JPH0455476A - Production of inorganic coating material - Google Patents
Production of inorganic coating materialInfo
- Publication number
- JPH0455476A JPH0455476A JP16772990A JP16772990A JPH0455476A JP H0455476 A JPH0455476 A JP H0455476A JP 16772990 A JP16772990 A JP 16772990A JP 16772990 A JP16772990 A JP 16772990A JP H0455476 A JPH0455476 A JP H0455476A
- Authority
- JP
- Japan
- Prior art keywords
- coating material
- conductivity
- value
- molecular weight
- minimum value
- 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
- 238000000576 coating method Methods 0.000 title abstract description 52
- 239000011248 coating agent Substances 0.000 title abstract description 50
- 239000000463 material Substances 0.000 title abstract description 35
- 238000004519 manufacturing process Methods 0.000 title description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008119 colloidal silica Substances 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 22
- 238000003860 storage Methods 0.000 abstract description 12
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 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
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- -1 silicon alkoxide Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、貯蔵安定性に優れた無機系コーティング材
を製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an inorganic coating material with excellent storage stability.
ケイ素アルコキシドを主成分とする無機系コーティング
材組成物は、耐候性があり、かつ、高硬度な塗膜を形成
することから、これまでにも種々研究されてきた。その
無機系コーティング材組成物の反応性は液のｐＨ値が大
きく関与しているものと思われる。たとえば、特開昭６
３−３６３５０号公報では、シリコーン被覆組成物のｐ
Ｈ値を、また、特開昭５１−２７３６号公報では、耐摩
耗性被覆組成物のｐＨ値の範囲を規定することにより組
成物の安定化をはかっている。BACKGROUND ART Inorganic coating material compositions containing silicon alkoxide as a main component have been studied in various ways because they are weather resistant and form highly hard coatings. It is thought that the reactivity of the inorganic coating material composition is largely influenced by the pH value of the liquid. For example, JP-A-6
No. 3-36350 discloses that p of a silicone coating composition
In JP-A No. 51-2736, stabilization of the composition is attempted by defining the range of the pH value of the wear-resistant coating composition.
しかし、コーティング材の真の安定領域を見つけるとい
う点では、上記２つの公報で開示されたｐＨ値の規定で
は問題が残っている。また、比較的小さなｐＨ値の違い
で、貯蔵時の分子量の増加が異なるため、長期保存した
後、基材に塗装すると同様の塗膜性能が得られない場合
があった。However, in terms of finding the true stable region of the coating material, problems remain with the pH value definitions disclosed in the above two publications. Furthermore, because the increase in molecular weight during storage differs due to a relatively small difference in pH value, the same coating performance may not be obtained when applied to a substrate after long-term storage.
この無機系コーティング材組成物は、加水分解および重
縮合反応を行わせることによりプレポリマーを生成する
わけであるが、高硬度な塗膜を得るためには、このプレ
ポリマーの重量平均分子量ＭＷがｃｐｃ ＜ゲル浸透ク
ロマトグラフィー）によるポリスチレン換算で６００〜
１５００である必要がある。前記プレポリマーの分子量
が前記範囲よりも小さいときには、縮重合の際の硬化収
縮が太き（なる傾向があり、焼付は後に塗膜にクランク
が発生やす（なる傾向になる。また、前記範囲よりも大
きいときには、反応が遅すぎて硬化しにくいか、または
、硬化しても柔らかい塗膜になったり、塗膜のレベリン
グ性が非常に悪いものとなる傾向にある。This inorganic coating material composition produces a prepolymer by performing hydrolysis and polycondensation reactions, but in order to obtain a highly hard coating film, the weight average molecular weight MW of this prepolymer must be cpc (gel permeation chromatography) polystyrene equivalent: 600~
Must be 1500. When the molecular weight of the prepolymer is smaller than the above range, curing shrinkage during polycondensation tends to be thicker, and cracks tend to occur in the coating film after baking. When the amount is too large, the reaction tends to be too slow and hard to cure, or even if cured, the coating film tends to be soft, or the leveling properties of the coating film tend to be very poor.
