚でも、ク
ラックが生じないで、耐熱性が高く且つ機械的強度に優
れた塗膜を形成させうるコーティング用組成物を提供し
ようとするものである。The present invention solves the above-mentioned problems in the prior art, and provides a coating film that does not cause cracks and has high heat resistance and excellent mechanical strength even when the film thickness is 3LL or more after multiple coatings. It is an object of the present invention to provide a coating composition that can be formed.
［課題を解決するための手段１
本発明のコーティング用組成物は、
下記一般式［Ｉ］
Ｒ’ ｎｓｉ （ＯＲ”） ４−ｎ・・・・・・ ［Ｉ
］（式中、Ｒ１は置換基を有することもあるアルキル基
、アルケニル基又はアリール基を表し、Ｒ２はアルキル
基、アシル基又はアリール基を表し、そしてｎはＯまた
は１の整数を表す、）
で示されるアルコキシシランの１種又は２種以上と、湿
式法により得られたシリカ微粉を湿式粉砕することによ
り得られるシリカゾル、好ましくは珪弗化水素酸又はそ
のアンモニウム塩を水性媒体中でアンモニアと反応させ
ることにより生成した析出シリカを上させることにより
生成した析出シリカの濃度２〜５０重量％において湿式
粉砕することにより得られるシリカゾルを、アルコキシ
シランをＳｉｎｇとして１００重量部に対してシリカゾ
ルに含有される５ｉｎ２を５〜４００重量部の比率に混
合し、加水分解及び縮合させてなることを特徴とするち
のである。[Means for Solving the Problems 1] The coating composition of the present invention has the following general formula [I] R' nsi (OR") 4-n... [I
] (In the formula, R1 represents an alkyl group, alkenyl group or aryl group that may have a substituent, R2 represents an alkyl group, acyl group or aryl group, and n represents an integer of O or 1.) A silica sol obtained by wet-pulverizing silica fine powder obtained by a wet method, preferably hydrosilicofluoric acid or its ammonium salt, is mixed with ammonia in an aqueous medium. A silica sol obtained by wet grinding at a concentration of 2 to 50% by weight of the precipitated silica produced by the reaction is added to the silica sol with respect to 100 parts by weight of the alkoxysilane. 5in2 is mixed in a ratio of 5 to 400 parts by weight, and the mixture is hydrolyzed and condensed.
本発明に用いられるアルコキシシランを表す上記一般式
［Ｉ］において、Ｒ’の例としては、−ＣＨ，、−ＣＨ
，ＣＨ，、−ＣＨｚＣＨｚＣＨｓ、ＣＨａ （ＣＨ２）
ｚｃＨａ、−ＣＨ２（ＣＨ２） ａＣＨａ、−ＣＨａ
ＣＨ（ＣＨｓ）ｚ 、−ＣＨ２ＣＨ２）６ＣＨ８、ＣＨ
ａ （Ｃ）Ｉ２） ５ＣＨｓ、−ＣＨ＝ ＣＨ２、−Ｃ
Ｈａ （ＣＨｚ） ＋６ＣＨｓ 、ＣＨ２ＣＨ２ＣＨ２
Ｃｌ、−ＣＨ２ＣＨ２ＣＨ２０Ｈ１
−Ｃ，Ｈ，、
等が挙げられる。好ましくは、炭素原子数１ないし５の
アルキル、アルケニル基である。In the above general formula [I] representing the alkoxysilane used in the present invention, examples of R' include -CH,, -CH
,CH,, -CHzCHzCHs, CHa (CH2)
zcHa, -CH2(CH2) aCHa, -CHa
CH(CHs)z, -CH2CH2)6CH8, CH
a (C)I2) 5CHs, -CH= CH2, -C
Ha (CHz) +6CHs, CH2CH2CH2
Cl, -CH2CH2CH20H1 -C,H, etc. are mentioned. Preferred are alkyl and alkenyl groups having 1 to 5 carbon atoms.
Ｒ２の例としては。As an example of R2.
−ｃＨｓ 、−ＣＨｌＣＨｘ、−ＣＨ，ＣＨ，ＣＨ，
、−ＣＨｚ（ＣＨ２）２ＣＨ３、−ＣＯＣＨｓ 、−
ＣＨ２（ＣＨ，） ５ＣＨｓ、 ＣＨ２ＣＨｆｃＨｉ）
２、”’−ＣｓＨｓ、
等が挙げられる。-cHs, -CHlCHx, -CH,CH,CH,
, -CHz(CH2)2CH3, -COCHs, -
CH2(CH,) 5CHs, CH2CHfcHi)
2, "'-CsHs, etc.
