JPH023468A - Coating composition - Google Patents
Coating compositionInfo
- Publication number
- JPH023468A JPH023468A JP63145315A JP14531588A JPH023468A JP H023468 A JPH023468 A JP H023468A JP 63145315 A JP63145315 A JP 63145315A JP 14531588 A JP14531588 A JP 14531588A JP H023468 A JPH023468 A JP H023468A
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- silica
- coating composition
- weight
- pts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000008199 coating composition Substances 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000002245 particle Substances 0.000 claims abstract description 59
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 55
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 4
- 239000010419 fine particle Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 230000002209 hydrophobic effect Effects 0.000 claims description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- 229910000077 silane Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 230000004313 glare Effects 0.000 abstract description 4
- 230000005661 hydrophobic surface Effects 0.000 abstract description 3
- 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
- 238000000576 coating method Methods 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002928 artificial marble Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 244000269722 Thea sinensis Species 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000006468 Thea sinensis Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000020279 black tea Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- 235000009569 green tea Nutrition 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 235000009161 Espostoa lanata Nutrition 0.000 description 1
- 240000001624 Espostoa lanata Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- -1 and among these Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- HZYAPKYFYYWOKA-UHFFFAOYSA-N tetrahexyl silicate Chemical compound CCCCCCO[Si](OCCCCCC)(OCCCCCC)OCCCCCC HZYAPKYFYYWOKA-UHFFFAOYSA-N 0.000 description 1
- KCTGOQZIKPDZNK-UHFFFAOYSA-N tetrapentyl silicate Chemical compound CCCCCO[Si](OCCCCC)(OCCCCC)OCCCCC KCTGOQZIKPDZNK-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はプラスチック製品、ガラス製品、金属製品、木
材製品等に耐擦傷性、耐候性、耐熱性、耐汚染性等を付
与すると同時に、製品表面の光沢度を制御し、グレア防
止効果を付与する目的で、製品の表面に塗布されるコー
ティング組成物に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention imparts scratch resistance, weather resistance, heat resistance, stain resistance, etc. to plastic products, glass products, metal products, wood products, etc. It relates to a coating composition applied to the surface of a product for the purpose of controlling the surface gloss and imparting an anti-glare effect.
［従来の技術］
各種物品表面のグレア防止を図る方法、すなわち、物品
表面の艶消し加工法としては、砂等を吹き付けて、ある
いは研磨剤で研磨して物品表面に凹凸や傷を形成させる
機械的方法がある。[Prior Art] A method for preventing glare on the surface of various articles, that is, a matting method for the surface of the article, is to use a machine that sprays sand or the like or polishes with an abrasive to form unevenness or scratches on the surface of the article. There is a method.
しかし、この方法では物品表面に耐擦傷性、耐候性、耐
汚染性等の特性を付与することができない。However, this method cannot impart properties such as scratch resistance, weather resistance, and stain resistance to the surface of the article.
一方、物品を塗装することでこれに耐擦傷性、耐候性、
耐汚染性等の特性を与え、同時にグレア防止効果を付与
することも従来から行われていて、これに使用される塗
膜形成用組成物としては、シリカ粉末を配合した塗料や
オルガノアルコキシシランの部分縮合物にコロイダルシ
リカを配合した組成物が知られている（特開昭５５−１
２１０７号、同５９−６８３７７号参照）、シかしなが
ら、シリカ粉末を配合した従来の塗料は、シリカ粉末が
沈降、凝集しやすいため分散安定性に欠け、またその塗
膜は乾燥時にシリカ粒子が凝集してしまう傾向があるた
め、光沢度の均一なむらのない乾燥塗膜を得ることが難
しい欠点がある。On the other hand, painting an item gives it scratch resistance, weather resistance,
It has been conventionally used to impart properties such as stain resistance and at the same time anti-glare effects, and coating compositions used for this purpose include coatings containing silica powder and organoalkoxysilane. A composition in which colloidal silica is blended with a partial condensate is known (Japanese Unexamined Patent Publication No. 55-1
2107, No. 59-68377), conventional paints containing silica powder lack dispersion stability because the silica powder tends to settle and aggregate, and the coating film dries to form silica particles. It has the disadvantage that it is difficult to obtain a dry coating film with uniform gloss and no unevenness because of its tendency to agglomerate.
また、オルガノアルコキシシランの部分縮合物にコロイ
ダルシリカを配合した従来の組成物は、コロイダルシリ
カの配合量をかなり多くしなければ、塗膜に満足なグレ
ア防止効果を持たせることができず、コロイダルシリカ
の配合量を増大させると、組成物の分散安定性が低下す
る上、光沢度の均一なむらのない塗膜を形成させること
が困難になる不都合がある。これに加えて。In addition, with conventional compositions in which colloidal silica is blended with a partial condensate of organoalkoxysilane, the coating film cannot have a satisfactory anti-glare effect unless the amount of colloidal silica is considerably increased. When the amount of silica added is increased, the dispersion stability of the composition decreases, and there are disadvantages in that it becomes difficult to form a uniform coating film with uniform gloss. In addition to this.
この組成物の塗膜では満足な耐汚染性を期待できない難
点もある。There is also the drawback that a coating film of this composition cannot be expected to have satisfactory stain resistance.