そこで、この発明は、ケイ素アルコキシド系コーティン
グ材の塗膜性能を損なわず、長期間にわたって貯蔵安定
化できる無機系コーティング材が得られる無機系コーテ
ィング材の製造方法を提供することを課題とする。Therefore, an object of the present invention is to provide a method for producing an inorganic coating material that does not impair the coating performance of the silicon alkoxide coating material and can be stored stably for a long period of time.
上記課題を解決するために、この発明は、下記（ａｌ、
（ｂｌおよび（Ｃ）を主成分として用い、全体の導電率
が最小値（ｍｉｎｉｍｕｍ値）または最小値よりも３μ
Ｓ／ｃ１１以内（ただし、このときのｐＨ値は最小値の
ときＯｐＨ値よりも酸性側、すなわちｐ）Ｉ値の小さい
側にくるようにする。）になるように無機系コーティン
グ材を調製する無機系コーティング材の製造方法を提供
する。In order to solve the above problems, this invention provides the following (al,
(Using bl and (C) as the main components, the overall conductivity is the minimum value or 3μ below the minimum value)
S/c is within 11 (however, the pH value at this time is set to be on the acidic side than the OpH value at the minimum value, that is, on the side where the p)I value is smaller. ) A method for producing an inorganic coating material is provided.
（ａ） 下記一般式［１］においてｎ＝ｏで表される
ケイ素化合物および／またはコロイド状シリカ２０〜２
００重量部（以下、「重量部」を単に「部」と言う）。(a) Silicon compound and/or colloidal silica 20 to 2 represented by n=o in the following general formula [1]
00 parts by weight (hereinafter, "parts by weight" is simply referred to as "parts").
（ｂ）下記一般式［１］においてｎ＝１で表されるケイ
素化合物１００部。(b) 100 parts of a silicon compound represented by n=1 in the following general formula [1].
（ｃ）下記一般式［１］においてｎ＝２で表されるケイ
素化合物３０〜８０部。(c) 30 to 80 parts of a silicon compound represented by n=2 in the following general formula [1].
Ｒ’、Ｓ ｉ （ＯＲ”）、−、”・■（ただし、■
式中、Ｒ１およびＲ２はそれぞれアルキル基であり、Ｒ
１およびＲ２がそれぞれ複数個の場合には、すべてのＲ
１またはＲ２が同じ基であってもよい。）
導電率の最小値または最小値よりも３μＳ ／ Ｃ１１
以内（ただし、このときＯｐＨ値は最小値のときのｐＨ
値よりも酸性側にくるようにする。）で貯蔵安定性をは
かる際の上記（ａ）成分としては、微粒子シリカ成分が
水、メタノール、イソプロピルアルコール等の有機溶剤
、これらの混合溶剤に分散されたものが挙げられるが、
その粒径、溶剤種等は特に限定されるものではない。な
お、上記成分（ａ）としてコロイド状シリカを用いる場
合は、配合量の数値は、分散媒も含む数値である。R', S i (OR"), -, "・■ (However, ■
In the formula, R1 and R2 are each an alkyl group, and R
If there are multiple 1 and R2, all R
1 or R2 may be the same group. ) Minimum value of conductivity or 3 μS/C11 below the minimum value
(However, in this case, the OpH value is the pH at the minimum value.)
Make sure it is on the more acidic side than the value. The above component (a) when measuring storage stability in ) includes those in which particulate silica components are dispersed in water, organic solvents such as methanol, isopropyl alcohol, and mixed solvents thereof.
The particle size, solvent type, etc. are not particularly limited. In addition, when colloidal silica is used as the component (a), the numerical value of the blending amount includes the dispersion medium.
上記成分の無機系コーティング材は、たとえば、成分（
ａｌ、（ｂ）および（Ｃ）を適当な溶剤で希釈し、そこ
に硬化剤および触媒を必要量添加して加水分解および重
縮合反応を行わせることによりプレポリマーを生成させ
て調製される。The inorganic coating material with the above components is, for example, the component (
It is prepared by diluting al, (b) and (C) with a suitable solvent, adding the required amount of a curing agent and a catalyst thereto, and carrying out hydrolysis and polycondensation reactions to produce a prepolymer.