本発明に用いられるシリカゾルは、湿式法により得られ
たシリカ微粉を湿式粉砕することにより得られる。湿式
粉砕に用いられる湿式法により得られたシリカ微粉には
、珪弗化水素酸又はそのアンモニウム塩をアンモニアと
反応させるか又は珪酸ナトリウムを中和することにより
得られるものがあるが、好ましくは、珪弗化水素酸又は
そのアンモニウム塩をアンモニアと反応させる事により
得られる析出シリカ微粉である。The silica sol used in the present invention is obtained by wet-pulverizing fine silica powder obtained by a wet method. Among the silica fine powders obtained by the wet method used for wet grinding, there are those obtained by reacting hydrofluorosilicic acid or its ammonium salt with ammonia or by neutralizing sodium silicate, but preferably, It is precipitated silica fine powder obtained by reacting hydrofluorosilicic acid or its ammonium salt with ammonia.
湿式粉砕には、通常の湿式粉砕機、例えば、コロイドミ
ル、ボールミル、ペブルミル、サンドグラインダー、ア
トライター、ホモジナイザー、デイスパー等が、用いら
れる。For wet pulverization, common wet pulverizers such as colloid mills, ball mills, pebble mills, sand grinders, attritors, homogenizers, dispers, etc. are used.
上記湿式粉砕の分散媒としては、水又は有機溶剤が用い
られ、それぞれ水性ゾル、オルガノゾルが得られるが、
アルコキシシランとの混合を考慮した場合、分散媒に有
機溶剤を用いたオルガノゾルが好ましい。Water or an organic solvent is used as the dispersion medium in the above-mentioned wet pulverization, and an aqueous sol or an organosol can be obtained, respectively.
In consideration of mixing with an alkoxysilane, an organosol using an organic solvent as a dispersion medium is preferable.
分散媒として用いられる有機溶剤は、特に制限は無いが
、例えば、メタノール、エタノール等のアルコール類、
エチルセロソルブ、ブチルセロソルブ、エチルカルピト
ール等のグリコールエーテル類、エチレングリコール、
ヘキシレングリコール等のグリコール類、アセトン、メ
チルエチルケトン等のケトン類、トルエン、キシレン等
の芳香族炭化水素類、及びＮ−メチルピロリドン、ジメ
チルホルムアルデヒド等が挙げられる。The organic solvent used as a dispersion medium is not particularly limited, but examples include alcohols such as methanol and ethanol;
Ethyl cellosolve, butyl cellosolve, glycol ethers such as ethyl carpitol, ethylene glycol,
Examples include glycols such as hexylene glycol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as toluene and xylene, and N-methylpyrrolidone and dimethyl formaldehyde.
上記シリカゾルは動的光散乱法による粒子径が１５０〜
６００ミリミクロンを有し、Ｓｉｎｇを２〜５０重量％
含有している。The above silica sol has a particle size of 150~150 by dynamic light scattering method.
600 millimicrons and 2-50% by weight of Sing
Contains.
本発明のアルコキシシランを加水分解及び縮合するため
に用いられる水の量は、上記一般式［Ｉ］で示されるア
ルコキシシランのアルコキシ基４−ｎモルに対して、
０．５から５倍モルの範囲が適当である。又、本発明に
用いられるシリカゾルの分散媒が水の場合には、シリカ
ゾルに含まれる水分が上記加水分解に用いられる水の量
に算入される。The amount of water used for hydrolyzing and condensing the alkoxysilane of the present invention is as follows:
A range of 0.5 to 5 times the mole is appropriate. Further, when the dispersion medium of the silica sol used in the present invention is water, the water contained in the silica sol is included in the amount of water used for the above hydrolysis.
本発明のアルコキシシランを加水分解及び縮合する際に
は、通常、触媒として酸が用いられる。触媒としての酸
の量は、アルコキシシランに対して０．１モル％以上が
良い、酸触媒は一般的に塩酸、硝酸又は硫酸等の鉱酸類
、宿酔、蟻酸、酢酸又はトルエンスルホン酸等の有機酸
類等が好ましい。When hydrolyzing and condensing the alkoxysilane of the present invention, an acid is usually used as a catalyst. The amount of acid as a catalyst is preferably 0.1 mol% or more based on the alkoxysilane.Acid catalysts are generally mineral acids such as hydrochloric acid, nitric acid, or sulfuric acid, or organic acids such as formic acid, acetic acid, or toluenesulfonic acid. Acids and the like are preferred.
本発明の組成物を得るための、上記アルコキシシランと
上記シリカゾルとの混合及び引き続き起こる加水分解及
び縮合は、通常水又は有機溶媒中で行われるが、有機溶
媒中が好ましい。The mixing of the alkoxysilane and the silica sol and the subsequent hydrolysis and condensation to obtain the composition of the invention is usually carried out in water or an organic solvent, preferably in an organic solvent.