ところで、天然大理石に近い質感、素材感を備えた材料
として、所謂人造大理石が知られており、なかでも不飽
和ポリエステル樹脂及びアクリル樹脂に、水酸化マグネ
シウムやアルミナ等を配合した人造大理石が良く知られ
ている。By the way, so-called artificial marble is known as a material with a texture and feel similar to natural marble, and among these, artificial marble made by blending magnesium hydroxide, alumina, etc. with unsaturated polyester resin and acrylic resin is well known. It is being
しかし１人造天理石の表面は、一般に耐擦傷性、耐熱性
、耐汚染性が貧弱であるので、これを改善する目的でそ
の表面をプラスチック製品用塗料で塗装するのが通例で
ある。しかし、この目的に使用される従来のプラスチッ
ク製品用塗料は、人造大理石との密着性が充分でないば
かりでなく、被膜の耐擦傷性、耐熱性、耐汚染性にも不
満が残り、さらに被膜の光沢にむらが出やすい欠点があ
る。However, the surface of artificial astronomical stone generally has poor scratch resistance, heat resistance, and stain resistance, so in order to improve these properties, it is customary to paint the surface with a paint for plastic products. However, conventional paints for plastic products used for this purpose not only do not have sufficient adhesion to artificial marble, but also leave unsatisfied with the scratch resistance, heat resistance, and stain resistance of the coating. The drawback is that the gloss tends to be uneven.
ここに於いて、本発明者等は特定なトリアルコキシシラ
ンとテトラアルコキシランの部分縮合物に、シリカ微粒
子を配合したコーティング組成物が、それも比較的平均
粒径が大きいシリカ微粒子と、疎水性でしかも比較的平
均粒径が小さいシリカ微粒子を配合したコーティング組
成物が、人造大理石を含む各種のプラスチック製品、ガ
ラス製品、金属製品、木材製品等に対して優れた密着性
を有し、しかもそれらの表面に形成される塗膜は耐擦傷
性、耐候性、耐熱性、耐汚染性等価れた特性を備ている
と同時に、光沢度、グレア防止性の点でもむらのない均
一性を備えていることを見出した。Here, the present inventors have developed a coating composition in which fine silica particles are blended with a partial condensate of a specific trialkoxysilane and a tetraalkoxylan, which also has a relatively large average particle size and a hydrophobic coating composition. Moreover, the coating composition containing fine silica particles with a relatively small average particle size has excellent adhesion to various plastic products including artificial marble, glass products, metal products, wood products, etc. The coating film formed on the surface has properties such as scratch resistance, weather resistance, heat resistance, and stain resistance, as well as uniformity in terms of gloss and anti-glare properties. I found out that there is.
［発明の構成］
本発明のコーティング組成物は、必須成分として、
（ａ）一般式：Ｒ８１（ＯＲ″）ｉ［Ｒ：炭素数１〜６
の炭化水素基、Ｒ１：炭素数１〜６のアルキル基〕で示
されるトリアルコキシシラン１００重量部と、一般式：
Ｓ ｉ （ＯＲ”）４（Ｒ” ：炭素数１〜６のアル
キル基）で示されるテトラアルコキシシラン２０〜１３
０重量部とからなる有機ケイ素化合物の部分縮合物。[Structure of the Invention] The coating composition of the present invention has, as an essential component, (a) General formula: R81(OR″)i [R: carbon number 1 to 6
hydrocarbon group, R1: alkyl group having 1 to 6 carbon atoms] and 100 parts by weight of trialkoxysilane represented by the general formula:
Tetraalkoxysilane 20-13 represented by S i (OR")4 (R": alkyl group having 1 to 6 carbon atoms)
A partial condensate of an organosilicon compound consisting of 0 parts by weight.
（ｂ）平均粒径が０．１μｍ以上のシリカ微粒子（ｃ）
平均粒径が前記（ｂ）のシリカ微粒子より小さく、しか
も表面が疎水化されているシリカ微粒子
を含有することを特徴とする。(b) Silica fine particles with an average particle size of 0.1 μm or more (c)
It is characterized by containing silica fine particles having a smaller average particle diameter than the silica fine particles of (b) above and whose surfaces are hydrophobicized.
上記トリアルコキシシランＲＳ ｘ （ＯＲ’ ）３に
於いて、Ｒはメチル基、エチル基、プロピル基、ブチル
基、ペンチル基、ヘキシル基、ビニル基、フェニル基等
で例示される炭素数１〜６の炭化水素基のいずれでもよ
く、またＲ１はメチル基、エチル基、プロピル基、ブチ
ル基、ペンチル基、ヘキシル基等で例示される炭素数１
〜６のアルキル基のいずれでもよい、従って１本発明の
トリアルコキシシランは、メチルトリメトキシシラン、
メチルトリエトキシシラン、エチルトリメトキシシラン
、エチルトリエトキシシラン、ｎ−プロピルトリメトキ
シシラン、ｎ−プロピルトリエトキシシラン、ｉ−プロ
ピルトリメトキシシラン、ｉ−プロピルトリエトキシシ
ラン、ビニルトリメトキシシラン、ビニルトリエトキシ
シラン、フェニルトリメトキシシラン等が包含される０
本発明では上記の各トリアルコキシシランを２種以上混
合して使用しても差し支えない。In the above trialkoxysilane RS x (OR')3, R has 1 to 6 carbon atoms, exemplified by methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, vinyl group, phenyl group, etc. may be any hydrocarbon group, and R1 has 1 carbon number, exemplified by methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc.
The trialkoxysilane of the present invention, which can be any of the following alkyl groups, is therefore methyltrimethoxysilane,
Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane Includes ethoxysilane, phenyltrimethoxysilane, etc.0
In the present invention, two or more of the above trialkoxysilanes may be used in combination.