硬化剤としては、たとえば、水が用いられるが、特に限
定されない。硬化剤の量は特に限定されないが、たとえ
ば、Ｈ，０１０部モル比で０．４〜２．５の割合とされ
る。触媒も、特に限定されないが、たとえば、塩酸、燐
酸、硫酸等の無機酸や無機塩、蟻酸、酢酸、クロロ酢酸
等の有機酸の希釈溶液などの酸性触媒；アミン類、アミ
ノシラン類などの塩基性触媒を単独であるいは２種類以
上併せて使用することができる。触媒の量は特に限定さ
れない。上記成分（ａｌとしてシリカゾルを用いる場合
で、そのシリカゾルが酸性または塩基性を示す場合、こ
れが触媒の代わりになる。しかし、シリカゾル成分が多
くなってくると酸性度あるいは塩基性度が強くなるため
反応が促進され、分子量が大きくなりすぎてしまう。As the curing agent, water is used, for example, but it is not particularly limited. The amount of the curing agent is not particularly limited, but may be, for example, in a molar ratio of 0.4 to 2.5 parts of H. Catalysts are not particularly limited, but include, for example, acidic catalysts such as dilute solutions of inorganic acids and inorganic salts such as hydrochloric acid, phosphoric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, and chloroacetic acid; basics such as amines and aminosilanes. Catalysts can be used alone or in combination of two or more. The amount of catalyst is not particularly limited. When using silica sol as the above component (al), if the silica sol is acidic or basic, it can be used in place of the catalyst. However, as the silica sol component increases, the acidity or basicity becomes stronger, so the reaction is promoted and the molecular weight becomes too large.
そのような場合やその他の理由で導電率が上記範囲を外
れている場合、コーティング材に塩基性試薬あるいは酸
性試薬を加えて処理してやるのである。つまり、液溝電
率を下げてやることにより、たとえば、Ｍｗ＝６００〜
１５００の分子量の範囲内で長期間にわたり、安定して
使用することができる。その際、導電率の値が最小値で
あるように調製されたコーティング材は、特に安定で長
期間の貯蔵が可能である。また、導電率の値が最小値か
ら３μ５Ｚａｌ１以内の酸性側（すなわち、導電率最小
値のときのｐＨ値よりも小さいｐＨ値を示す）の範囲で
も比較的安定にコーティング材を保つことができる。In such cases or when the conductivity is outside the above range for other reasons, a basic or acidic reagent is added to the coating material for treatment. In other words, by lowering the liquid groove electrical efficiency, for example, Mw=600~
It can be used stably for a long period of time within a molecular weight range of 1500. Coating materials prepared in such a way that the conductivity value is minimal are particularly stable and can be stored for long periods of time. Furthermore, the coating material can be kept relatively stable even in the acidic range where the conductivity value is within 3μ5Zal1 from the minimum value (that is, the pH value is smaller than the pH value at the minimum conductivity value).
この発明の製造方法で調製された無機系コーティング材
の塗装方法は、たとえば、スプレー塗装、ロール塗装、
フローコーター塗装、浸せき塗装などが挙げられ、特に
限定されない。また、塗装後の乾燥・焼付は条件につい
ても特に限定されないが、たとえば、６０〜２００℃程
度で行うことが好ましい。The coating method for the inorganic coating material prepared by the production method of the present invention includes, for example, spray coating, roll coating,
Examples include flow coater painting, dip painting, etc., and are not particularly limited. Further, the conditions for drying and baking after painting are not particularly limited, but it is preferable to carry out the drying and baking at, for example, about 60 to 200°C.