用い６れる有機溶媒の例としては、メタノール、エタノ
ール等のアルコール類、エチルセロソルブ、ブチルセロ
ソルブ、エチルカルピトール等のグリコールエーテル類
、エチレングリコール、ヘキシレングリコール等のグリ
コール類、アセトン、メチルエチルケトン等のケトン類
、トルエン、キシレン等の芳香族炭化水素類、及びＮ−
メチルピロリドン、ジメチルホルムアルデヒド等が挙げ
られ、これらの２種以上を混合して用いてち良い。Examples of organic solvents that can be used include alcohols such as methanol and ethanol, glycol ethers such as ethyl cellosolve, butyl cellosolve, and ethyl carpitol, glycols such as ethylene glycol and hexylene glycol, and ketones such as acetone and methyl ethyl ketone. , aromatic hydrocarbons such as toluene and xylene, and N-
Examples include methylpyrrolidone and dimethylformaldehyde, and two or more of these may be used in combination.
上記アルコキシシランと上記シリカゾルとは、アルコキ
シシランを５ｉＯａに換算して、その１００重量部に対
して、シリカゾルを５ｉＯａ分として５〜４００重量部
、好ましくは５〜３００重量部混合される。The alkoxysilane and the silica sol are mixed in an amount of 5 to 400 parts by weight, preferably 5 to 300 parts by weight of the silica sol, based on 5 iOa of the alkoxysilane and 100 parts by weight of the alkoxysilane.
加水分解反応は、上記アルコキシシランと上記シリカゾ
ルを十分混合したのち、水と触媒を有機溶媒と共に添加
することによっても起こさせる事が出来、又アルコキシ
シランの有機溶媒液に水と触媒とシリカゾルの混合物を
添加することによっても起こさせる事が出来るが、好ま
しくは、水と触媒とシリカゾルの混合物をアルコキシシ
ランの有機溶媒溶液に加える方法により行うことが出来
る。The hydrolysis reaction can also be caused by thoroughly mixing the alkoxysilane and the silica sol, and then adding water and a catalyst together with an organic solvent, or by adding a mixture of water, catalyst, and silica sol to the organic solvent solution of the alkoxysilane. This can also be caused by adding, but preferably, it can be carried out by adding a mixture of water, a catalyst, and silica sol to an organic solvent solution of alkoxysilane.
加水分解反応は通常室温で行われるが、必要に応じて加
熱下に行われる。この室温での加水分解反応は、約３０
公租度行えば良い、加水分解反応に引き続く縮合反応は
、−数的には５０°Ｃ以上１５０℃以下の温度で数時間
行われる。The hydrolysis reaction is usually carried out at room temperature, but if necessary, it may be carried out under heating. This hydrolysis reaction at room temperature is approximately 30
The condensation reaction following the hydrolysis reaction, which can be carried out in a controlled manner, is carried out at a temperature of 50° C. to 150° C. for several hours.
本発明のコーティング用組成物としては、アルコキシシ
ランに由来のＳｉＯ□と、シリカゾル由来のＳｉｎｇと
の合計ＳｉＯ□を、 ０．１〜５０重量％、好ましくは
５〜３５重量％の範囲に含むちのである。The coating composition of the present invention contains a total of SiO□ derived from alkoxysilane and Sing derived from silica sol in a range of 0.1 to 50% by weight, preferably 5 to 35% by weight. It is.
本発明のコーティング用組成物には、必要に応じてコロ
イダルシリカ、界面活性剤、有機又は無機増粘剤、その
化フィラーとしての無機粉末等を含有させてら良い。The coating composition of the present invention may contain colloidal silica, a surfactant, an organic or inorganic thickener, an inorganic powder as a filler, etc., if necessary.
更に上記アルコキシシランとシリカゾル混合の際に、下
記一般式［ＩＩ ］
Ｒ”＋ａＳ１ （ＯＲ’）４−１１１ ”’ ”・［Ｉ
Ｉ ］（式中、Ｒ３は置換基を有することらあるアルキ
ル基、アルケニル基又はアリール基を表し、Ｒ４はアル
キル基、アシル基又はアリール基を表し、そしてｍは２
または３の整数を表す、）
で表されるモノアルコキシシラン、ジアルコキシシラン
又はこれらの混合物を少量併用してち良い、上記［ＩＩ
］式のＲ３の例としては、上記［１１式のＲ１例が、
モしてＲ４としてはＲ２の例が挙げられる。Furthermore, when mixing the alkoxysilane and silica sol, the following general formula [II] R"+aS1 (OR')4-111 "'"・[I
I ] (wherein R3 represents an alkyl group, alkenyl group or aryl group that may have a substituent, R4 represents an alkyl group, acyl group or aryl group, and m is 2
or an integer of 3) may be used in combination with a small amount of monoalkoxysilane, dialkoxysilane, or a mixture thereof.
] As an example of R3 in the formula, an example of R1 in the above formula [11] is
An example of R4 is R2.