テトラアルコキシシランＳ ｉ （ＯＲ”）４に於ける
Ｒ２は、メチル基、エチル基、プロピル基、ブチル基、
ペンチル基、ヘキシル基等で例示される炭素数１〜６の
直鎖又は分岐鎖アルキル基のいずれでもよい、従って、
直鎖アルキル基を有するテトラアルコキシシランを例示
すれば、テトラメトキシシラン、テトラエトキシシラン
、テトラプロポキシシラン、テトラブトキシシラン、テ
トラペンチルオキシシラン、テトラヘキシルオキシシラ
ン等を挙げることができる。そして、これらテトラアル
コキシシランは２種以上混合して使用することもできる
。R2 in the tetraalkoxysilane S i (OR")4 is a methyl group, an ethyl group, a propyl group, a butyl group,
It may be any straight chain or branched alkyl group having 1 to 6 carbon atoms, exemplified by pentyl group, hexyl group, etc.; therefore,
Examples of tetraalkoxysilanes having a linear alkyl group include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetrapentyloxysilane, and tetrahexyloxysilane. Two or more of these tetraalkoxysilanes can also be used in combination.
本発明ψコーティング組成物に使用きれる部分縮合物は
、上記したトリアルコキシシランとテトラアルコキシシ
ランを後述する割合で混合し、この混合物を加水分解す
る方法により、あるいはまたトリアルコキシシランとテ
トラアルコキシシランを別々に加水分解し、しかる後そ
れぞれの加水分解生成物を混合する方法によりで調製す
ることができる。しかし、予めテトラアルコキシシラン
を加水分解することで、平均分子量が好ましくは３００
〜７００程度の部分縮合物を調製し、この部分縮合物又
はこれに相当する市販品を、所定の割合でトリアルコキ
シシランと混合し、これを加水分解することが好ましい
。The partial condensate that can be used in the ψ coating composition of the present invention can be obtained by mixing the above-mentioned trialkoxysilane and tetraalkoxysilane in the ratios described below and hydrolyzing this mixture, or alternatively by mixing the trialkoxysilane and tetraalkoxysilane. It can be prepared by separately hydrolyzing and then mixing the respective hydrolyzed products. However, by hydrolyzing the tetraalkoxysilane in advance, the average molecular weight is preferably 300.
It is preferable to prepare about 700 partial condensates, mix this partial condensate or a commercially available product equivalent thereto with trialkoxysilane in a predetermined ratio, and hydrolyze this.
いずれの方法を採用する場合でも、トリアルコキシシラ
ンとテトラアルコキシシランとの混合割合は、前者１０
０重量部当り後者２０〜１３０重量部、好ましくは３５
〜７０重量部であることを可とする。後者が２０重量部
未満では被膜の耐擦傷性、耐熱水性が低下し、１３０重
量部を越えると、被膜にクラックが入り易く、またコー
ティング組成物自体の安定性が劣化するからである。加
水分解は適当な有機溶媒中で、水及び加水分解触媒の存
在下に、約１０〜９０℃、好ましくは約２０〜８０℃の
温度範囲で行おれる。この場合の有機溶媒には、アルコ
ール類、エーテル類、エステル類、グリコール類が使用
でき、加水分解触媒としては各種の無機酸又は有機酸が
使用可能である。No matter which method is adopted, the mixing ratio of trialkoxysilane and tetraalkoxysilane is 10% of the former.
20 to 130 parts by weight of the latter per 0 parts by weight, preferably 35 parts by weight
~70 parts by weight is allowed. If the latter is less than 20 parts by weight, the abrasion resistance and hot water resistance of the coating will decrease, and if it exceeds 130 parts by weight, the coating will tend to crack and the stability of the coating composition itself will deteriorate. Hydrolysis is carried out in a suitable organic solvent in the presence of water and a hydrolysis catalyst at a temperature range of about 10-90°C, preferably about 20-80°C. In this case, alcohols, ethers, esters, and glycols can be used as the organic solvent, and various inorganic acids or organic acids can be used as the hydrolysis catalyst.
本発明のコーティング組成物の第２の必須成分はシリカ
微粒子であって、本発明ではシリカ微粒子として平均粒
径が０．１μｍ以上のシリカ微粒子（以下大粒径シリカ
と言う）と、表面が疎水化され、平均粒径が前記の大粒
径シリカより小さいシリカ微粒子（以下小粒径シリカと
言う）を併用する。一般にシリカ微粒子はその表面に活
性な水酸基を持っており、粒径が小さくなる程その表面
活性が高くなる。従って、粒径の小さい粒子程分散媒中
で凝集し易い、大粒径のシリカと小粒径のシリガが共存
すると、大粒径のシリカの水酸基と小粒径のシリカの水
酸基が脱水縮合し、大粒径のシリカ表面に小粒径のシリ
カが凝集する。その結果、大粒径のシリカ同志の凝集が
促進される。The second essential component of the coating composition of the present invention is silica fine particles, and the present invention uses silica fine particles having an average particle size of 0.1 μm or more (hereinafter referred to as large particle size silica) and hydrophobic surfaces. Fine silica particles (hereinafter referred to as small particle size silica) having a smaller average particle size than the large particle size silica described above are used in combination. Generally, silica fine particles have active hydroxyl groups on their surfaces, and the smaller the particle size, the higher the surface activity. Therefore, when large particle size silica and small particle size silica coexist, the smaller the particle size, the more likely they are to aggregate in the dispersion medium. , small particle size silica aggregates on the surface of large particle size silica. As a result, aggregation of large-sized silica particles is promoted.
そこで、本発明では表面活性の大きな小粒径のシリカを
疎水化して不活性化し、大粒径のシリカの間にこのよう
な不活性粒子を介在させることにより、大粒径のシリカ
同志の凝集も防止している。このことは１組成物の分散
安定性を向上させる上で有効であるばかりでなく、成膜
時に於いても両シリカ微粒子を凝集させることなく最終
形成膜中に均一に分布させ、乾燥機−の過度の光沢を抑
えて所望のグレア防止性を持ったむらのない均一な塗膜
を得る上で極めて有効である。Therefore, in the present invention, small particle size silica with large surface activity is made hydrophobic and inactivated, and by interposing such inert particles between large particle size silica particles, the large particle size silica particles agglomerate together. It also prevents This is not only effective in improving the dispersion stability of one composition, but also allows the silica fine particles to be uniformly distributed in the final formed film without agglomerating during film formation, so that it can be used in the dryer. It is extremely effective in suppressing excessive gloss and obtaining a uniform, even coating film with the desired anti-glare properties.
本発明の大粒径シリカには、既述した通り、その平均粒
径が０．１μｍ以上、好ましくは０．５μ鳳以上のシリ
カ微粒子が使用され、その表面に疎水化処理が施されて
いないことが好ましい、平均粒径が０．ｂｔｍより小さ
くなると、塗膜に微小なりラックが入り（白化現象）、
密着性、耐擦傷性等の点で本発明が目的とする膜を得る
ことができない、しかし、平均粒径が余り大きすぎると
、平滑な塗膜を得ることができないので、大粒径シリカ
の平均粒径の上限は約５．０μ請程度とすることが好ま
しい、このようなシリカ微粒子は、例えば、市販のシリ
カゾル又はシリカヒドロゲルを噴霧乾燥して得られるほ
か、本出願人の出願に係る特開昭６２−２７５００５号
に記載された方法によって得ることもできる。本発明の
組成物に配合するに際しては、粉末状の大粒径シリカを
そのまま配合しても、またこれを適当な有機溶媒に分散
させて配合してもよい。As mentioned above, the large particle size silica of the present invention uses fine silica particles whose average particle size is 0.1 μm or more, preferably 0.5 μm or more, and whose surface is not subjected to hydrophobization treatment. It is preferable that the average particle size is 0. If it is smaller than btm, there will be minute racks in the paint film (whitening phenomenon),
However, if the average particle size is too large, it is impossible to obtain a smooth coating film, so it is difficult to obtain a film that is intended by the present invention in terms of adhesion, scratch resistance, etc. The upper limit of the average particle size is preferably about 5.0 μm.Such fine silica particles can be obtained, for example, by spray drying commercially available silica sol or silica hydrogel, or can be obtained by spray-drying commercially available silica sol or silica hydrogel. It can also be obtained by the method described in JP-A No. 62-275005. When blending into the composition of the present invention, powdered large particle size silica may be blended as is, or it may be dispersed in a suitable organic solvent and blended.
本発明の小粒径シリカには、前記した大粒径シリカより
平均粒径が小さく、且つ表面に疎水化処理を施したシリ
カ微粒子が使用される。しかし、小粒径シリカの平均粒
径が大きくなると。The small particle size silica of the present invention uses silica fine particles which have a smaller average particle size than the above-mentioned large particle size silica and whose surfaces have been subjected to hydrophobization treatment. However, when the average particle size of small particle size silica increases.
光沢度の低い塗膜しか得られず、塗膜の幅広いコントロ
ールが困難になるので、小粒径シリカの平均粒径は５０
ｍμ以下であることが好ましい。The average particle size of small-particle silica is 50% because only a coating film with low gloss can be obtained and it is difficult to control the coating over a wide range.
It is preferable that it is mμ or less.
このようなシリカ微粒子は、例えば四塩化ケイ素を熱分
解して得られる微粒子シリカを、シランカップリング剤
等で疎水化する方法、あるいは水又は有機溶媒を分散媒
とするシリカゾルを適宜な手段で疎水化する方法により
取得することができる。Such fine silica particles can be produced, for example, by making fine silica particles obtained by thermally decomposing silicon tetrachloride hydrophobic using a silane coupling agent, or by making a silica sol using water or an organic solvent as a dispersion medium by appropriate means. It can be obtained by the method of
本発明のコーティング組成物では、大粒径シリカの配合
量が少なすぎると、乾燥塗膜の光沢度をコントロールす
ることが難しくなって、所望のグレア防止効果を得るこ
とができず、逆に多すぎると、塗膜と基材との密着性が
低下する。In the coating composition of the present invention, if the amount of large particle size silica blended is too small, it will be difficult to control the gloss of the dried coating film, making it impossible to obtain the desired glare prevention effect; If it is too high, the adhesion between the coating film and the base material will decrease.
一方、小粒径シリカの配合量が少なすぎると、均一な塗
膜を形成することが困難になり、多すぎた場合は、塗膜
に充分な耐擦傷性を保持させることができない、従って
、本発明では大粒径シリカの配合量が、上記した本発明
の部分締金物を調製するに際して使用したトリアルコキ
シシランをＲＳ Ｉ Ｏａ／ｌとして計算し、同じくテ
トラアルコキシシランをＳ ｉ Ｏ２として計算して画
成分の部分締金物の量を（ＲＳ ｉ Ｏ，Ａ＋ Ｓ ｉ
Ｏ，）で算出した場合に於いて、その１００重量部当
り５〜５０重量部、好ましく１０〜３０重量部の範囲に
あり、小粒径シリカの配合量は、大粒径シリカと同様な
基準で１〜３０重量部、好ましくは５〜２０重量部の範
囲にある。そして、組成物の分散安定性と、塗膜の均一
性を確保し、適度な光沢を有してグレアのない塗膜を得
るためには、小粒径シリカ／大粒径シリカの重量比を約
０．２〜約５の範囲とすることが好ましい。On the other hand, if the amount of small particle size silica is too small, it will be difficult to form a uniform coating, and if it is too large, the coating will not have sufficient scratch resistance. In the present invention, the blending amount of large particle size silica is calculated by calculating the trialkoxysilane used in preparing the above-mentioned partially fastened article of the present invention as RSI Oa/l, and similarly calculating the tetraalkoxysilane as S i O2. The amount of partial fasteners of the image component is (RS i O, A+ S i
O,), it is in the range of 5 to 50 parts by weight, preferably 10 to 30 parts by weight per 100 parts by weight, and the blending amount of small particle size silica is based on the same standard as that of large particle size silica. The amount is in the range of 1 to 30 parts by weight, preferably 5 to 20 parts by weight. In order to ensure the dispersion stability of the composition and the uniformity of the coating film, and to obtain a coating film with appropriate gloss and no glare, the weight ratio of small particle size silica/large particle size silica must be adjusted. Preferably, it ranges from about 0.2 to about 5.
なお１本発明に於ける小粒径シリカの平均粒径は、ＢＥ
Ｔ法によりその比表面積（ＳＡ）を求め、次式により算
出した。Note that the average particle size of the small particle size silica in the present invention is BE
The specific surface area (SA) was determined by the T method and calculated by the following formula.
また、大粒径シリカの場合は、遠心式自動粒度分布測定
装置！！（堀場製作所製、 ＣＡＰＡ−５００型）によ
り粒度分布を求め、その累積分布の５０％（体積）のと
ころに相当する粒径を平均粒径とした。In addition, in the case of large particle size silica, we use a centrifugal automatic particle size distribution measuring device! ! (manufactured by Horiba, Model CAPA-500) to determine the particle size distribution, and the particle size corresponding to 50% (volume) of the cumulative distribution was defined as the average particle size.
本発明のコーティング組成物の分散媒は、−般に本発明
のアルコキシシラン化合物を部分締金物に加水分解する
に際して使用された有機溶媒である。従って、この分散
媒には少量の水の共存が許される。コーティング組成物
中の（ａ）〜（ｃ）成分の量は、形成させようとする被
膜の厚さや組成物の塗工方法を勘案して任意に選ぶこと
ができるが、標準的には、本発明のコーティング組成物
の固形分濃度は、１０〜２０ｗｔ％程度である。また、
本発明のコーティング組成物には、その使用目的に応じ
てタレ止め剤、湿潤剤。The dispersion medium of the coating composition of the present invention is generally an organic solvent used in hydrolyzing the alkoxysilane compound of the present invention into a partially fastened article. Therefore, a small amount of water is allowed to coexist in this dispersion medium. The amounts of components (a) to (c) in the coating composition can be arbitrarily selected taking into consideration the thickness of the film to be formed and the method of applying the composition, but typically, The solid content concentration of the coating composition of the invention is about 10 to 20 wt%. Also,
The coating composition of the present invention may contain an anti-sagging agent and a wetting agent depending on its intended use.
硬化剤、レベリング剤等の塗料一般に使用される適当量
の添加剤が配合可能である。基材への塗工は、スプレー
、ロールコータ−、ハケ塗り等任意の手段で行うことが
でき、塗工後は自然乾燥するか、あるいは約４００℃以
下の温度で加熱乾燥することで、基材表面に目的の塗膜
を形成させることができる。被膜の厚さは約１〜５μｍ
であれば、その塗膜に所期の性能を発揮させることか可
能である。Appropriate amounts of additives commonly used in coatings, such as curing agents and leveling agents, can be blended. Coating to the base material can be done by any means such as spraying, roll coater, brushing, etc. After coating, the base material can be dried naturally or heated at a temperature of about 400°C or less. A desired coating film can be formed on the surface of the material. The thickness of the coating is approximately 1 to 5 μm
If so, it is possible to make the coating film exhibit the desired performance.
［発明の効果］
大粒径シリカと小粒径シリカを併用する本発明のコーテ
ィング組成物にあっては１両シリカ微粒子の配合量を所
定の範囲内で、調節することによりｆｉ！ＩｗＡの光沢
度を任意に制御し、所望のグレア防止性を付与すること
ができる。また、本発明で使用される小粒径シリカはそ
の表面が疎水化されているため、組成物中ではもちろん
、塗膜を形成させた場合でも凝集してしまうことがなく
、むらのない均一な塗膜を得ることができる。これに加
えて１本発明のコーティング組成物から得られる塗膜は
、基材との密着性が強く、しかも耐擦傷性、耐熱性、耐
汚染性等に優れているので、人造大理石を含む各種のプ
ラスチック製品、ガラス製品、金属製品、木材製品等に
対する被覆材として極めて好適である。[Effects of the Invention] In the coating composition of the present invention that uses both large particle size silica and small particle size silica, fi! The glossiness of IwA can be controlled arbitrarily to provide desired anti-glare properties. In addition, since the small particle size silica used in the present invention has a hydrophobic surface, it does not aggregate in the composition or when forming a coating film, and provides an even and uniform surface. A coating film can be obtained. In addition to this, the coating film obtained from the coating composition of the present invention has strong adhesion to the base material and has excellent scratch resistance, heat resistance, stain resistance, etc. It is extremely suitable as a coating material for plastic products, glass products, metal products, wood products, etc.
［実 施 例］
実施例１
モノメチルトリメトキシシラン１００ｇに、テトラメト
キシシランの部分縮合物（平均分子量４７０、三菱化成
製の「メチルシリケート５１Ｊ）３７ｇを混合し、さら
にイソプロピルアルコール１３０ｇを添加して５分間攪
拌した。これに０．４ｖｔ％の酢酸水溶液１５１ｇを添
加し、５０℃で６０分間加熱した。こうして得た部分縮
合物を２５℃まで冷却した後、ｎ−ブチルアルコールと
メチルセロソルブを１＝１の重址比で混合した混合液を
１６０ｇ添加して部分縮合物の溶液を調製した。[Example] Example 1 100 g of monomethyltrimethoxysilane was mixed with 37 g of a partial condensate of tetramethoxysilane (average molecular weight 470, "Methyl Silicate 51J" manufactured by Mitsubishi Kasei), and 130 g of isopropyl alcohol was added. The mixture was stirred for 1 minute. 151 g of 0.4 vt% acetic acid aqueous solution was added and heated at 50°C for 60 minutes. After cooling the partial condensate thus obtained to 25°C, n-butyl alcohol and methyl cellosolve were mixed in 1=1 A solution of the partial condensate was prepared by adding 160 g of a liquid mixture mixed at a weight ratio of 1.
これとは別に、小粒径シリカとして平均粒径１２ｍμの
疎水性シリカ微粉末（日本アエロジル■製の「アエロジ
ル−Ｒ８０５Ｊ） ８ ｇと、大粒径シリカとして平均
粒径１μのシリカ微粒子（触媒化成工業■製、真綿球）
１９ｇをエチルアルコール２３ｇに添加して混合し、こ
れを先に調製した部分縮合物の溶液に添加してコーティ
ング組成物（Ａ）を得た。Separately, 8 g of hydrophobic silica fine powder with an average particle size of 12 mμ (Aerosil-R805J manufactured by Nippon Aerosil ■) was used as small particle size silica, and 8 g of silica fine powder with an average particle size of 1 μm as large particle size silica (catalyst chemical (Industrial made, cotton balls)
19 g was added to 23 g of ethyl alcohol and mixed, and this was added to the solution of the partial condensate prepared previously to obtain a coating composition (A).
実施例２〜３
組成物（Ａ）の調製において使用したテトラメトキシシ
ランの部分縮合物の量を、２０ｇ及び８０ｇに変更した
以外は、実施例１と同様な方法によりコーティング組成
物（Ｂ）及び（ｃ）を調製した。Examples 2 to 3 Coating compositions (B) and (c) was prepared.
実施例４〜１１
テトラメトキシシランの部分縮合物の使用量、疎水性シ
リカ微粉末及びこれと併用する大粒径シリカ微粒子の配
合量や平均粒径などの変えて、実施例１と同様に、表１
に示すコーティング組成物（Ｄ）〜（Ｋ）を調製した。Examples 4 to 11 The same procedure as in Example 1 was carried out by changing the amount of the partial condensate of tetramethoxysilane used, the amount of hydrophobic silica fine powder and the large-sized silica fine particles used in combination, and the average particle size. Table 1
Coating compositions (D) to (K) shown below were prepared.
比較例
疎水性シリカ微粉末を使用しない以外は実施例１と同様
にしてコーティング組成物（Ｌ）を調製し、また小粒径
シリカとして疎水性シリカ微粉末の代わりに、平均粒径
１２ｍμの親木性シリカ微粉末（日本アエロジル■製「
アエロジル−２００Ｊ）を使用した以外は実施例１と同
様にしてコーティング組成物（Ｍ）を調製した。Comparative Example A coating composition (L) was prepared in the same manner as in Example 1 except that no hydrophobic silica fine powder was used. Fine wood silica powder (manufactured by Nippon Aerosil)
A coating composition (M) was prepared in the same manner as in Example 1 except that Aerosil-200J) was used.
（以下余白）
試験例
アクリル樹脂系人造大理石（旭硝子■製のエバーフレッ
シュ）の表面を研摩紙で研摩した後、これに上記の各実
施例及び比較例で！５１製したコーティング組成物（Ａ
）〜（Ｌ）をそれぞれ、スプレー法で塗布し、８０℃で
熱風乾燥して膜厚２μの塗膜を形成させ、各塗膜につい
て、下記のような試験を行った。(Leaving space below) Test Example After polishing the surface of acrylic resin-based artificial marble (Everfresh manufactured by Asahi Glass ■) with abrasive paper, the above Examples and Comparative Examples were applied to it! Coating composition prepared in 51 (A
) to (L) were respectively applied by a spray method and dried with hot air at 80° C. to form a coating film with a thickness of 2 μm, and the following tests were conducted on each coating film.
（１）乾燥後の外ｗＡ：表面の「むら」、「ひび」の有
無を目視ｗｔ察。(1) Outside wA after drying: Visually inspect wt for presence or absence of "unevenness" and "cracks" on the surface.
（２）表面光沢度：ＪＩＳ Ｋ ７１０５に準拠する測
定。(2) Surface gloss: Measured according to JIS K 7105.
（３）密着性：セロテープを貼り付けた後、これを剥が
し、被膜の剥離状況を目視観察。(3) Adhesion: After pasting cellophane tape, peel it off and visually observe the peeling status of the film.
（４）耐熱性二人のついたタバコを塗膜上に１分間放置
し、その後水洗して痕跡の有無
を目視ｗｔ祭。(4) Heat resistance Two cigarettes were left on the coating for 1 minute, then washed with water and visually inspected for any traces.
（５）耐擦傷性： ５００ｇの荷重をかけたスチールウ
ール＃０ＯＯＯにて１００回摩擦し、傷の有無を目視Ｉ
ｌｔ察。(5) Scratch resistance: Rub 100 times with steel wool #0OOO under a load of 500g and visually check for scratches.
I guess.
（６）耐汚染性：１０％クエン酸水溶液、緑茶、紅茶（
０，３ｇの緑茶、紅茶を熱水３０ｃｃに６分浸したもの
）及びタバスコを被膜上
滴下し、室温で２４時間放置した後、
水洗して外観を目視ａ察。(6) Stain resistance: 10% citric acid aqueous solution, green tea, black tea (
0.3 g of green tea or black tea soaked in 30 cc of hot water for 6 minutes) and Tabasco were dropped on the film, left at room temperature for 24 hours, washed with water, and visually inspected the appearance.
試験結果を表２に示す。The test results are shown in Table 2.
表 ２ ×印：著しく剥離、痕跡、きず著しいTable 2 × mark: Significant peeling, traces, and scratches
Claims (1)
数１〜６の炭化水素基、Ｒ＾１：炭素数１〜６のアルキ
ル基〕のトリアルコキシシラン１００重量部と、一般式
Ｓｉ（ＯＲ＾２）＿４〔Ｒ＾２：炭素数１〜６のアルキ
ル基〕のテトラアルコキシシラン２０〜１３０重量部と
からなる有機ケイ素化合物の部分縮合物、 （ｂ）平均粒径が０．１μｍ以上のシリカ微粒子（ｃ）
平均粒径が前記（ｂ）のシリカ微粒子より小さく、しか
も表面が疎水化されているシリカ微粒子 を含有することを特徴とするコーティング組成物。 ２、疎水化シリカ微粒子の平均粒径が５０ｍμ以下であ
ることを特徴とする請求項１記載のコーティング組成物
。 ３、前記トリアルコキシシランの部分縮合物をＲＳｉＯ
＿３＿／＿２とし、前記テトラアルコキシシランの部分
縮合物をＳｉＯ＿２として計算して（ＲＳｉＯ＿３＿／
＿２＋ＳｉＯ＿２）１００重量部に対し、前記（ｂ）の
シリカ微粒子の含有量が５〜５０重量部、前記（ｃ）の
シリカ微粒子の含有量が１〜３０重量部であることを特
徴とする請求項１記載のコーティング組成物。 ４、請求項１〜３のいずれかに記載された組成物にて、
表面に被膜を形成させたことを特徴とする被膜形成物品
。[Claims] 1. (a) Trialkoxy of general formula: RSi(OR^1)_3 [R: hydrocarbon group having 1 to 6 carbon atoms, R^1: alkyl group having 1 to 6 carbon atoms] A partial condensate of an organosilicon compound consisting of 100 parts by weight of silane and 20 to 130 parts by weight of tetraalkoxysilane of the general formula Si(OR^2)_4 [R^2: alkyl group having 1 to 6 carbon atoms], ( b) Silica fine particles with an average particle size of 0.1 μm or more (c)
A coating composition characterized in that it contains fine silica particles having a smaller average particle size than the fine silica particles described in (b) above and whose surfaces have been made hydrophobic. 2. The coating composition according to claim 1, wherein the average particle size of the hydrophobized silica particles is 50 mμ or less. 3. The partial condensate of the trialkoxysilane is converted into RSiO
_3_/_2, and the partial condensate of the tetraalkoxysilane is calculated as SiO_2 (RSiO_3_/
A claim characterized in that the content of the silica fine particles in (b) is 5 to 50 parts by weight and the content of the silica fine particles in (c) is 1 to 30 parts by weight relative to 100 parts by weight of _2+SiO_2). Coating composition according to 1. 4. In the composition according to any one of claims 1 to 3,
A film-formed article characterized by having a film formed on its surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63145315A JP2730552B2 (en) | 1988-06-13 | 1988-06-13 | Coating composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63145315A JP2730552B2 (en) | 1988-06-13 | 1988-06-13 | Coating composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH023468A true JPH023468A (en) | 1990-01-09 |
| JP2730552B2 JP2730552B2 (en) | 1998-03-25 |
Family
ID=15382318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63145315A Expired - Fee Related JP2730552B2 (en) | 1988-06-13 | 1988-06-13 | Coating composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2730552B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171402A (en) * | 1991-11-06 | 1993-07-09 | Asahi Kagaku Kogyo Kk | Roll having corrosion resistance to molten metal |
| JPH10130576A (en) * | 1996-10-24 | 1998-05-19 | Nof Corp | Coating material composition |
| JP2000017227A (en) * | 1998-07-03 | 2000-01-18 | Nihon Yamamura Glass Co Ltd | Coating composition |
| US6022919A (en) * | 1995-04-28 | 2000-02-08 | Nof Corporation | Coating composition, process for preparing coating composition and process for preparing dispersing component of inorganic oxide sol |
| JP2002105386A (en) * | 2000-09-27 | 2002-04-10 | Nippon Yushi Basf Coatings Kk | Paint composition |
| JP2002309170A (en) * | 2001-04-11 | 2002-10-23 | Nippon Yushi Basf Coatings Kk | Coating composition, coating finishing method and coated article |
| JP2007183674A (en) * | 2007-03-22 | 2007-07-19 | Toppan Printing Co Ltd | Antiglare antireflection film |
| WO2008062605A1 (en) * | 2006-11-21 | 2008-05-29 | Nittetsu Mining Co., Ltd | Resin composition, anti-reflection coating material, anti-dazzling coating material, anti-reflection coating, anti-reflection film, anti-dazzling film, corrosion protective coating, corrosion protective coating material, coating material, and coating film |
| WO2009029979A1 (en) * | 2007-09-03 | 2009-03-12 | Deakin University | Coating composition and process for the preparation thereof |
| JP2010144083A (en) * | 2008-12-19 | 2010-07-01 | Panasonic Electric Works Co Ltd | Coating material composition, coated article and coating method |
| JP2013177604A (en) * | 2013-04-17 | 2013-09-09 | Panasonic Corp | Coating composition, coated article, and coating method |
| JP2013208815A (en) * | 2012-03-30 | 2013-10-10 | Toppan Printing Co Ltd | Water-repellent laminate |
| JP2014051295A (en) * | 2012-09-06 | 2014-03-20 | Toppan Printing Co Ltd | Lid material, and sealed container using the same |
| JP2014201598A (en) * | 2013-04-01 | 2014-10-27 | 三菱マテリアル株式会社 | Composition for forming low refractive index film and production method of the same, and formation method of low refractive index film |
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1988
- 1988-06-13 JP JP63145315A patent/JP2730552B2/en not_active Expired - Fee Related
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|---|---|---|---|---|
| JPH05171402A (en) * | 1991-11-06 | 1993-07-09 | Asahi Kagaku Kogyo Kk | Roll having corrosion resistance to molten metal |
| US6022919A (en) * | 1995-04-28 | 2000-02-08 | Nof Corporation | Coating composition, process for preparing coating composition and process for preparing dispersing component of inorganic oxide sol |
| US6376559B1 (en) | 1995-04-28 | 2002-04-23 | Basf Nof Coatings Co., Ltd. | Process for preparing a dispersing component comprising an inorganic oxide sol |
| JPH10130576A (en) * | 1996-10-24 | 1998-05-19 | Nof Corp | Coating material composition |
| JP2000017227A (en) * | 1998-07-03 | 2000-01-18 | Nihon Yamamura Glass Co Ltd | Coating composition |
| JP2002105386A (en) * | 2000-09-27 | 2002-04-10 | Nippon Yushi Basf Coatings Kk | Paint composition |
| JP2002309170A (en) * | 2001-04-11 | 2002-10-23 | Nippon Yushi Basf Coatings Kk | Coating composition, coating finishing method and coated article |
| WO2008062605A1 (en) * | 2006-11-21 | 2008-05-29 | Nittetsu Mining Co., Ltd | Resin composition, anti-reflection coating material, anti-dazzling coating material, anti-reflection coating, anti-reflection film, anti-dazzling film, corrosion protective coating, corrosion protective coating material, coating material, and coating film |
| JP2007183674A (en) * | 2007-03-22 | 2007-07-19 | Toppan Printing Co Ltd | Antiglare antireflection film |
| WO2009029979A1 (en) * | 2007-09-03 | 2009-03-12 | Deakin University | Coating composition and process for the preparation thereof |
| JP2010144083A (en) * | 2008-12-19 | 2010-07-01 | Panasonic Electric Works Co Ltd | Coating material composition, coated article and coating method |
| JP2013208815A (en) * | 2012-03-30 | 2013-10-10 | Toppan Printing Co Ltd | Water-repellent laminate |
| JP2014051295A (en) * | 2012-09-06 | 2014-03-20 | Toppan Printing Co Ltd | Lid material, and sealed container using the same |
| JP2014201598A (en) * | 2013-04-01 | 2014-10-27 | 三菱マテリアル株式会社 | Composition for forming low refractive index film and production method of the same, and formation method of low refractive index film |
| JP2013177604A (en) * | 2013-04-17 | 2013-09-09 | Panasonic Corp | Coating composition, coated article, and coating method |
| US9644113B2 (en) | 2014-04-25 | 2017-05-09 | Mitsubishi Materials Corporation | Composition for forming a thin layer with low refractive index, manufacturing method thereof, and manufacturing method of a thin layer with low refractive index |
| JP2016094254A (en) * | 2016-02-04 | 2016-05-26 | 凸版印刷株式会社 | Packaging bag |
| JP2016128261A (en) * | 2016-02-04 | 2016-07-14 | 凸版印刷株式会社 | Laminate and lid material |
| WO2022054644A1 (en) * | 2020-09-14 | 2022-03-17 | 大日本印刷株式会社 | Matted article |
| WO2022054646A1 (en) * | 2020-09-14 | 2022-03-17 | 大日本印刷株式会社 | Matte article |
| JP2022048110A (en) * | 2020-09-14 | 2022-03-25 | 大日本印刷株式会社 | Matte article |
| JP2022048111A (en) * | 2020-09-14 | 2022-03-25 | 大日本印刷株式会社 | Matte article |
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| Publication number | Publication date |
|---|---|
| JP2730552B2 (en) | 1998-03-25 |
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