上記成分（ａ）および（Ｃ）の量が、成分（ｂ） １０
０部に対する割合で、上記範囲を外れていると次のよう
な問題が生じるため、上記範囲内に保つ必要がある。上
記（ａｌ成分の割合が２０部未満であると、塗膜が軟ら
かかったり、レベリング性が悪いという問題がある。ま
た、２００部を越えると、耐クランク性が悪いという問
題がある。上記成分（Ｃ）の割合が３０部未満だと、耐
クランク性が悪いという問題があり、８０部を越えると
、塗膜が軟らかすぎ、非実用的であるという問題がある
。そこで、上記成分の範囲内の無機系コーティング材組
成物を用いて導電率処理を行うこととする。The amount of the above components (a) and (C) is 10
If the ratio to 0 parts is out of the above range, the following problems will occur, so it is necessary to keep it within the above range. If the proportion of the above (Al component) is less than 20 parts, there will be a problem that the coating film will be soft and the leveling property will be poor.If it exceeds 200 parts, there will be a problem that the crank resistance will be poor. If the proportion of (C) is less than 30 parts, there will be a problem of poor crank resistance, and if it exceeds 80 parts, there will be a problem that the coating film will be too soft and impractical. Conductivity treatment will be performed using an inorganic coating material composition.
なお、無機系コーティング材の導電率が上述の範囲を外
れていると、反応が遅いため焼付は時の塗膜が硬化しに
くいか、または、硬化しても柔らかい塗膜になったり、
レベリング性が悪くなったりするという問題がある。If the conductivity of the inorganic coating material is outside the above range, the reaction will be slow and the coating will be difficult to cure during baking, or the coating will be soft even after curing.
There is a problem in that the leveling performance deteriorates.
以下に、この発明の具体的な実施例および比較例を示す
が、この発明は下記実施例に限定されない。実施にあた
り、導電率の測定には、堀場製作所のコンダクティビテ
ィーメーター（ＣＯＮＤＵＣＴＩν■ＴＹ ＭＥＴＥＲ
） Ｄ Ｓ −１５を、電極は＃３５５２−１０Ｄを使
用した。塗装基材にはＪＩＳ Ａ３４０３の石綿スレ
ート系のフレキシブル板６ｍ厚を１２ｍＸ１Ｂｍの大き
さに切断して使用した。また、プライマーとして、東芝
シリコーン株式会社製のシリコーン変性ウレタン系プラ
イマーを膜厚で３μｍになるように塗布して使用した。Specific examples and comparative examples of the present invention are shown below, but the present invention is not limited to the following examples. To measure the conductivity, use a Horiba conductivity meter (CONDUCTIν■TY METER).
) DS-15 and #3552-10D were used as electrodes. A JIS A3403 asbestos slate-based flexible board 6 m thick was cut into a size of 12 m x 1 Bm and used as the coating base material. Further, as a primer, a silicone-modified urethane primer manufactured by Toshiba Silicone Co., Ltd. was applied to a film thickness of 3 μm.
このようにプライマーを施した基材へ、下記実施例およ
び比較例で得られたコーティング材組成物をスプレーで
、硬化後の膜厚が５μｍになるように塗装し、セツティ
ングを５分間とった後、１６０℃で焼付けた。The coating material compositions obtained in the following Examples and Comparative Examples were sprayed onto the base material coated with the primer so that the film thickness after curing was 5 μm, and the coating was allowed to set for 5 minutes. After that, it was baked at 160°C.
、なお、分子量の測定には、ＧＰＣ（ゲル浸透クロマト
グラフィー）装置として、東ソー■製ＨＬＣ８０２Ａお
よびＨＬＣ８０２０を使用し、ポリスチレンを標準試料
として用いた。To measure the molecular weight, HLC802A and HLC8020 manufactured by Tosoh Corporation were used as GPC (gel permeation chromatography) devices, and polystyrene was used as a standard sample.
以下では、コーティング材の導電率最小値の把握のため
の電導度滴定に１重量％のアンモニア水を用い、導電率
の調整にも同じ濃度のアンモニア水を用いているが、電
導度滴定に用いる薬剤と導電率調整に用いる薬剤とは、
種類、濃度などが一致している必要はない。In the following, 1% by weight ammonia water is used for conductivity titration to determine the minimum value of the conductivity of the coating material, and the same concentration of ammonia water is used to adjust the conductivity. What are the chemicals and the chemicals used for conductivity adjustment?
It is not necessary that the types, concentrations, etc. match.