本発明のコーティング用組成物の塗布法としては、ディ
ッピング、スピンコード、ロールコート、転写印刷、刷
毛塗り、スプレー等、通常使用される塗布法を用いるこ
とが出来る６〔作 用〕
［Ｒ１式で表されるアルコキシシランを、湿式粉砕法に
よらないで得られたシリカゾルの存在下に加水分解及び
縮合反応させた場合、コロイダルシリカそのものの乏し
い皮膜性によって、得られたコーテイング液の性能はさ
ほど向上せず、膜厚が厚いとクラックが生じる。それに
対し、本発明で用いられる湿式粉砕法によるシリカゾル
はコロイダルシリカの形状が不定形であって、乾燥膜に
クラックを生じさせない性質を有している。このような
シリカゾルを用いて得られる本発明の組成物ではそのシ
リカゾルが顕著に作用し、厚い膜を形成させてもその塗
膜に耐クラツク性を与える。As a method for applying the coating composition of the present invention, commonly used methods such as dipping, spin cord, roll coating, transfer printing, brushing, and spraying can be used.6 [Function] [For R1 formula] When the expressed alkoxysilane is subjected to a hydrolysis and condensation reaction in the presence of a silica sol obtained without using a wet grinding method, the performance of the resulting coating liquid is not significantly improved due to the poor film properties of colloidal silica itself. If the film is not thick enough, cracks will occur. On the other hand, in the silica sol produced by the wet pulverization method used in the present invention, the colloidal silica has an amorphous shape and has the property of not causing cracks in the dried film. In the composition of the present invention obtained using such a silica sol, the silica sol acts significantly and provides crack resistance to the coating film even if a thick film is formed.
珪弗化水素酸又はそのアンモニウム塩を水性媒体中でア
ンモニアと反応させることにより生成した湿式粉砕法に
よるシリカ微粉を、湿式粉砕することにより得られるシ
リカゾルは、その固形分濃度が高くてち粘度が低い性質
を有しており、そのシリカゾルとアルコキシシランを用
いて得られるコーティング用組成物ち、高５ｉＯｚ濃度
でありながら低粘度を示す、又、上記湿式法によるシリ
カ微粉より得られるシリカゾルを用いたために、組成物
中には金属、ハロゲン等の不純物が少ない。Silica sol obtained by wet-pulverizing silica fine powder produced by wet-pulverizing method by reacting hydrofluorosilicic acid or its ammonium salt with ammonia in an aqueous medium has a high solid content concentration and a low viscosity. The coating composition obtained using the silica sol and alkoxysilane has a low viscosity despite having a high 5iOz concentration. Moreover, there are few impurities such as metals and halogens in the composition.
シリカゾルの分散媒が有機溶媒であるシリカゾルを用い
ると、アルコキシシランとの混合時、混合物の分離及び
不均一化が起こらない。When a silica sol whose dispersion medium is an organic solvent is used, separation and non-uniformity of the mixture do not occur when mixed with an alkoxysilane.
又、加水分解に必要な水の量を正確に加えることが出来
る。Also, the amount of water required for hydrolysis can be added accurately.
上記一般式［Ｎで示されるアルコキシシランのアルコキ
シ基４−ｎモルに対して、 ０．５から５倍モルの水を
用いて加水分解する事により、本発明のコーティング用
組成物は優れた塗布性と、保存安定性を示す。加水分解
に用いる水の量が上記比率０．５より少ないとアルコキ
シシランの加水分解及び縮合反応が不十分となり、成膜
性、塗布膜の強度等が向上しない。By hydrolyzing the 4-n mol of alkoxy group of the alkoxysilane represented by the general formula [N] using 0.5 to 5 times the mol of water, the coating composition of the present invention has excellent coating properties. properties and storage stability. If the amount of water used for hydrolysis is less than the above ratio of 0.5, the hydrolysis and condensation reactions of the alkoxysilane will be insufficient, and the film formability, strength of the coating film, etc. will not improve.
方、上記比率の５倍より多くなると、コーテイング液の
貯蔵安定性が乏しくなり、且っ成膜時に塗膜のはじき等
を起こす。On the other hand, if the ratio is more than 5 times the above ratio, the storage stability of the coating liquid will be poor, and the coating will repel during film formation.
本発明の組成物は、５ｉＯｉ？１度０．１〜５０重量％
の範囲に於いて良好な塗布性を示す、 ３１０２濃度が
０．１重量％より少ないと一回の塗布により得られる塗
布膜の厚みが薄くなり、所定の厚みを有する塗膜を得る
ためには多数回の塗布が必要となり、不経済になるうえ
ピンホールが発生しやすい、また、ＳｉＯ□濃度が５０
重量％を越えると、組成物の粘度が高くなり、均一な塗
膜を得ることか困難になり、又、貝？蔵安定性も乏しく
なる。The composition of the present invention has 5iOi? 1 degree 0.1-50% by weight
If the 3102 concentration is less than 0.1% by weight, the thickness of the coating film obtained by one application will be thinner, and in order to obtain a coating film with a predetermined thickness, It requires multiple coatings, which is uneconomical, pinholes are likely to occur, and the SiO□ concentration is 50%.
If the percentage by weight is exceeded, the viscosity of the composition becomes high, making it difficult to obtain a uniform coating film, and causing shellfish? Storage stability will also be poor.
アルコキシシラン由来のＳｉＯ□分１００重量部に対し
てシリカゾル由来のＳｉＯ□分が５重量部より少ないと
塗膜の耐クラツク性が劣り、又４００重量部を越えた場
合には、塗膜の結合力が不足する為に、耐クラツク性、
機械的強度、基板への密着力等が低下し、塗膜に割れが
生じたり、塗膜の剥離等が発生する。If the content of SiO□ derived from silica sol is less than 5 parts by weight per 100 parts by weight of SiO□ derived from alkoxysilane, the crack resistance of the coating film will be poor, and if it exceeds 400 parts by weight, the coating film will be bonded. Due to lack of force, crack resistance,
Mechanical strength, adhesion to the substrate, etc. decrease, and the coating film may crack or peel.
アルコキシシランとシリカゾルを混合する際は、加水分
解に必要な水と触媒とシリカゾルの混合物をアルコキシ
シランの有機溶媒溶液に加えるという好ましい方法によ
って、アルコキシシランの様な親油性の物質にシリカゾ
ルを加えた場合に起こるゾルの凝集を防ぐ事ができ、更
にシリカゾルが分散媒として水を多量に含む場合でも、
加水分解時の反応系の不均一化を防ぐ事が出来る。When mixing alkoxysilanes and silica sol, the preferred method is to add the silica sol to a lipophilic material such as an alkoxysilane by adding the mixture of water, catalyst, and silica sol required for hydrolysis to a solution of the alkoxysilane in an organic solvent. It can prevent sol agglomeration that occurs in some cases, and even when silica sol contains a large amount of water as a dispersion medium,
It is possible to prevent the reaction system from becoming heterogeneous during hydrolysis.
加水分解速度の異なるアルコキシシラン、例えばＣＨｓ
Ｓｉ （ＯＣＨ３） ｓと Ｓｉ （ＯＣＨ２ＣＨ，Ｃ
Ｈ，ＣＨ，）、の２種を組み合わせて用いる場合には、
加水分解速度差を解消し、均一反応を進めるため、５０
℃以上の温度が好ましい。Alkoxysilanes with different hydrolysis rates, e.g. CHs
Si (OCH3)s and Si (OCH2CH,C
When using two types of H, CH, ) in combination,
In order to eliminate the difference in hydrolysis rate and proceed with a uniform reaction, 50
Temperatures of 0.degree. C. or higher are preferred.
加水分解反応に引き続（、縮合反応を行うことによって
、塗膜の耐クラツク性、機械的強度は向上する。縮合反
応の時間は温度により異なり、低温では長時間を要する
が、高温では短時間で良い、例えば８０℃の場合、１時
間から５時間程度が適当である。１時間以内では十分な
性能が得られず、又５時間以上行ってちそれ以上性能が
向上しないばかりかコーテイング液の貯蔵安定性が乏し
くなる。Following the hydrolysis reaction, the crack resistance and mechanical strength of the coating film are improved by carrying out the condensation reaction. The time for the condensation reaction varies depending on the temperature; it takes a long time at low temperatures, but it takes a short time at high temperatures. For example, in the case of 80℃, about 1 to 5 hours is appropriate.Sufficient performance may not be obtained within 1 hour, and if the temperature is maintained for more than 5 hours, not only will the performance not improve any further, but the coating liquid will deteriorate. Poor storage stability.
【実施例］
本発明を具体的に説明するために、実施例を述べる。な
お、本発明はこれら実施例によって何ら制限されるもの
ではない。[Example] In order to specifically explain the present invention, an example will be described. Note that the present invention is not limited in any way by these Examples.
（シリカゾルの製造）
撹拌機と温度計をつけた１００２反応容器に２５％アン
モニア水２．７２ｋｇと１５％弗化アンモニウム水溶液
９．８６ｋｇを仕込み、これに２０％珪弗化水素酸水溶
液１４．４ｋｇを投入した１反応部度は２５°Ｃから４
０℃に上昇し、弗化アンモニウムを含有する珪弗化アン
モニウム水溶液を得た。(Manufacture of silica sol) 2.72 kg of 25% ammonia water and 9.86 kg of 15% aqueous ammonium fluoride solution were placed in a 1002 reaction vessel equipped with a stirrer and a thermometer, and 14.4 kg of 20% aqueous hydrosilicic acid solution was added to this. The temperature of 1 reaction part injected is 4 from 25°C.
The temperature rose to 0°C, and an aqueous ammonium fluorosilicate solution containing ammonium fluoride was obtained.
この溶液中に２５％アンモニア水１６．３２ｋｇを１５
分かけて添加した。反応温度は５５℃まで上昇した。更
にこれに２０％珪弗化水素酸水溶液１４．４ｋｇを３０
分間添加し、反応を終了した。この反応により得られた
析出シリカを含有するスラリーが得られた。Add 16.32 kg of 25% ammonia water to this solution.
Added in portions. The reaction temperature rose to 55°C. Furthermore, 14.4 kg of 20% hydrosilicofluoric acid aqueous solution was added to this for 30 minutes.
The reaction was completed. A slurry containing precipitated silica was obtained by this reaction.
この得られたシリカパウダースラリーをフィルタープレ
スを用いて加圧濾過しシリカパウダーのウェットケーキ
を得た。このウェットケーキを水と少量の酸水溶液で洗
浄した後１１０℃で加熱乾燥し、シリカパウダーのドラ
イケーキ２．４６ｋｇを得た。これを粉砕し、高純度シ
リカパウダーとして得られたシリカパウダー３００ｇを
エチルアルコール７００ｇに分散させた後、５ｍｍφの
ジルコニアビーズを用い、回転数８Ｏｒｐｍで１２時間
回転ボールミルで湿式粉砕し、エチルアルコール分散シ
リカゾルを得た。このゾルの動的光散乱法による粒子径
は２９０ｍμであった。The obtained silica powder slurry was filtered under pressure using a filter press to obtain a wet cake of silica powder. This wet cake was washed with water and a small amount of acid aqueous solution, and then heated and dried at 110°C to obtain 2.46 kg of a dry cake of silica powder. After pulverizing this and dispersing 300 g of silica powder obtained as high purity silica powder in 700 g of ethyl alcohol, wet pulverization was carried out in a rotary ball mill using zirconia beads of 5 mm diameter at a rotation speed of 8 orpm for 12 hours to obtain ethyl alcohol-dispersed silica sol. I got it. The particle diameter of this sol was determined by dynamic light scattering to be 290 mμ.
（塗布液の製造）
冷却管、滴下ロートを備えた反応フラスコに表−１記載
の組成でアルコキシシランとエチルアルコールを投入し
撹拌混合した。この混合液に、上記エチルアルコール分
散シリカゾルと水と触媒としての３５重量％塩酸との混
合物を、３０分かけて滴下した０滴下後、撹拌下、還流
温度で２時間保持した後、室温まで冷却し、下記の表−
１記載の固形分濃度を有する本発明塗布液Ｎｏ、 １〜
ｌＯを得た０表−１にその仕込み組成と反応条件を示す
。(Production of coating liquid) Alkoxysilane and ethyl alcohol having the composition shown in Table 1 were charged into a reaction flask equipped with a cooling tube and a dropping funnel, and mixed with stirring. To this mixture, a mixture of the ethyl alcohol-dispersed silica sol, water, and 35% by weight hydrochloric acid as a catalyst was added dropwise over 30 minutes. After the dropwise addition, the mixture was kept at reflux temperature for 2 hours with stirring, and then cooled to room temperature. and the table below −
Coating liquid No. 1 of the present invention having a solid content concentration described in 1-
Table 1 shows the charging composition and reaction conditions.
試験例１〜１３
実施例の表−１塗布液Ｎｏ、 ｌ ＝ １０の塗布液を
、デイツプ法を用いて一定の速度で引上げる事によりス
ライドグラスに塗布し、室温で乾燥後５００℃で３０分
焼成した。引上げ速度及び焼成結果を下記の表−２に示
す。Test Examples 1 to 13 Coating solution No. 1 in Examples, l = 10, was applied to a slide glass by pulling up at a constant speed using the dip method, dried at room temperature, and then heated at 500°C for 30 minutes. Fired separately. The pulling speed and firing results are shown in Table 2 below.
焼成塗膜について試験した、表−２中に記載の項目につ
いて説明する。The items listed in Table 2 that were tested for the fired coating film will be explained.
硬度 ＪＩＳ Ｋ５４００ 鉛筆硬度試験によ
り表面硬度を測定した。Hardness Surface hardness was measured by JIS K5400 pencil hardness test.
クラック 目視により観察し、クラックの有無を判定し
た。Cracks The presence or absence of cracks was determined by visual observation.
密着強度 粘着テープ剥離試験により塗膜の剥離の有無
を調べた。全く剥離が観察
されない場合は○、一部剥離が認め
られた物については△とした。Adhesion strength The presence or absence of peeling of the coating film was examined by adhesive tape peeling test. When no peeling was observed at all, it was rated ◯, and when some peeling was observed, it was rated △.
外観（目視により観察した透明度）
透明性微白色・・・塗膜は透明であるが僅かに白色が認
められる。Appearance (transparency observed visually) Transparency: Slight white color...The coating film is transparent, but a slight white color is observed.
透明性乳白色・・・塗膜は透明で有るが上記より白色度
が強い。Transparent milky white...The coating is transparent, but the whiteness is stronger than the above.
半透明性乳白色・・・塗膜は光は通すが透明性が低下し
、白色を呈している。Translucent milky white...The coating film allows light to pass through, but its transparency is reduced and it appears white.