一実施例１
メチルトリメトキシシラン１００部に、テトラエトキシ
シラン１０部、ＩＰＡオルガノシリカゾル（触媒化成工
業株式会社製ｒＯ５ｃＡＬ１４３２」、ＳｉＯ！含有量
３０％）１０部、ジメチルジメトキシシラン３０部、お
よび、ＩＰＡ１００部を混合し、さらに、Ｈ１０８０部
を添加し、攪拌した。この混合物を２日間常温で保存し
た後、アンモニア水（アンモニア１％含有）を用いて電
導度滴定を行い、導電率の最小値７．３０μＳ ／ ｃ
ｍを把握した。その後、全体の導電率を最小値に調整し
、コーティング材を得た。導電率調整１日後、このコー
ティング材の分子量を測定したところＭｗ＝８６０で、
常温保存で液間製４か月後の分子量はＭｗ−１０３０で
あった。Example 1 100 parts of methyltrimethoxysilane, 10 parts of tetraethoxysilane, 10 parts of IPA organosilica sol (rO5cAL1432 manufactured by Catalysts & Chemicals Co., Ltd., SiO! content 30%), 30 parts of dimethyldimethoxysilane, and IPA100 1080 parts of H were added and stirred. After storing this mixture at room temperature for 2 days, conductivity titration was performed using ammonia water (containing 1% ammonia), and the minimum value of conductivity was 7.30 μS/c.
I understood m. Thereafter, the overall conductivity was adjusted to the minimum value to obtain a coating material. One day after the conductivity adjustment, the molecular weight of this coating material was measured and found that Mw = 860.
The molecular weight after 4 months of storage at room temperature was Mw-1030.
一実施例２一
実施例１と同じ配合の混合物を２日間常温で保存した後
、導電率が最小値よりおよそ２．０μＳ／口大きく、ｐ
Ｈ値が導電率最小のときのｐＨに比べて酸性側となるよ
うにアンモニア水（アンモニ７１％含有）を用いて調整
した。導電率調整１日後、このコーティング材の分子量
を測定したところＭｗ＝９１０で、常温保存で波調製４
か月後の分子量はＭｗ＝１３４０であった。Example 2 After storing a mixture with the same formulation as Example 1 at room temperature for 2 days, the conductivity was approximately 2.0 μS/mouth larger than the minimum value, and p
Aqueous ammonia (containing 71% ammonia) was used to adjust the H value to be on the acidic side compared to the pH at the minimum conductivity. One day after conductivity adjustment, the molecular weight of this coating material was measured and found that Mw = 910.
The molecular weight after a month was Mw=1340.
上記実施例１．２および比較例１〜３のコーティング材
の導電率調整値と、４か月保存後の分子量との関係を第
１図に示した。この図にみるように、実施例１および２
では４か月保存後も分子量が１５００以下であるのに対
し、比較例１〜３ではいずれも４か月保存後の分子量が
１５００を越えている。FIG. 1 shows the relationship between the electrical conductivity adjustment values of the coating materials of Example 1.2 and Comparative Examples 1 to 3 and the molecular weight after storage for 4 months. As seen in this figure, Examples 1 and 2
In Comparative Examples 1 to 3, the molecular weight is still over 1500 even after storage for 4 months, whereas in Comparative Examples 1 to 3, the molecular weight is over 1500 even after storage for 4 months.
一実施例３〜５−
第１表に示す配合のコーティング材を、実施例１と同様
に液導電率が最小値になるように調整し、導電率調整１
日後と常温保存４か月後の各分子量を第１表に併せて示
した。Examples 3 to 5 - The coating material having the composition shown in Table 1 was adjusted so that the liquid conductivity became the minimum value in the same manner as in Example 1, and conductivity adjustment 1
The molecular weights after 1 day and after 4 months of storage at room temperature are also shown in Table 1.
一実施例６一
実施例１の配合で触媒化成工業株式会社製のＩＰＡオル
ガノシリカゾルを日産化学株式会社製のＩＰＡオルガノ
シリカゾルに替えて実施例１と同様の実験を行ったとこ
ろ、導電率調整１日後、このコーティング材の分子量は
ＭＷ＝８１０で、常温保存で４か月後の分子量はＭＷ＝
１１５０であった。Example 6 An experiment similar to Example 1 was conducted using the formulation of Example 1, replacing IPA organosilica sol manufactured by Catalysts & Chemicals Co., Ltd. with IPA organosilica sol manufactured by Nissan Chemical Co., Ltd., and found that conductivity adjustment 1 After days, the molecular weight of this coating material is MW = 810, and after 4 months of storage at room temperature, the molecular weight is MW =
It was 1150.