乳白色・・・塗膜は不透明な白色である。Milky white...The coating film is opaque white.
得られた塗膜の中で透明性乳白色、半透明性乳白色のち
のの表面状態を観察したところ、深さ約０．３μの細か
な凹凸を有しており、光の乱反射により乳白色を、呈し
ている事が分かった。When we observed the surface condition of the resulting coating film, which was transparent and milky white, and then translucent and milky white, we found that it had fine irregularities with a depth of about 0.3 μm, and the surface became milky white due to the diffused reflection of light. I found out that
筬腹艶」
実施例の表−１塗布液Ｎｏ、 ８の塗布液を、銅板にデ
イツプ法で４５ｃｍ／分の速度で引上げ、塗布し、室温
で乾燥後５００℃で３０分焼成した。Coating liquid No. 8 in Table 1 of Examples was drawn and applied onto a copper plate at a speed of 45 cm/min, dried at room temperature, and then baked at 500°C for 30 minutes.
焼成後の銅板は、コーテイング膜が若干白濁しているも
のの金属色を失わず熱酸化を受けていなかった。Although the coating film of the fired copper plate was slightly cloudy, it did not lose its metallic color and was not thermally oxidized.
汰１１Ｌ■
実施例の表−１塗布液Ｎｏ、１０の塗布液を、ポリカー
ボネート板にデイツプ法で４５ｃｍ／分の速度で引上げ
、塗布し、室温で乾燥後１２０℃で３０分乾燥した。約
４μの半透明乳白色乾燥塗膜が得られ、表面硬度は鉛筆
硬度で７Ｈであった。Table 11L of Examples Table 1 Coating liquid No. 10 was applied onto a polycarbonate plate using a dip method at a rate of 45 cm/min, dried at room temperature, and then dried at 120°C for 30 minutes. A translucent milky white dry coating film with a thickness of about 4 μm was obtained, and the surface hardness was 7H on a pencil hardness scale.
ま艷監長
実施例の表−１塗布液Ｎｏ、８の塗布液を、スライドグ
ラスにデイツプ法で４５ｃｍ／分の速度で引上げ、塗布
し、室温で乾燥後５００℃で３０分焼成し、半透明乳白
色の塗膜を形成させた。Coating liquid No. 8 in Table 1 of Superintendent's Example was applied onto a slide glass using the dip method at a speed of 45 cm/min. After drying at room temperature, it was baked at 500°C for 30 minutes. A transparent milky white coating was formed.
このものに、ＳｉＯ□コーティング液（、−ツサン無機
コート剤 ＮＴＬ−５００７）をデイツプ法で４５ｃｍ
／分の速度で引上げて重ね塗りし５００℃で焼成したと
ころ、表面の凹凸が埋まり無色透明な塗膜が得られた。Apply SiO□ coating liquid (-TSAN inorganic coating agent NTL-5007) to this material by dip method for 45 cm.
When the coating was pulled up at a speed of 1/2 min, overcoated and baked at 500°C, the surface irregularities were filled in and a colorless and transparent coating film was obtained.
（比較例）
希釈水ガラスから陽イオン交換法により得られた粒子径
１８０ｍμの球状コロイダルシリカのメタノール分散シ
リカゾルを、実施例の表−１塗布液Ｎｏ、 ４において
用いたシリカゾルの代わりに用いた以外は、実施例と同
様にして塗布液を製造した。この塗布液から、試験例６
と同様にして塗膜を形成させたところ、塗膜の割れが発
生し、スライドグラスより剥離した。(Comparative Example) A methanol-dispersed silica sol of spherical colloidal silica with a particle size of 180 mμ obtained from diluted water glass by a cation exchange method was used instead of the silica sol used in Table 1 Coating Solution No. 4 of the Example. A coating liquid was produced in the same manner as in the example. From this coating liquid, Test Example 6
When a coating film was formed in the same manner as above, the coating cracked and peeled off from the slide glass.
そこで引上げ速度を変更して遅くしたところ割れの無い
塗膜が得られたが、クラックの無い塗膜を得る為の膜厚
は、１．０μ以下を必要とした。Therefore, when the pulling speed was changed to make it slower, a crack-free coating film was obtained, but the film thickness needed to be 1.0 μm or less in order to obtain a crack-free coating film.
〔発明の効果Ｊ
本発明のコーティング用組成物は、長期間にわたって安
定な塗布性を維持し、耐クラツク性、密着強度、機械強
度等に優れた厚い塗膜を形成せしめる。[Effect of the Invention J The coating composition of the present invention maintains stable coating properties over a long period of time and forms a thick coating film with excellent crack resistance, adhesion strength, mechanical strength, etc.
又、−回の塗布により、クラック、ピンホールの無い、
３μ以上の厚みの塗膜が得られるため、基板の表面平滑
化、金属の防食等に適している。Also, by applying the coating twice, there are no cracks or pinholes.
Since a coating film with a thickness of 3μ or more can be obtained, it is suitable for smoothing the surface of substrates, preventing corrosion of metals, etc.
又、コーテイング液は、金属、ハロゲン等の不純物含有
量が少ないため、電子材料等に用いるのに好適である。Furthermore, since the coating liquid has a low content of impurities such as metals and halogens, it is suitable for use in electronic materials and the like.
Claims (2)
［ I ］（式中、Ｒ＾１は置換基を有することもあるア
ルキル基、アルケニル基又はアリール基を 表し、Ｒ＾２はアルキル基、アシル基又はアリール基を
表し、そしてｎは０または１の 整数を表す。） で示されるアルコキシシランの１種又は２種以上をＳｉ
Ｏ＿２として１００重量部と、湿式法で得られたシリカ
微粉を湿式粉砕することにより得られたシリカゾルをＳ
ｉＯ＿２として５〜４００重量部の割合に混合し、上記
アルコキシシランを加水分解及び縮合させてなるコーテ
ィング用組成物。(1) The following general formula [I] R^1_nSi(OR^2)_4_-_n...
[I] (wherein R^1 represents an alkyl group, alkenyl group, or aryl group that may have a substituent, R^2 represents an alkyl group, acyl group, or aryl group, and n is 0 or 1 (represents an integer of ).
S
A coating composition prepared by hydrolyzing and condensing the alkoxysilane described above by mixing 5 to 400 parts by weight of iO_2.
ム塩を水性媒体中でアンモニアと反応させることにより
生成した析出シリカを、上記水性媒体から分離し、当該
析出シリカの濃度２〜５０重量％において湿式粉砕する
ことにより得られたものである、請求項１記載の コーティング用組成物。(2) The silica sol separates precipitated silica produced by reacting hydrosilicic acid or its ammonium salt with ammonia in an aqueous medium from the aqueous medium, and at a concentration of 2 to 50% by weight of the precipitated silica. The coating composition according to claim 1, which is obtained by wet grinding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5550790A JPH03258878A (en) | 1990-03-07 | 1990-03-07 | Coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5550790A JPH03258878A (en) | 1990-03-07 | 1990-03-07 | Coating composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03258878A true JPH03258878A (en) | 1991-11-19 |
Family
ID=13000589
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5550790A Pending JPH03258878A (en) | 1990-03-07 | 1990-03-07 | Coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03258878A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090873A (en) * | 1995-04-21 | 2000-07-18 | Matsushita Electric Works, Ltd. | Coating resin composition containing a hydrolyzable organosilane and an acrylic resin |
| JP2007138144A (en) * | 2005-10-18 | 2007-06-07 | Hitachi Chem Co Ltd | Silica-based coated film-forming composition |
| JP2007268344A (en) * | 2006-03-30 | 2007-10-18 | Dainippon Toryo Co Ltd | Old coating film-repairing method |
| JP2007268343A (en) * | 2006-03-30 | 2007-10-18 | Dainippon Toryo Co Ltd | Coating film-depositing method |
| JP2009161772A (en) * | 2007-07-10 | 2009-07-23 | Aica Kogyo Co Ltd | Composition, transfer sheet, melamine decorative board, and method for manufacturing melamine decorative board |
| WO2014005272A1 (en) * | 2012-07-03 | 2014-01-09 | 蚌埠鑫源石英材料有限公司 | Silicon dioxide powder material and preparation process therefor |
-
1990
- 1990-03-07 JP JP5550790A patent/JPH03258878A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6090873A (en) * | 1995-04-21 | 2000-07-18 | Matsushita Electric Works, Ltd. | Coating resin composition containing a hydrolyzable organosilane and an acrylic resin |
| US6329456B1 (en) | 1995-04-21 | 2001-12-11 | Matsushita Electric Works, Ltd. | Coating resin composition containing hydrolyzable organosilane, acrylic resin and polyorganosiloxane |
| JP2007138144A (en) * | 2005-10-18 | 2007-06-07 | Hitachi Chem Co Ltd | Silica-based coated film-forming composition |
| JP2007268344A (en) * | 2006-03-30 | 2007-10-18 | Dainippon Toryo Co Ltd | Old coating film-repairing method |
| JP2007268343A (en) * | 2006-03-30 | 2007-10-18 | Dainippon Toryo Co Ltd | Coating film-depositing method |
| JP4674815B2 (en) * | 2006-03-30 | 2011-04-20 | 大日本塗料株式会社 | Repair method of old paint film |
| JP2009161772A (en) * | 2007-07-10 | 2009-07-23 | Aica Kogyo Co Ltd | Composition, transfer sheet, melamine decorative board, and method for manufacturing melamine decorative board |
| WO2014005272A1 (en) * | 2012-07-03 | 2014-01-09 | 蚌埠鑫源石英材料有限公司 | Silicon dioxide powder material and preparation process therefor |
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