一実施例７一
実施例１の配合で触媒化成工業株式会社製のＩＰＡオル
ガノシリカゾルを日産化学株式会社製のメタノールシリ
カゾルに替えて実施例１と同様の実験を行ったところ、
導電率調整１日後、このコーティング材の分子量はＭＷ
＝８６０で、常温保存で４か月後の分子量はＭｗ＝１０
００であった一比較例１一
実施例１と同じ配合の混合物を無処理でポリ容器に入れ
て密閉し、３日間常温で保存した後、分子量を測定した
ところＭｗ＝９９０であった。さらに、常温保存で波調
製から４か月後に分子量を測定したところＭｗ＝ １５
３０であった。Example 7 An experiment similar to Example 1 was conducted using the formulation of Example 1, replacing IPA organosilica sol manufactured by Catalysts & Chemicals Co., Ltd. with methanol silica sol manufactured by Nissan Chemical Co., Ltd.
After one day of conductivity adjustment, the molecular weight of this coating material was MW.
= 860, and the molecular weight after 4 months of storage at room temperature is Mw = 10
00 Comparative Example 1 A mixture having the same formulation as Example 1 was placed in a plastic container without treatment, sealed, and stored at room temperature for 3 days.The molecular weight was measured and found to be Mw=990. Furthermore, when the molecular weight was measured 4 months after the wave preparation when stored at room temperature, Mw = 15
It was 30.
−比較例２一
実施例１と同じ配合の混合物を２日間常温で保存した後
、導電率が最小値よりおよそ１．０μＳ／１大きく、塩
基性側となるようにアンモニア水を用いて調製した。１
日後、塩基性側に調製されたコーティング材の分子量を
測定したところＭｗ＝１２５０で、波調製４か月後の分
子量はＭｗ＝３９１０であった。- Comparative Example 2 - After storing a mixture with the same formulation as in Example 1 at room temperature for 2 days, it was prepared using ammonia water so that the conductivity was approximately 1.0 μS/1 larger than the minimum value and on the basic side. . 1
After a day, the molecular weight of the coating material prepared on the basic side was measured and found to be Mw=1250, and the molecular weight after 4 months of wave preparation was Mw=3910.
一比較例３一
実施例１と同じ配合の混合物を２日間常温で保存した後
、導電率を最小値よりも３μＳ／３以上離れた酸性側に
アンモニア水を用いて調製して分子量を測定したところ
ＭＷ＝９３０であった。また、波調製４か月後の分子量
は１５８０であった実施例１〜７および比較例２．３の
原材料配合、電導度滴定により求めた導電率の最小値、
１重量％のアンモニア水で導電率を調整した後の導電率
およびｐＨ（導電率最小値のときのｐＨ値に比べて小さ
い（酸性側）か大きいく塩基性側）かで表示）、重量平
均分子量（初期と波調製４か男後）、ならびに、塗膜状
態を第１表にまとめた。Comparative Example 3 A mixture with the same formulation as in Example 1 was stored at room temperature for 2 days, and then the conductivity was adjusted to the acidic side at least 3 μS/3 from the minimum value using ammonia water and the molecular weight was measured. However, the MW was 930. In addition, the molecular weight after 4 months of wave preparation was 1580.The raw material composition of Examples 1 to 7 and Comparative Example 2.3, the minimum value of conductivity determined by conductivity titration,
Conductivity and pH after adjusting conductivity with 1% by weight ammonia water (displayed as whether it is smaller (acidic side) or larger (more basic side) than the pH value at the minimum conductivity value), weight average The molecular weight (initial and after 4 months of wave preparation) and coating film condition are summarized in Table 1.
第１表にみるように、実施例のコーティング材は、導電
率が最小値または最小値よりも３μｓ／１以内（このと
きのｐＨ値は、導電率最小値のときのｐＨ値よりも酸性
側にくるようにされていた）に調整されており、液間製
４か月後の分子量が１５００以下であった。また、塗膜
の状態も良好であった。これに対し、比較例のコーティ
ング材は、導電率が上記範囲に調整されておらず、液間
製４か月後の分子量が１５００を越えており、塗膜の状
態も悪かった。As shown in Table 1, the coating material of the example has a minimum conductivity or within 3 μs/1 of the minimum value (the pH value at this time is on the acidic side than the pH value at the minimum conductivity value). The molecular weight was 1500 or less after 4 months of liquid production. Moreover, the condition of the coating film was also good. On the other hand, the conductivity of the coating material of the comparative example was not adjusted to the above range, the molecular weight after 4 months of liquid production exceeded 1500, and the condition of the coating film was also poor.
この発明にかかる無機系コーティング材の製造方法は、
液全体の導電率が最小値または最小値よりも３μＳ ／
ｃｓ以内（ただし、このときのｐＨ値は最小値のとき
のｐＨ値よりも酸性側にくるようにする。）になるよう
にｉｌｌ製するので、長期間保存してもプレポリマーの
分子量をＭＷ−６００〜１５００以内にとどめることが
できる。プレポリマーの分子量Ｍｗ＝６００〜１５００
であると、この発明により得られるコーティング材は、
塗膜にクランクがより発生しにくかったり、反応が遅す
ぎなかったり、柔らかい塗膜になりにくかったり、！！
Ｉｌｌのレベリング性がよくなったりする。The method for producing an inorganic coating material according to this invention includes:
The electrical conductivity of the entire liquid is at the minimum value or 3 μS / below the minimum value.
cs (however, the pH value at this time should be on the more acidic side than the minimum pH value), so even if stored for a long period of time, the molecular weight of the prepolymer will not change to MW. It can be kept within -600 to 1500. Molecular weight Mw of prepolymer = 600 to 1500
Then, the coating material obtained by this invention is
The paint film is less prone to cranking, the reaction is not too slow, and the paint film is less likely to become soft! !
The leveling properties of Ill will improve.
第１図は、無機系コーティング材の分子量の導電率依存
性を表すグラフである。
代理人 弁理士 松 本 武 彦FIG. 1 is a graph showing the conductivity dependence of the molecular weight of an inorganic coating material. Agent Patent Attorney Takehiko Matsumoto
Claims (1)
い、全体の導電率が最小値または最小値よりも３μＳ／
ｃｍ以内（ただし、このときのｐＨ値は最小値のときの
ｐＨ値よりも酸性側にくるようにする。）になるように
無機系コーティング材を調製する無機系コーティング材
の製造方法。 （ａ）下記一般式［１］においてｎ＝０で表されるケイ
素化合物および／またはコロイド状シリカ２０〜２００
重量部。 （ｂ）下記一般式［１］においてｎ＝１で表されるケイ
素化合物１００重量部。 （ｃ）下記一般式［１］においてｎ＝２で表されるケイ
素化合物３０〜８０重量部。 Ｒ＾１＿ｎＳｉ（ＯＲ＾２）＿４＿−＿ｎ・・・［１］
（ただし、［１］式中、Ｒ＾１およびＲ＾２はそれぞれ
アルキル基であり、Ｒ＾１およびＲ＾２がそれぞれ複数
個の場合には、すべてのＲ＾１またはＲ＾２が同じ基で
あってもよい。）[Claims] 1. Using the following (a), (b) and (c) as main components, the overall conductivity is the minimum value or 3 μS/
cm (however, the pH value at this time should be on the more acidic side than the minimum pH value). (a) Silicon compound and/or colloidal silica 20 to 200 represented by n=0 in the following general formula [1]
Weight part. (b) 100 parts by weight of a silicon compound represented by n=1 in the following general formula [1]. (c) 30 to 80 parts by weight of a silicon compound represented by n=2 in the following general formula [1]. R^1_nSi(OR^2)_4_-_n...[1]
(However, in formula [1], R^1 and R^2 are each an alkyl group, and if there are multiple R^1 and R^2, all R^1 or R^2 are the same) (It may be a base.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2167729A JP2594375B2 (en) | 1990-06-25 | 1990-06-25 | Manufacturing method of inorganic coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2167729A JP2594375B2 (en) | 1990-06-25 | 1990-06-25 | Manufacturing method of inorganic coating material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0455476A true JPH0455476A (en) | 1992-02-24 |
| JP2594375B2 JP2594375B2 (en) | 1997-03-26 |
Family
ID=15855074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2167729A Expired - Fee Related JP2594375B2 (en) | 1990-06-25 | 1990-06-25 | Manufacturing method of inorganic coating material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2594375B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262349A (en) * | 2006-03-30 | 2007-10-11 | Atomix Co Ltd | Coating composition and resin-coated article coated therewith |
| JP2009001185A (en) * | 2007-06-22 | 2009-01-08 | Honda Motor Co Ltd | Car body rear structure |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6046501A (en) * | 1983-08-25 | 1985-03-13 | Seiko Epson Corp | plastic cleanse |
| JPS6443570A (en) * | 1987-08-11 | 1989-02-15 | Osaka Organic Chem Ind | Colorable coating composition |
| JPH01245062A (en) * | 1988-03-25 | 1989-09-29 | Asahi Glass Co Ltd | Coating composition and plastic molded article with film therefrom |
| JPH02150430A (en) * | 1988-04-25 | 1990-06-08 | General Electric Co <Ge> | Flexible silicone coating for plastic base, and manufacture of thermoformable abrasion-resistant thermoplastic article |
-
1990
- 1990-06-25 JP JP2167729A patent/JP2594375B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6046501A (en) * | 1983-08-25 | 1985-03-13 | Seiko Epson Corp | plastic cleanse |
| JPS6443570A (en) * | 1987-08-11 | 1989-02-15 | Osaka Organic Chem Ind | Colorable coating composition |
| JPH01245062A (en) * | 1988-03-25 | 1989-09-29 | Asahi Glass Co Ltd | Coating composition and plastic molded article with film therefrom |
| JPH02150430A (en) * | 1988-04-25 | 1990-06-08 | General Electric Co <Ge> | Flexible silicone coating for plastic base, and manufacture of thermoformable abrasion-resistant thermoplastic article |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262349A (en) * | 2006-03-30 | 2007-10-11 | Atomix Co Ltd | Coating composition and resin-coated article coated therewith |
| JP2009001185A (en) * | 2007-06-22 | 2009-01-08 | Honda Motor Co Ltd | Car body rear structure |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2594375B2 (en) | 1997-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2776259B2 (en) | Antibacterial inorganic paint | |
| TWI594947B (en) | Inorganic polymer material, method for forming the same, and inorganic polymer coatingproduced therefrom | |
| JPH0786183B2 (en) | Coating composition for coating | |
| JPH0455476A (en) | Production of inorganic coating material | |
| CN100396751C (en) | A kind of organosilicon fluorine waterproofing agent and preparation method thereof | |
| JPH0830169B2 (en) | Coating composition | |
| JPS63137972A (en) | Coating composition | |
| JPH028273A (en) | Silicon alkoxide-based coating material | |
| JPH0485380A (en) | Inorganic coating material | |
| JP2637793B2 (en) | Composition for coating | |
| JP2005154397A (en) | Water soluble titanium composition | |
| US5270428A (en) | Corrosion-resistant silane polymer coating compositions | |
| JPH0236282A (en) | Silicon alkoxide-based coating material and production thereof | |
| JPH0478663B2 (en) | ||
| JPH01168A (en) | Silicon alkoxide coating agent | |
| JP2000327996A (en) | Coating method and silicon-containing liquid composition | |
| JP2009209250A (en) | Photocatalyst coating film forming composition, photocatalyst coating film, and forming method of photocatalyst coating film | |
| JPH0356576A (en) | Silicon alkoxide-based coating material | |
| JPH093402A (en) | Composition for coating | |
| JP3193832B2 (en) | Coating composition and method for producing the same | |
| JPH0819379B2 (en) | Inorganic coating material manufacturing method | |
| JPH02222475A (en) | Silicon alkoxide coating material | |
| JPH01163277A (en) | Silicon alkoxide-based coating material | |
| JP3023392B2 (en) | Painted article and method of manufacturing the same | |
| JPH01163275A (en) | Silicon alkoxide-based coating material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |