JP2006328424A - Siloxane compound and liquid composition using the same - Google Patents
Siloxane compound and liquid composition using the same Download PDFInfo
- Publication number
- JP2006328424A JP2006328424A JP2006237719A JP2006237719A JP2006328424A JP 2006328424 A JP2006328424 A JP 2006328424A JP 2006237719 A JP2006237719 A JP 2006237719A JP 2006237719 A JP2006237719 A JP 2006237719A JP 2006328424 A JP2006328424 A JP 2006328424A
- Authority
- JP
- Japan
- Prior art keywords
- siloxane compound
- compound
- organic
- liquid composition
- liquid
- 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
Abstract
Description
本発明は、シロキサン化合物並びにこれを含有する液状組成物及びこれらの硬化物に関する。 The present invention relates to a siloxane compound, a liquid composition containing the same, and a cured product thereof.
有機樹脂にアルコキシシリル基を導入することにより、塗膜の硬度、耐酸性、耐候性等の改善が従来より試みられている。更に近年、テトラエトキシシラン、テトラメトキシシラン、メチルトリメトキシシラン、エチルトリメトキシシラン、ジメチルジメトキシシラン、ビニルトリメトキシシラン等のアルコキシシラン、及びこれらを部分加水分解縮合したオリゴマーを単独でコーティング剤として用いたり、或いはこれらを樹脂と配合して用いることが検討されている。本発明者らは先に、それ自身で、或いは各種の樹脂、シランカップラー等の有機成分と配合して極めて有用な硬化組成物を供することのできる、下記の示性式に示すシロキサン化合物を用いた組成物を提案している（特願平７−１５７８９７）。
（化２）
ＳｉＯａ（ＯＨ）ｂ（ＯＲ１）ｃ（ＯＲ２）ｄ
（ただし０．８≦ａ≦１．６、０．３≦ｂ≦１．３、０．２≦ｃ＋ｄ≦１．９、ｂ＝４−（２ａ＋ｃ＋ｄ）、Ｒ１はメチル基又はエチル基、Ｒ２はＲ１以外の有機基）
Attempts have been made to improve the hardness, acid resistance, weather resistance, etc. of the coating film by introducing alkoxysilyl groups into the organic resin. In recent years, alkoxysilanes such as tetraethoxysilane, tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, dimethyldimethoxysilane, vinyltrimethoxysilane, and oligomers obtained by partially hydrolytic condensation of these have been used alone as coating agents. Or using these in combination with a resin has been studied. The present inventors previously used a siloxane compound represented by the following formula, which can provide a very useful cured composition by itself or by blending with various components such as various resins and silane couplers. The proposed composition is proposed (Japanese Patent Application No. 7-157897).
(Chemical formula 2)
SiO a (OH) b (OR 1 ) c (OR 2 ) d
(However, 0.8 ≦ a ≦ 1.6, 0.3 ≦ b ≦ 1.3, 0.2 ≦ c + d ≦ 1.9, b = 4- (2a + c + d), R 1 is a methyl group or an ethyl group, R 2 is an organic group other than R 1 )
しかし、このシロキサン化合物は、外観上は安定な液状を長期間保つものの、一定期間以上の保存をした液は、硬化して得られる塗膜の硬度、耐沸騰水性等の特性が低下してくる場合があることが判った。これは、この物の有する反応性官能基の経時変化が徐々に進行するためと考えられ、より一層の安定化が図れれば、非常に有用であると考えられた。 However, although this siloxane compound maintains a stable liquid state for a long period of time, a liquid that has been stored for a certain period or longer deteriorates properties such as hardness and boiling water resistance of a coating film obtained by curing. It turns out that there is a case. This is thought to be due to the gradual change of the reactive functional group possessed by this product, and it was thought that it would be very useful if further stabilization was achieved.
そこで、本発明者らは更に鋭意検討したところ、官能基の経時変化が少なくかつ安定に液状で存在する、特定示性式で表されるシロキサン化合物を得ることに成功し、本発明に到達した。すなわち、本発明は、
（１）以下の示性式で表されるシロキサン化合物、
Thus, the present inventors have further studied earnestly, and succeeded in obtaining a siloxane compound represented by a specific formula, which has a small functional group change over time and stably exists in liquid form, and has reached the present invention. . That is, the present invention
(1) A siloxane compound represented by the following formula:
（化３）
ＳｉＯａ（ＯＨ）ｂ（ＯＲ１）ｃ（ＯＲ２）ｄ
（ただし１．０≦ａ≦１．６、０≦ｂ＜０．３、ｂ＝４−（２ａ＋ｃ＋ｄ）、０≦ｃ≦２．０、０≦ｄ≦２．０、Ｒ１はメチル基又はエチル基、Ｒ２はＲ１と相異なる有機基）
（２）上記シロキサン化合物を含有する液状組成物、
及び（３）上記シロキサン化合物と相溶しうる有機化合物を配合してなる液状組成物、に存する。
(Chemical formula 3)
SiO a (OH) b (OR 1 ) c (OR 2 ) d
(However, 1.0 ≦ a ≦ 1.6, 0 ≦ b <0.3, b = 4- (2a + c + d), 0 ≦ c ≦ 2.0, 0 ≦ d ≦ 2.0, R 1 is a methyl group or Ethyl group, R 2 is an organic group different from R 1 )
(2) a liquid composition containing the siloxane compound,
And (3) a liquid composition comprising an organic compound compatible with the siloxane compound.
以下、本発明を詳細に説明する。
まず、本発明のシロキサン化合物は、以下の示性式で表されるものである。
（化４）
ＳｉＯａ（ＯＨ）ｂ（ＯＲ１）ｃ（ＯＲ２）ｄ
（ただし１．０≦ａ≦１．６、０≦ｂ＜０．３、ｂ＝４−（２ａ＋ｃ＋ｄ）、０≦ｃ≦２．０、０≦ｄ≦２．０、Ｒ１はメチル基又はエチル基、Ｒ２はＲ１と相異なる有機基）
Hereinafter, the present invention will be described in detail.
First, the siloxane compound of the present invention is represented by the following formula.
(Chemical formula 4)
SiO a (OH) b (OR 1 ) c (OR 2 ) d
(However, 1.0 ≦ a ≦ 1.6, 0 ≦ b <0.3, b = 4- (2a + c + d), 0 ≦ c ≦ 2.0, 0 ≦ d ≦ 2.0, R 1 is a methyl group or Ethyl group, R 2 is an organic group different from R 1 )
ここで、ｂ＜０．３であることが重要である。何故ならば、ｂが０．３を超えると塗膜化した場合の塗膜特性の劣化を起こし易い。これは、ｂが０．３を超えた場合、シラノール基はアルコキシ基との脱アルコール縮合反応によるシロキサンの生成、又はシラノール基相互の脱水縮合反応によるシロキサンの生成を誘発し、官能基の経時的な減少を引き起こしているためではないかと考えられる。ここで、特に本発明のシロキサン化合物においては、特にｂ＜０．３とすることにより、液での貯蔵安定性を大きく向上させることができることが見出されたものである。
好ましくはｂ≦０．２、更に好ましくはｂ≦０．１である。これにより、液の貯蔵安定性が極めて優れたものとすることができる上、得られる塗膜の特性を優れたものとして保持できる。
Here, it is important that b <0.3. This is because if b exceeds 0.3, the coating film characteristics are likely to be deteriorated when the coating film is formed. This is because when b exceeds 0.3, the silanol group induces the formation of a siloxane by a dealcoholization condensation reaction with an alkoxy group or the formation of a siloxane by a dehydration condensation reaction between silanol groups. It is thought that it is because of causing a decrease. Here, especially in the siloxane compound of the present invention, it has been found that the storage stability in the liquid can be greatly improved by setting b <0.3 in particular.
Preferably b ≦ 0.2, more preferably b ≦ 0.1. Thereby, the storage stability of the liquid can be made extremely excellent, and the properties of the obtained coating film can be kept excellent.
また、１．０≦ａ≦１．６である。ａ＜１．０では、重合度が十分でなく、このシロキサン化合物自身を塗膜化、又はこのシロキサン化合物と後述する有機高分子等の有機化合物と配合して得られる液状組成物を塗膜化した場合の耐擦傷性、耐溶剤性等の向上効果の発現が乏しい。
ａ＞１．６では、得られたシロキサン化合物の高分子量化が進み過ぎゲル化し易く、貯蔵安定性の悪いものになってしまう。
Further, 1.0 ≦ a ≦ 1.6. When a <1.0, the degree of polymerization is not sufficient, and this siloxane compound itself is coated, or a liquid composition obtained by blending this siloxane compound with an organic compound such as an organic polymer described later is coated. In this case, the improvement effect such as scratch resistance and solvent resistance is poor.
When a> 1.6, the resulting siloxane compound is too high in molecular weight and easily gelled, resulting in poor storage stability.
ここで、Ｒ１はメチル基又はエチル基である。特にメチル基の場合、反応性が高く高重合化し易いため、特に得られる硬化物の硬度、耐薬品性等の特性に優れる。
しかしながら、上記示性式の係数ａで表されるシロキサン化合物のシロキサン重合度が高くなると、後述する有機高分子等の有機化合物と配合して用いる場合に「相溶性の低下」から使用上、問題を生じることがある。このときの「相溶性の低下」とは、シロキサン化合物と有機化合物が配合時に白濁又は分液もしくは何れかが析出する様な状況であり、このような場合には均一かつ透明な混合液が得られないため、これを塗膜化しても、透明な均一膜を得ることは困難となる。
Here, R 1 is a methyl group or an ethyl group. In particular, in the case of a methyl group, since it has high reactivity and is easily polymerized, it is excellent in properties such as hardness and chemical resistance of the obtained cured product.
However, when the degree of siloxane polymerization of the siloxane compound represented by the coefficient a in the above-mentioned formula increases, when using it in combination with an organic compound such as an organic polymer to be described later, there is a problem in use due to “decrease in compatibility”. May occur. The “decrease in compatibility” at this time is a situation in which the siloxane compound and the organic compound are clouded or separated or any of them is precipitated at the time of blending. In such a case, a uniform and transparent mixed solution is obtained. Therefore, even if this is formed into a coating film, it becomes difficult to obtain a transparent uniform film.
そこで、本発明者らの更なる検討によりＲ１の一部もしくは全部を、例えばＲ１よりも有機性の高い官能基であるＲ２で置換することにより、種々の有機高分子等の有機化合物との相溶性を改良できることが見出されたものである。つまり、シロキサン化合物に有機化合物を配合する場合には、以下説明するＲ２を適宜選択することにより、シロキサン化合物と有機化合物との相溶性を向上させることができるのである。
すなわち、Ｒ２はＲ１以外の有機基である。好ましくはＲ１をエステル交換して得られる有機基であればよく、具体的には１価もしくは２価のアルコール類とエステル交換して得られる有機基、例えばアルキル基、アリール基、アラルキル基、アリル基、１−メトキシ−２−エチル基、１−エトキシ−２−プロピル基、１−メトキシ−２−プロピル基、２−メトキシエチル基、２−エトキシエチル基、Ｃ２Ｈ５ＯＣ２Ｈ４ＯＣ２Ｈ４−、ＣＨ３Ｃ２Ｈ４ＯＣ２Ｈ４−、Ｃ２Ｈ５ＯＣ２Ｈ４−、ＣＨ３ＯＣ２Ｈ４−等が挙げられ、例えば特開平２−２５６６８７号公報に記載されている様な活性水素含有化合物を用いてＲ１の一部または全部を置換したものでもよい。更に、Ｒ２として複数種類の基を導入することも可能である。
Therefore, the part or all R 1 by further study of the present inventors, for example, by replacing R 2 than R 1 is a highly organic functional group, an organic compound such as various organic polymers It has been found that the compatibility with can be improved. That is, when an organic compound is added to the siloxane compound, the compatibility between the siloxane compound and the organic compound can be improved by appropriately selecting R 2 described below.
That is, R 2 is an organic group other than R 1 . Preferably, it may be an organic group obtained by transesterification of R 1 , specifically, an organic group obtained by transesterification with a monovalent or divalent alcohol, such as an alkyl group, an aryl group, an aralkyl group, Allyl group, 1-methoxy-2-ethyl group, 1-ethoxy-2-propyl group, 1-methoxy-2-propyl group, 2-methoxyethyl group, 2-ethoxyethyl group, C 2 H 5 OC 2 H 4 OC 2 H 4 —, CH 3 C 2 H 4 OC 2 H 4 —, C 2 H 5 OC 2 H 4 —, CH 3 OC 2 H 4 — and the like can be mentioned, for example, described in JP-A-2-256687. A part or all of R 1 may be substituted with an active hydrogen-containing compound as described above. Furthermore, it is also possible to introduce a plurality of types of groups as R 2.
通常、これらＲ２の導入は、シロキサン化合物の官能基がＲ１だけでは配合する有機化合物及びその溶剤成分と相溶しない場合に行うことができる。このときのＲ２の種類及びＲ１との比率は、配合する有機化合物との相溶性および所望の硬化物の特性等から適宜選択すればよい。 In general, the introduction of R 2 can be performed when the functional group of the siloxane compound is not compatible with the organic compound to be blended and its solvent component only by R 1 . The type of R 2 and the ratio with R 1 at this time may be appropriately selected from the compatibility with the organic compound to be blended, the properties of the desired cured product, and the like.
ここで、０．５≦（ｃ＋ｄ）≦２．０の範囲が好ましい。（ｃ＋ｄ）＜０．５では得られたシロキサン化合物がゲル化し易い。一方（ｃ＋ｄ）＞２．０ではシロキサン化合物自身を塗膜化した場合、又はこのシロキサン化合物と有機高分子等の有機化合物と配合して得られる液状組成物を塗膜化した場合の耐擦傷性、耐溶剤性等の向上効果の発現が乏しい傾向にある。シロキサン化合物の重合度が十分でないためと考えられる。 Here, the range of 0.5 ≦ (c + d) ≦ 2.0 is preferable. When (c + d) <0.5, the obtained siloxane compound is easily gelled. On the other hand, when (c + d)> 2.0, the scratch resistance when the siloxane compound itself is coated or a liquid composition obtained by blending this siloxane compound with an organic compound such as an organic polymer is coated. There is a tendency that the improvement effect such as solvent resistance is poor. This is probably because the degree of polymerization of the siloxane compound is not sufficient.
このような本発明のシロキサン化合物を得るための方法は特に限定されず、いずれの方法で得られた物も該当するが、例えば、以下に述べる本発明の方法により本発明のシロキサン化合物を得ることができる。
すなわち、Ｓｉ（ＯＲ１）４で表されるテトラアルコキシシランに、通常１．１〜１．６モル倍量程度の水を加え、所望の程度まで加水分解縮合反応を進行させる。この反応は、触媒及び溶媒の存在下で行うことが好ましく、溶媒としてはＲ１ＯＨを用いることが反応の制御のし易さから好ましい。反応自体は、溶媒の還流下の様な加熱系又は室温下で行ってもよく、通常、用いる触媒にもよるが還流下で２〜４時間、室温で１〜３日間でｂ＜０．３とすることが可能である。
The method for obtaining such a siloxane compound of the present invention is not particularly limited, and the product obtained by any method is applicable. For example, the siloxane compound of the present invention is obtained by the method of the present invention described below. Can do.
That is, about 1.1 to 1.6 moles of water is usually added to tetraalkoxysilane represented by Si (OR 1 ) 4 and the hydrolysis condensation reaction proceeds to a desired degree. This reaction is preferably carried out in the presence of a catalyst and a solvent, and R 1 OH is preferably used as the solvent because of easy control of the reaction. The reaction itself may be carried out under a heating system such as under reflux of the solvent or at room temperature. Usually, although depending on the catalyst used, b <0.3 at reflux for 2 to 4 hours and at room temperature for 1 to 3 days. Is possible.
また、Ｓｉ（ＯＲ１）のＲ１をＲ２に置換する場合は、引き続きこの液に所定量のＲ２ＯＨを添加した後、加温し副生するＲ１ＯＨ及び／又は溶媒のＲ１ＯＨを留去しながらエステル交換反応を進行させればよい。このとき、用いるＲ２ＯＨはＲ１ＯＨよりも高沸点のものが留去によるロスが少なく、反応制御し易いため好ましい。尚、溶媒がＲ１ＯＨの場合で、これを留去することでシロキサン化合物が高粘度になり過ぎ安定性が問題となる場合は、エステル交換しないような溶媒をエステル交換反応の前もしくは後に添加して、安定化を図ることも可能である。 In addition, when replacing R 1 of Si (OR 1 ) with R 2 , a predetermined amount of R 2 OH is subsequently added to this solution, followed by heating and by-product R 1 OH and / or solvent R 1. What is necessary is just to advance transesterification, distilling off OH. At this time, R 2 OH having a higher boiling point than R 1 OH is preferable because it has less loss due to distillation and is easy to control the reaction. When the solvent is R 1 OH, and the siloxane compound becomes too viscous to cause stability problems by distilling it off, a solvent that does not transesterify is added before or after the transesterification reaction. Thus, stabilization can also be achieved.
このように、比較的単純且つ容易な方法で、しかも様々な用途に有用な本発明のシロキサン化合物を得ることができるのである。例えば、このような方法により得られる本発明のシロキサン化合物は、通常、重合度の異なる化合物の混合物からなる液状シロキサン化合物であるが、この液状シロキサン化合物の示性式は、例えば以下の方法で求めることができる。
（１）２９Ｓｉ−ＮＭＲにより、Ｓｉ原子に結合しているＯ原子の数を求め、係数ａの値を求める。
（２）１３Ｃ−ＮＭＲ又は１Ｈ−ＮＭＲにより、Ｓｉ原子に結合しているメトキシ基等のアルコキシ基の数を求め、係数ｃを求める。
（３）ｂ＝４−（２ａ＋ｃ）より、本発明の示性式における、係数ｂを求める。尚、ｄ＝０の場合は、反応の前提を以下の通りとして計算を行うことができる。
（化５）
Ｓｉ（ＯＲ１）４ ＋ Ｈ２Ｏ
→ ＳｉＯａ（ＯＨ)ｂ（ＯＲ１）ｃ ＋（４−ｃ）Ｒ１ＯＨ
また、ｄ＝０でない場合は、反応の前提を以下の通りとして計算を行うことができる。
（化６）
Ｓｉ（ＯＲ１）４ ＋ Ｈ２Ｏ ＋ Ｒ２ＯＨ
→ ＳｉＯａ（ＯＨ)ｂ（ＯＲ１）ｃ（ＯＲ２）ｄ ＋（４−ｃ）Ｒ１ＯＨ
Thus, the siloxane compound of the present invention useful for various applications can be obtained by a relatively simple and easy method. For example, the siloxane compound of the present invention obtained by such a method is usually a liquid siloxane compound comprising a mixture of compounds having different degrees of polymerization, and the formula of this liquid siloxane compound is obtained, for example, by the following method. be able to.
(1) The number of O atoms bonded to Si atoms is determined by 29 Si-NMR, and the value of coefficient a is determined.
(2) The number of alkoxy groups such as a methoxy group bonded to the Si atom is determined by 13 C-NMR or 1 H-NMR, and the coefficient c is determined.
(3) From b = 4- (2a + c), the coefficient b in the equation of the present invention is obtained. In addition, when d = 0, the calculation can be performed on the assumption that the reaction is as follows.
(Chemical formula 5)
Si (OR 1 ) 4 + H 2 O
→ SiO a (OH) b (OR 1 ) c + (4-c) R 1 OH
Further, when d = 0 is not satisfied, the calculation can be performed on the assumption that the reaction is as follows.
(Chemical formula 6)
Si (OR 1 ) 4 + H 2 O + R 2 OH
→ SiO a (OH) b (OR 1 ) c (OR 2 ) d + (4-c) R 1 OH
なお、上述した製造方法は、本発明のシロキサン化合物を得るための代表的な手法であり、他の方法で本発明のシロキサン化合物を得てもよいことは言うまでもない。 In addition, the manufacturing method mentioned above is a typical method for obtaining the siloxane compound of this invention, and it cannot be overemphasized that the siloxane compound of this invention may be obtained with another method.
こうして得られる本発明のシロキサン化合物は、高重合度でありながら貯蔵安定性は１年以上、透明且つ組成変化のない液状態を保つことが可能である。
このように、従来存在したシロキサン化合物とは違った特徴を有する本発明のシロキサン化合物は、様々な用途に用いることができる。例えばこれを含有する液状組成物を粉体処理、塗布液、各種基材への含浸、添加剤、変性剤等として用いることができる。また、本発明のシロキサン化合物を例えば加水分解溶液としてハードコートに用いることも可能である。また、樹脂等の有機化合物を配合した液状組成物として用いることで、得られる塗膜は、配合前の樹脂等の有機化合物だけの塗膜に比べ、耐擦傷性、親水性付与、耐汚染性、耐酸性、耐候性、耐熱性等の特性向上に優れた効果を発現する。勿論、本発明のシロキサン化合物自体、あるいはこれに樹脂を配合した組成物を更に各種の溶媒等で希釈して塗布液等の用途に用いることも可能である。
The thus obtained siloxane compound of the present invention has a high degree of polymerization, but has a storage stability of 1 year or more, and can maintain a liquid state without any change in composition.
As described above, the siloxane compound of the present invention having characteristics different from those of conventional siloxane compounds can be used for various applications. For example, a liquid composition containing this can be used as a powder treatment, a coating solution, impregnation into various substrates, additives, modifiers, and the like. Moreover, it is also possible to use the siloxane compound of this invention for a hard coat as a hydrolysis solution, for example. In addition, by using it as a liquid composition in which an organic compound such as a resin is blended, the resulting coating film is more resistant to scratches, imparting hydrophilicity, and stain resistance than a coating film of only an organic compound such as a resin before blending. It exhibits excellent effects in improving properties such as acid resistance, weather resistance and heat resistance. Of course, it is also possible to dilute the siloxane compound of the present invention itself or a composition in which a resin is blended therein with various solvents to be used for a coating solution or the like.
ここで本発明のシロキサン化合物に配合する有機化合物は、本発明のシロキサン化合物と相溶可能なものが好ましい。相溶可能であるとは、これらを配合した時に白濁又は分液もしくは何れかが析出する様なことがなく、外観上均一かつ透明な混合液が得られることをいう。すなわち、シロキサン化合物が完全に溶解しているものに限られるものではない。 Here, the organic compound blended with the siloxane compound of the present invention is preferably compatible with the siloxane compound of the present invention. “Compatible” means that when these are blended, there is no white turbidity or liquid separation or any precipitation, and a uniform and transparent mixed liquid is obtained in appearance. In other words, it is not limited to those in which the siloxane compound is completely dissolved.
このような有機化合物としては、例えば、カルボキシル基、ヒドロキシル基、アルコキシ基等を有するものが挙げられ、具体的には、例えば
（Ｉ）シランカップラー（一般にはＲＳｉＸ３ ：Ｘは加水分解性基、Ｒは有機基）
（II）アルキルアルコキシシリコーン類
（III）アクリル樹脂、エポキシ樹脂、ポリエステル樹脂、ウレタン樹脂等のポリマー類
（IV）１，４ブタンジオール、グリセリン、カテコール、レゾルシン等の多価アルコール等が挙げられる。
Examples of such an organic compound include those having a carboxyl group, a hydroxyl group, an alkoxy group, and the like. Specifically, for example, (I) a silane coupler (generally RSiX 3 : X is a hydrolyzable group, R is an organic group)
(II) Alkyl alkoxysilicones (III) Polymers such as acrylic resins, epoxy resins, polyester resins, urethane resins (IV) Polyhydric alcohols such as 1,4 butanediol, glycerin, catechol, and resorcin.
より具体的には、例えば（Ｉ）のシランカップラーとしては、
（化７）
(Chemical formula 7)
（化８）
（化９）
Ｈ２ＮＣ３Ｈ６Ｓｉ（ＯＣ２Ｈ５）３ 、
Ｈ２ＮＣ２Ｈ４ＮＨＣ３Ｈ６Ｓｉ（ＯＣＨ３）３ 、
Ｈ２ＮＣＯＮＨＣ３Ｈ６Ｓｉ（ＯＣ２Ｈ５）３ 、
等のアミン系、
(Chemical 9)
H 2 NC 3 H 6 Si (OC 2 H 5 ) 3 ,
H 2 NC 2 H 4 NHC 3 H 6 Si (OCH 3 ) 3 ,
H 2 NCONHC 3 H 6 Si (OC 2 H 5 ) 3 ,
Amines such as
（化１０）
ＣＨ２＝ＣＨＳｉ（ＯＣ２Ｈ５）３ 、
ＣＨ２＝ＣＨＳｉ（ＯＣＨ３）３ 、
ＣＨ２＝ＣＨＳｉ（ＯＣ２Ｈ４ＯＣＨ３）３ 、
等のビニル系、
(Chemical formula 10)
CH 2 = CHSi (OC 2 H 5) 3,
CH 2 = CHSi (OCH 3 ) 3 ,
CH 2 = CHSi (OC 2 H 4 OCH 3) 3,
Vinyl-based, etc.
（化１１）
ＨＳ−Ｃ３Ｈ６Ｓｉ（ＯＣＨ３）３ 、
ＨＳ−Ｃ３Ｈ６Ｓｉ（ＯＣ２Ｈ５）３ 、
ＨＳ−Ｃ３Ｈ６Ｓｉ（ＯＣ２Ｈ４ＯＣＨ３）３ 、
等のメルカプト系、
等が挙げられる。
(Chemical Formula 11)
HS-C 3 H 6 Si ( OCH 3) 3,
HS-C 3 H 6 Si ( OC 2 H 5) 3,
HS-C 3 H 6 Si ( OC 2 H 4 OCH 3) 3,
Mercapto, such as
Etc.
これらはいずれも好適に用いることができるが、例えばコーティングを施す場合には基材の種類又は目的とする膜特性等により適宜、適応するシランカップラーを選択することで、より密着性の優れたコーティングを得ることができる。 Any of these can be suitably used. For example, when coating is performed, a coating with more excellent adhesion can be obtained by appropriately selecting a suitable silane coupler depending on the type of base material or desired film characteristics. Can be obtained.
また、（II）のアルキルアルコキシシリコーン類としては、
（化１２）
（ＣＨ３Ｏ）３Ｓｉ−{ＯＳｉ（ＣＨ３）２}ｎ−{ＯＳｉ（ＯＣＨ３）２}ｍ−ＯＣＨ３
ｎ，ｍ＝１〜１０
等が挙げられる。
In addition, as (II) alkyl alkoxy silicones,
(Chemical formula 12)
(CH 3 O) 3 Si- { OSi (CH 3) 2} n - {OSi (OCH 3) 2} m -OCH 3
n, m = 1-10
Etc.
(III)のポリマー類としては、
（１）アクリル樹脂
（ａ）
（化１３）
(1) Acrylic resin (a)
(Chemical Formula 13)
（ｂ）上記（ａ）構造にγーＭＴＳ（γーメタクリロキシプロピルトリメトキシシラン）を付加したもの (B) γ-MTS (γ-methacryloxypropyltrimethoxysilane) added to the structure (a)
（２）エポキシ樹脂
（化１４）
（３）ポリエステル樹脂
（化１５）
（化１６）
これらは、本発明のシロキサン化合物と配合し得る有機化合物の例示であり、本発明で用いることのできる有機化合物はこれらに限られるものではなく、上述した本発明のシロキサン化合物と相溶し得るものであれば、いずれも用いることができる。
又、上記の有機化合物は、目的に応じて２種以上を併用することもできる。
These are examples of organic compounds that can be blended with the siloxane compound of the present invention, and the organic compounds that can be used in the present invention are not limited to these, and can be compatible with the siloxane compound of the present invention described above. Any of them can be used.
In addition, two or more of the above organic compounds may be used in combination depending on the purpose.
例えば、エポキシ樹脂とエポキシ系シランカップラー、アクリル樹脂とアクリル系シランカップラー、ポリエステル樹脂とエポキシ系シランカップラー等、樹脂成分とシランカップラーとを併用することにより、コーティング材として用いた場合の基材との密着性が向上し、又樹脂成分とシロキサン化合物との相溶性が更に向上し得られるコーティング膜の特性がより優れたものとなる等、目的に応じ適時選択することができる。尚、併用に際しては、２種以上を予め配合しても、各々をシロキサン化合物に添加してもよい。 For example, by using a resin component and a silane coupler together, such as an epoxy resin and an epoxy silane coupler, an acrylic resin and an acrylic silane coupler, a polyester resin and an epoxy silane coupler, and a base material when used as a coating material The adhesion can be improved, and the compatibility between the resin component and the siloxane compound can be further improved, so that the properties of the coating film can be further improved. In combination, two or more kinds may be blended in advance or each may be added to the siloxane compound.
また、シロキサン化合物と有機化合物との配合は室温下または場合によっては加熱下で行っても構わない。更に、必要に応じて、溶媒、分散媒、硬化触媒等を添加することができる。 Further, the blending of the siloxane compound and the organic compound may be performed at room temperature or in some cases under heating. Furthermore, a solvent, a dispersion medium, a curing catalyst, etc. can be added as needed.
有機化合物とシロキサン化合物との配合割合は、不揮発成分として通常、シロキサン化合物１００重量部に対して、有機化合物１〜５０００重量部と広い範囲での使用で効果を発揮する。例えば、本発明のシロキサン化合物の有する硬度、高耐熱性等の特性の発現を重視する場合は、有機化合物は１〜４００重量部の範囲が好ましい。この時の、配合液の不揮発成分中のＳｉＯ２換算濃度は１０〜９５％の範囲が好ましい。一方、有機化合物特に有機樹脂による柔軟性、厚膜化等の特性を維持しながら、シロキサン化合物を添加剤的に用いることにより有機化合物が主成分である塗膜等に低汚染性、耐候性等を付与することを重視する場合は、有機化合物は５００〜５０００重量部の範囲で配合することが好ましい。この時の、配合液の不揮発成分中のＳｉＯ２換算濃度は１〜１０％が好ましい。
なお、配合液中の各成分、特にシロキサン化合物と上述の有機化合物は、縮合した状態で液中に存在してもよいし、あるいは単に混合している状態で存在してもよい。用途及び有機化合物の種類に応じ、適宜選択すればよい。加熱、及び／又は副生するアルコールを系外に除去することにより縮合反応を促進させることもできる。
なお、本発明のシロキサン化合物と上述の有機化合物とを相溶状態とするには、各種の溶媒又は分散媒を添加した液状組成物とすることにより、相溶状態とすることも可能である。また、有機化合物の種類によっては本発明のシロキサン化合物と配合した後に一定時間放置、攪拌することにより相溶状態とすることもできる。
本発明のシロキサン化合物又は本発明の液状組成物を用いて各種粉体を処理する場合の処理方法は、一般的な湿式法又は乾式法で行うことができる。例えば、乾式法の場合はヘンシェルミキサー等の混合攪拌機付きで且つ乾燥可能な機器を用いれば好適である。
The compounding ratio of the organic compound and the siloxane compound is effective as a non-volatile component in a wide range of 1 to 5000 parts by weight of the organic compound with respect to 100 parts by weight of the siloxane compound. For example, when emphasizing the expression of characteristics such as hardness and high heat resistance of the siloxane compound of the present invention, the organic compound is preferably in the range of 1 to 400 parts by weight. At this time, SiO 2 concentration calculated in the non-volatile components of the formulation liquid is preferably in the range of 10% to 95%. On the other hand, while maintaining the properties such as flexibility and thickening of organic compounds, especially organic resins, the use of siloxane compounds as additives makes it possible to reduce contamination, weather resistance, etc. on coatings and the like containing organic compounds as the main component. In the case where importance is attached to the organic compound, the organic compound is preferably blended in the range of 500 to 5000 parts by weight. At this time, the SiO2 equivalent concentration in the non-volatile component of the blended liquid is preferably 1 to 10%.
Each component in the blending liquid, particularly the siloxane compound and the organic compound described above, may be present in the liquid in a condensed state, or may be present in a state of being simply mixed. What is necessary is just to select suitably according to a use and the kind of organic compound. The condensation reaction can also be promoted by heating and / or removing by-product alcohol out of the system.
In addition, in order to make the siloxane compound of this invention and the above-mentioned organic compound into a compatible state, it is also possible to set it as a compatible state by setting it as the liquid composition which added the various solvent or the dispersion medium. Further, depending on the type of the organic compound, it can be made in a compatible state by mixing with the siloxane compound of the present invention and then standing for a certain period of time and stirring.
The processing method in the case of processing various powders using the siloxane compound of the present invention or the liquid composition of the present invention can be performed by a general wet method or dry method. For example, in the case of the dry method, it is preferable to use a drying apparatus equipped with a mixing stirrer such as a Henschel mixer.
原料粉体と所定量のシロキサン化合物とを仕込み、原料粉体表面が充分濡れるまで室温で攪拌し、次に、攪拌を続けながら１００〜１５０℃に加熱しシロキサン化合物の架橋反応を促進させ、且つ水分等の揮発成分を蒸発させることにより表面処理された粉体を得ることができる。尚、所定量のシロキサン化合物で原料粉体が均一に濡れにくい場合は、シロキサン化合物を水等で希釈して用いてもよい。また、特にマトリクスとの親和性を高める場合、原料粉体をシロキサン化合物、特に本発明のシロキサン化合物あるいはこれを水等で希釈した液で予め原料粉体を表面処理し、必要に応じて乾燥等を行った後、更に本発明の液状組成物で処理することもできる。 The raw material powder and a predetermined amount of the siloxane compound are charged, stirred at room temperature until the surface of the raw material powder is sufficiently wetted, and then heated to 100 to 150 ° C. while continuing the stirring to promote the crosslinking reaction of the siloxane compound, and Surface-treated powder can be obtained by evaporating volatile components such as moisture. If the raw material powder is difficult to wet uniformly with a predetermined amount of siloxane compound, the siloxane compound may be diluted with water or the like. In particular, in order to increase the affinity with the matrix, the raw material powder is surface-treated in advance with a siloxane compound, in particular the siloxane compound of the present invention or a solution obtained by diluting this with water, and if necessary, dried. After performing, it can also be processed with the liquid composition of the present invention.
本発明のシロキサン化合物或いは液状組成物は様々な基材との親和性に優れるので、処理の対象となる原料粉体も特に制限されず、例えばガラス、セメント、コンクリート、鉄、銅、ニッケル、金、銀、アルミニウム、希土類、コバルト等の金属、カーボンブラック、グラファイト、炭素繊維、活性炭、炭素中空球等の炭素材、シリカ、アルミナ、酸化チタン、酸化ベリリウム、酸化鉄、酸化亜鉛、酸化マグネシウム、酸化スズ、酸化アンチモン、バリウムフェライト、ストロンチウムフェライト等の酸化物、水酸化アルミニウム、水酸化マグネシウム等の水酸化物、炭酸カルシウム、炭酸マグネシウム等の炭酸塩、硫酸カルシウム等の硫酸塩、タルク、クレー、マイカ、ケイ酸カルシウム、ガラス、ガラス中空球、ガラス繊維等のケイ酸塩、その他チタン酸カルシウム、チタン酸ジルコン酸鉛、窒
化アルミニウム、炭化ケイ素、硫化カドミニウム等の各種無機粉体、木粉、デンプン、各種有機顔料、ポリスチレン、ナイロン等の有機物充填材等、汎用充填材であると導電性・電磁波シールド性、磁性・遮音性・熱伝導性・遅燃性・難燃性。耐磨耗性等付与の為の機能性充填材であるとを問わず、本発明のポリシロキサン化合物或いは珪素含有組成物で処理することができる。そして、これらの原料粉体を本発明のポリシロキサン化合物或いは珪素含有組成物で処理してなる表面処理の成された粉体は、例えば油性塗料、合成樹脂塗料、水溶性樹脂塗料、エマルジョン塗料、骨材入りエマルジョン塗料、トラフィックペイント、パテ・コーキング等の塗料、靴底、電線、タイヤ、工業用品、ベルト、ホース、ゴム引布、ゴム糊、粘着テープ、ラテックス、バックサイジング等のゴム製品、塗工用、内
填用、合成紙等の紙用途、ＰＶＣ、ポリオレフィン、エポキシ・フェノール、不飽和ポリエステル等の合成樹脂製品、電気溶接棒、ガラス、酸中和、医薬品、食品、製糖、歯磨、クレンザー、バンカーサンド、農薬、配合飼料、建材等の各種充填材等に用いたり、充填材として繊維及び樹脂成分に配合して成型し、ＦＲＰ（Ｆｉｂｅｒ Ｒｅｉｎｆｏｒｃｅｄ Ｐｌａｓｔｉｃ）とすることもできる。
Since the siloxane compound or liquid composition of the present invention is excellent in affinity with various substrates, the raw material powder to be treated is not particularly limited. For example, glass, cement, concrete, iron, copper, nickel, gold Metals such as silver, aluminum, rare earth, cobalt, carbon black, graphite, carbon fiber, activated carbon, carbon hollow sphere, etc., silica, alumina, titanium oxide, beryllium oxide, iron oxide, zinc oxide, magnesium oxide, oxidation Oxides such as tin, antimony oxide, barium ferrite and strontium ferrite, hydroxides such as aluminum hydroxide and magnesium hydroxide, carbonates such as calcium carbonate and magnesium carbonate, sulfates such as calcium sulfate, talc, clay and mica Silicates such as calcium silicate, glass, glass hollow sphere, glass fiber Other general-purpose fillers such as calcium titanate, lead zirconate titanate, aluminum nitride, silicon carbide, cadmium sulfide and other inorganic powders, wood powder, starch, various organic pigments, polystyrene, nylon and other organic fillers And conductivity, electromagnetic shielding, magnetism, sound insulation, thermal conductivity, slow flame retardant, flame retardant. Regardless of whether it is a functional filler for imparting wear resistance or the like, it can be treated with the polysiloxane compound or silicon-containing composition of the present invention. And, the surface-treated powder obtained by treating these raw material powders with the polysiloxane compound or silicon-containing composition of the present invention is, for example, an oil-based paint, a synthetic resin paint, a water-soluble resin paint, an emulsion paint, Emulsion paint with aggregate, paint for traffic paint, putty caulking, etc., shoe soles, electric wires, tires, industrial products, belts, hoses, rubberized cloth, rubber glue, adhesive tape, latex, backsizing, etc. For industrial use, filling, synthetic paper, PVC, polyolefin, epoxy / phenol, unsaturated polyester and other synthetic resin products, electric welding rods, glass, acid neutralization, pharmaceuticals, food, sugar, toothpaste, cleanser , Used for various fillers such as bunker sands, agricultural chemicals, compound feeds, building materials, etc., blended with fibers and resin components as fillers, molded, FR Can also (Fiber Reinforced Plastic) to it.
また、本発明のシロキサン化合物或いは液状組成物を紙等の多孔質素材に含浸する場合は、これら素材をシロキサン化合物或いは液状組成物にティッピングした後乾燥すればよい。常温或いは加熱下、架橋反応を進行させれば、難燃性、平滑性等の特性を付与することができる。本発明のシロキサン化合物或いは液状組成物を接着用途に用いる場合は、被接着面にシロキサン化合物或いは液状組成物を塗布し完全に硬化する前に被接着面同士を圧着する。又は、予め被接着面を本発明のシロキサン化合物又はその加水分解液等でプリコートしておけば、更に接着強度が上がる。
さらに、これらの本発明の液状組成物、あるいは本発明のシロキサン化合物はそれ自体で、あるいは更に顔料を添加して塗料としたり、無機、有機の各種充填材を配合してなる硬化性組成物とし、硬化させて複合材とすることもできる。
顔料としては、無機系顔料として鉛白等の鉛化合物、亜鉛華、リトポン等の亜鉛化合物、酸化チタン等のチタン化合物、オーレオリン、コバルトグリーン、セルリアンブルー２、コバルトブルー、コバルトバイオレット等のコバルト化合物、酸化鉄等の鉄化合物、酸化クロム、クロム酸鉛、クロム酸バリウム等のクロム化合物、硫酸カドミウム、硫セレン化カドミウム等のカドミウム化合物、カーボンブラック等が挙げられる。また、有機系顔料として水に不溶のフタロシアニン系、ジオキサジン系、アントラキノン系、キノフタロン系等の有色化合物、又はこれらの金属含有化合物などが挙げられる。以上、列記した化合物以外でも本発明の液状組成物を着色する目的で使用できる物であれば、何れも用いることができることは言うまでもない。これらは、単独で用いたり、又は２種類以上を併用
することも可能である。
充填材としては、カーボンブラック、グラファイト、炭素繊維等の炭素材、シリカ、アルミナ、酸化マグネシウム等の酸化物、水酸化アルミニウム、水酸化マグネシウム等の水酸化物、炭酸カルシウム、炭酸マグネシウム等の炭酸塩、硫酸カルシウム等の硫酸鉛、タルク、クレー、マイカ、珪酸カルシウム、ガラス繊維等の珪酸化合物などの無機物充填材、ポリスチレン、ポリエチレン、ポリプロピレン、ナイロン等の有機高分子化合物、木粉、デンプンなどの有機物充填材等が挙げられる。これらは、単独で用いたり、又は２種類以上を併用することも可能である。
本発明のシロキサン化合物あるいは液状組成物にさらに顔料を添加した塗料とする場合は、予め有機化合物に分散しておけば、均一に顔料分散した珪素含有塗膜を容易に得ることができる。
このように、本発明のシロキサン化合物及び液状組成物、並びにこれらを硬化してなる硬化物は、様々な使用分野で種々の優れた特性を発揮する、非常に有用なものである。
Further, when a porous material such as paper is impregnated with the siloxane compound or liquid composition of the present invention, these materials may be tipped onto the siloxane compound or liquid composition and then dried. If the crosslinking reaction is allowed to proceed at room temperature or under heating, properties such as flame retardancy and smoothness can be imparted. When the siloxane compound or liquid composition of the present invention is used for bonding applications, the adherend surfaces are pressure-bonded before the siloxane compound or liquid composition is applied to the adherend surfaces and completely cured. Alternatively, if the surface to be bonded is precoated with the siloxane compound of the present invention or a hydrolyzate thereof, the adhesive strength is further increased.
Further, these liquid compositions of the present invention, or the siloxane compounds of the present invention, are curable compositions by themselves or by adding pigments to paints or blending various inorganic and organic fillers. It can also be cured to form a composite material.
As pigments, lead compounds such as lead white as inorganic pigments, zinc compounds such as zinc white and lithopone, titanium compounds such as titanium oxide, cobalt compounds such as aureoline, cobalt green, cerulean blue 2, cobalt blue and cobalt violet, Examples thereof include iron compounds such as iron oxide, chromium compounds such as chromium oxide, lead chromate and barium chromate, cadmium compounds such as cadmium sulfate and cadmium sulfate, carbon black and the like. Examples of organic pigments include phthalocyanine-based, dioxazine-based, anthraquinone-based, and quinophthalone-based colored compounds insoluble in water, and metal-containing compounds thereof. As described above, it goes without saying that any compounds other than those listed can be used as long as they can be used for the purpose of coloring the liquid composition of the present invention. These can be used alone or in combination of two or more.
Fillers include carbon materials such as carbon black, graphite and carbon fiber, oxides such as silica, alumina and magnesium oxide, hydroxides such as aluminum hydroxide and magnesium hydroxide, carbonates such as calcium carbonate and magnesium carbonate , Lead sulfate such as calcium sulfate, inorganic fillers such as silicate compounds such as talc, clay, mica, calcium silicate, glass fiber, organic polymer compounds such as polystyrene, polyethylene, polypropylene, nylon, and organic substances such as wood flour and starch A filler etc. are mentioned. These can be used alone or in combination of two or more.
In the case of preparing a coating material in which a pigment is further added to the siloxane compound or liquid composition of the present invention, a silicon-containing coating film in which the pigment is uniformly dispersed can be easily obtained by dispersing in advance in an organic compound.
As described above, the siloxane compound and liquid composition of the present invention, and a cured product obtained by curing these compounds are very useful, exhibiting various excellent properties in various fields of use.
以下、本発明を実施例により更に詳細に説明する。
実施例１
〔シロキサン化合物−１の合成〕
攪拌器、ジムロートコンデンサー、温度計を備えたガラス製２リットル四ツ口丸底フラスコにテトラメトキシシラン５０６．８ｇ、メタノール４２１．３ｇを仕込み５分攪拌した後、０．１規定塩酸水６．８ｇと水６５．３ｇの混合液を添加した。この時の、テトラメトキシシランに対する水の量は１．２モル倍に相当する。
その後、還流状態（６５℃）となるまで加熱し、還流下で４時間反応させた。このものを、室温まで放冷したのち取り出して液状で無色透明なシロキサン化合物−１、９９８．０ｇを得た。
Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
[Synthesis of Siloxane Compound-1]
A glass 2-liter four-necked round bottom flask equipped with a stirrer, Dimroth condenser and thermometer was charged with 506.8 g of tetramethoxysilane and 421.3 g of methanol and stirred for 5 minutes, and then 6.8 g of 0.1N hydrochloric acid water. And a mixture of 65.3 g of water were added. At this time, the amount of water with respect to tetramethoxysilane corresponds to 1.2 mol times.
Then, it heated until it became a recirculation | reflux state (65 degreeC), and was made to react under recirculation | reflux for 4 hours. This was allowed to cool to room temperature and then taken out to obtain 998.0 g of a liquid, colorless and transparent siloxane compound-1.
このシロキサン化合物−１の示性式
（化１７）
ＳｉＯａ（ＯＨ）ｂ（ＯＣＨ３）ｃ
を、以下の方法により求めた。
（１）２９Ｓｉ−ＮＭＲにより、Ｓｉ原子に結合しているＯ原子の数を求め、係数ａの値を求める。
（２）１３Ｃ−ＮＭＲにより、Ｓｉ原子に結合しているメトキシ基等のアルコキシ基の数を求め、係数ｃを求める。
（３）ｂ＝４−（２ａ＋ｃ）より、上記の示性式における、係数ｂを求める。尚、反応の前提を以下の通りとして計算を行った。
Schematic formula of this siloxane compound-1
SiO a (OH) b (OCH 3 ) c
Was determined by the following method.
(1) The number of O atoms bonded to Si atoms is determined by 29 Si-NMR, and the value of coefficient a is determined.
(2) The number of alkoxy groups such as a methoxy group bonded to the Si atom is determined by 13 C-NMR, and the coefficient c is determined.
(3) From b = 4- (2a + c), the coefficient b in the above equation is obtained. The calculation was performed on the premise of the reaction as follows.
（化１８）
Ｓｉ（ＯＣＨ３）４ ＋ Ｈ２Ｏ
→ ＳｉＯａ（ＯＨ）ｂ（ＯＣＨ３）ｃ ＋ （４−ｃ）ＣＨ３ＯＨ
この方法で、シロキサン化合物−１を示性式で表すと、
ＳｉＯ１．１５（ＯＨ）０．０５（ＯＣＨ３）１．６５
であった。
又、このシロキサン化合物−１について、密閉下で５０℃、４５日間（室温換算約１年間相当）の加速保存試験を実施したが、液粘度は当初の１．１ｃｐから１．２ｃｐ程度しか上昇せず、貯蔵安定性良好な液状物であった。
(Chemical formula 18)
Si (OCH 3 ) 4 + H 2 O
→ SiO a (OH) b (OCH 3 ) c + (4-c) CH 3 OH
In this method, when siloxane compound-1 is represented by a formula,
SiO 1.15 (OH) 0.05 (OCH 3 ) 1.65
Met.
In addition, this siloxane compound-1 was subjected to an accelerated storage test at 50 ° C. for 45 days (equivalent to about one year in terms of room temperature) in a sealed state, but the liquid viscosity increased only from the initial 1.1 cp to about 1.2 cp. It was a liquid with good storage stability.
実施例２
〔シロキサン化合物−２の合成〕
攪拌器、ジムロートコンデンサー、温度計を備えたガラス製２リットル四ツ口丸底フラスコにテトラメトキシシラン５０６．８ｇ、メタノール４０９．３ｇを仕込み５分攪拌した後、０．１規定塩酸水６．８ｇと水７７．３ｇの混合液を添加した。この時の、テトラメトキシシランに対する水の量は１．４モル倍に相当する。
その後、還流状態（６５℃）となるまで加熱し、還流下で４時間反応させた。このものを、室温まで放冷したのち取り出して液状で無色透明なシロキサン化合物−２、９９７．０ｇを得た。
Example 2
[Synthesis of Siloxane Compound-2]
A glass 2 liter four-necked round bottom flask equipped with a stirrer, Dimroth condenser and thermometer was charged with 506.8 g of tetramethoxysilane and 409.3 g of methanol and stirred for 5 minutes, and then 6.8 g of 0.1N hydrochloric acid water. And a mixture of 77.3 g of water were added. At this time, the amount of water with respect to tetramethoxysilane corresponds to 1.4 mol times.
Then, it heated until it became a recirculation | reflux state (65 degreeC), and was made to react under recirculation | reflux for 4 hours. This was allowed to cool to room temperature and then taken out to obtain 997.0 g of a liquid, colorless and transparent siloxane compound-2.
このシロキサン化合物−２を、実施例１と同様にＮＭＲ法で解析したところ、示性式は、
（化１９）
ＳｉＯ１．３５（ＯＨ）０．０６（ＯＣＨ３）１．２４
であった。
又、このシロキサン化合物−２について、密閉下で５０℃、４５日間（室温換算約１年間相当）の加速保存試験を実施したが、液粘度は当初の１．３ｃｐから１．６ｃｐ程度しか上昇せず、貯蔵安定性良好な液状物であった。
When this siloxane compound-2 was analyzed by NMR as in Example 1, the formula was
(Chemical formula 19)
SiO 1.35 (OH) 0.06 (OCH 3 ) 1.24
Met.
In addition, this siloxane compound-2 was subjected to an accelerated storage test at 50 ° C. for 45 days (equivalent to about one year in terms of room temperature) in a sealed state, but the liquid viscosity increased only from the initial 1.3 cp to about 1.6 cp. It was a liquid with good storage stability.
実施例３
〔シロキサン化合物−３の合成〕
攪拌器、ジムロートコンデンサー、温度計を備えたガラス製２リットル四ツ口丸底フラスコにテトラメトキシシラン５０６．８ｇ、メタノール３９７．３ｇを仕込み５分攪拌した後、０．１規定塩酸水６．８ｇと水８９．３ｇの混合液を添加した。この時の、テトラメトキシシランに対する水の量は１．６モル倍に相当する。
その後、還流状態（６５℃）となるまで加熱し、還流下で４時間反応させた。このものを、室温まで放冷したのち取り出して液状で無色透明なシロキサン化合物−３、９９８．７ｇを得た。
Example 3
[Synthesis of Siloxane Compound-3]
A glass 2-liter four-necked round bottom flask equipped with a stirrer, Dimroth condenser and thermometer was charged with 506.8 g of tetramethoxysilane and 397.3 g of methanol and stirred for 5 minutes, and then 6.8 g of 0.1N hydrochloric acid water. And a mixture of 89.3 g of water were added. At this time, the amount of water relative to tetramethoxysilane corresponds to 1.6 mol times.
Then, it heated until it became a recirculation | reflux state (65 degreeC), and was made to react under recirculation | reflux for 4 hours. This was allowed to cool to room temperature and then taken out to obtain 998.7 g of a liquid, colorless and transparent siloxane compound-3.
このシロキサン化合物−３を、実施例１と同様にＮＭＲ法で解析したところ、示性式は、
（化２０）
ＳｉＯ１．４６（ＯＨ）０．０８（ＯＣＨ３）１．００
であった。
又、このシロキサン化合物−３について、密閉下で５０℃、３０日間（室温換算約８ヶ月相当）の加速保存試験を実施したが、液粘度は当初の２．３ｃｐから２．７ｃｐ程度しか上昇せず、貯蔵安定性良好な液状物であった。
When this siloxane compound-3 was analyzed by NMR as in Example 1, the formula was
(Chemical formula 20)
SiO 1.46 (OH) 0.08 (OCH 3 ) 1.00
Met.
Moreover, this siloxane compound-3 was subjected to an accelerated storage test at 50 ° C. for 30 days (equivalent to about 8 months at room temperature) in a sealed state, but the liquid viscosity increased only from the initial 2.3 cp to about 2.7 cp. It was a liquid with good storage stability.
実施例４
〔シロキサン化合物−４の合成〕
ガラス製５００ｍｌ四ツ口丸底フラスコに攪拌器、温度計、リービッヒコンデンサーを取り付けた簡単な単蒸留装置に、実施例１で得られたシロキサン化合物１３０．０ｇとキシレン１０３．３ｇを仕込み攪拌しながら徐々に加熱して、留出温度が約６５℃でメタノールを留去させた。最終的には内温を１４６℃、留出温度約１４４℃まで昇温した後、冷却してメタノール含有量１ｗｔ％以下、キシレン５６．２ｗｔ％の液状で無色透明なシロキサン化合物−４、２３２．４ｇを得た。
Example 4
[Synthesis of Siloxane Compound-4]
A simple simple distillation apparatus equipped with a glass 500 ml four-necked round bottom flask equipped with a stirrer, thermometer and Liebig condenser was charged with 130.0 g of the siloxane compound obtained in Example 1 and 103.3 g of xylene while stirring. By gradually heating, methanol was distilled off at a distillation temperature of about 65 ° C. Finally, after raising the internal temperature to 146 ° C. and the distillation temperature to about 144 ° C., the solution was cooled and liquid, colorless and transparent siloxane compound-4 having a methanol content of 1 wt% or less and 56.2 wt% of xylene. 4 g was obtained.
このシロキサン化合物−４を、実施例１と同様にＮＭＲ法で解析したところ、示性式は、
（化２１）
ＳｉＯ１．１７（ＯＨ）０．０４（ＯＣＨ３）１．６２
であった。
又、このシロキサン化合物−４について、密閉下で５０℃、４５日間（室温換算約１年間相当）の加速保存試験を実施したが、液粘度は当初の２．０ｃｐから２．６ｃｐ程度しか上昇せず、貯蔵安定性良好な液状物であった。
When this siloxane compound-4 was analyzed by NMR as in Example 1, the formula was
(Chemical formula 21)
SiO 1.17 (OH) 0.04 (OCH 3 ) 1.62
Met.
Further, this siloxane compound-4 was subjected to an accelerated storage test at 50 ° C. for 45 days (equivalent to about one year in terms of room temperature) in a sealed state, but the liquid viscosity increased only from the initial 2.0 cp to about 2.6 cp. It was a liquid with good storage stability.
実施例５
〔シロキサン化合物−５の合成〕
攪拌器、ジムロートコンデンサー、温度計を備えたガラス製１リットル四ツ口丸底フラスコにテトラメトキシシラン３０４．０ｇ、メタノール９６．０ｇを仕込み５分攪拌した後、０．１規定塩酸水４．０ｇと水３９．０ｇの混合液を添加した。この時の、テトラメトキシシランに対する水の量は１．２モル倍に相当する。
その後、還流状態（６５℃）となるまで加熱し、還流下で４時間反応させた。このものを、室温まで放冷してジムロートコンデンサーをリービッヒコンデンサーに取り替えた後、キシレン３００．０ｇ及び２−フェノキシエタノール２２１．０ｇ及びテトライソプロポキシチタン０．１２ｇを仕込み、攪拌しながら徐々に加熱して、留出温度が約６５℃でメタノールを留去させながらエステル交換反応を進行させた。最終的には内温を１４６℃、留出温度約１４４℃まで昇温した後、冷却してキシレン１１９．５ｇを加えて、メタノール含有量０．３ｗｔ％、未反応の２−フェノキシエタノール含有量１．９ｗｔ％、キシレン４０．５ｗｔ％の液状で無色透明なシロキサン化合物−５、５９０．２ｇを得た。
Example 5
[Synthesis of Siloxane Compound-5]
A glass 1-liter four-necked round bottom flask equipped with a stirrer, Dimroth condenser and thermometer was charged with 304.0 g of tetramethoxysilane and 96.0 g of methanol and stirred for 5 minutes, and then 0.1 g of 0.1N hydrochloric acid water was added. And 39.0 g of water were added. At this time, the amount of water with respect to tetramethoxysilane corresponds to 1.2 mol times.
Then, it heated until it became a recirculation | reflux state (65 degreeC), and was made to react under recirculation | reflux for 4 hours. This was allowed to cool to room temperature and the Dimroth condenser was replaced with a Liebig condenser. Then, 300.0 g of xylene, 221.0 g of 2-phenoxyethanol and 0.12 g of tetraisopropoxytitanium were charged, and gradually heated while stirring. The ester exchange reaction was allowed to proceed while distilling off the methanol at a distillation temperature of about 65 ° C. Finally, after raising the internal temperature to 146 ° C. and the distillation temperature to about 144 ° C., the mixture was cooled and 119.5 g of xylene was added, the methanol content was 0.3 wt%, and the unreacted 2-phenoxyethanol content was 1 590.2 g of a liquid, colorless and transparent siloxane compound-5 containing 9.9 wt% and xylene 40.5 wt% was obtained.
このシロキサン化合物−５の示性式
（化２２）
ＳｉＯａ（ＯＨ）ｂ（ＯＣＨ３）ｃ（ＯＣ２Ｈ４ＯＣ６Ｈ５）ｄ
を、実施例１と同様にＮＭＲ法で解析し、反応の前提を以下の通りとして計算を行った。
Schematic formula of this siloxane compound-5
SiO a (OH) b (OCH 3 ) c (OC 2 H 4 OC 6 H 5 ) d
Was analyzed by the NMR method in the same manner as in Example 1, and the calculation was performed under the following reaction premise.
（化２３）
Ｓｉ（ＯＣＨ３）４ ＋ Ｈ２Ｏ ＋ Ｃ６Ｈ５ＯＣ２Ｈ４ＯＨ
→ＳｉＯａ（ＯＨ）ｂ（ＯＣＨ３）ｃ（ＯＣ２Ｈ４ＯＣ６Ｈ５）ｄ＋(４−Ｃ)ＣＨ３ＯＨ
(Chemical Formula 23)
Si (OCH 3) 4 + H 2 O + C 6 H 5 OC 2 H 4 OH
→ SiO a (OH) b (OCH 3 ) c (OC 2 H 4 OC 6 H 5 ) d + (4-C) CH 3 OH
この方法で、シロキサン化合物−５を示性式で表すと
（化２４）
ＳｉＯ１．１１(ＯＨ)０．１６(ＯＣＨ３)０．８９(ＯＣ２Ｈ４ＯＣ６Ｈ５)０．７３
であった。
又、このシロキサン化合物−５について、密閉下で５０℃、４５日間（室温換算約１年間相当）の加速保存試験を実施したが、液粘度は当初の７．８ｃｐから８．４ｃｐ程度しか上昇せず、貯蔵安定性良好な液状物であった。
In this method, when the siloxane compound-5 is represented by a chemical formula,
SiO 1.11 (OH) 0.16 (OCH 3 ) 0.89 (OC 2 H 4 OC 6 H 5 ) 0.73
Met.
In addition, this siloxane compound-5 was subjected to an accelerated storage test at 50 ° C. for 45 days (equivalent to about 1 year in terms of room temperature) in a sealed state, but the liquid viscosity increased only from the initial 7.8 cp to about 8.4 cp. It was a liquid with good storage stability.
比較例１
〔シロキサン化合物−６の合成〕
テトラメトキシシラン・オリゴマー（「ＭＫＣシリケートＭＳ５１」、三菱化学（株）製）３８．４６ｇ、エタノール５３．０ｇを混合した液に、アルミニウムトリスアセチルアセトネート０．３８ｇ、を加え、室温下で攪拌して溶解した。次いで、水８．１５ｇを添加し室温密閉化で３日間放置してシロキサン化合物−６、９９．９ｇを得た。
Comparative Example 1
[Synthesis of Siloxane Compound-6]
To a solution obtained by mixing 38.46 g of tetramethoxysilane oligomer (“MKC silicate MS51”, manufactured by Mitsubishi Chemical Corporation) and 53.0 g of ethanol, 0.38 g of aluminum trisacetylacetonate was added and stirred at room temperature. And dissolved. Next, 8.15 g of water was added, and the mixture was allowed to stand at room temperature for 3 days to obtain siloxane compound-6, 99.9 g.
このシロキサン化合物−６の示性式
（化２５）
ＳｉＯａ（ＯＨ）ｂ（ＯＣＨ３）ｃ（ＯＣ２Ｈ５）ｄ
を、実施例１と同様にＮＭＲ法で解析し、反応の前提を以下の通りとして計算を行った。
Schematic formula of this siloxane compound-6
SiO a (OH) b (OCH 3 ) c (OC 2 H 5 ) d
Was analyzed by the NMR method in the same manner as in Example 1, and the calculation was performed under the following reaction premise.
（化２６）
ＳｉＯ０．８（ＯＣＨ３）２．４ ＋ Ｈ２Ｏ ＋Ｃ２Ｈ５ＯＨ
→ＳｉＯａ（ＯＨ）ｂ（ＯＣＨ３）ｃ（ＯＣ２Ｈ５）ｄ＋（２．４−ｃ）ＣＨ３ＯＨ
この方法で、シロキサン化合物−６の示性式を求めると
ＳｉＯ１．１５（ＯＨ）０．６８（ＯＣＨ３）０．３７（ＯＣ２Ｈ５）０．６５
であった。
又、このシロキサン化合物−６について、密閉下で５０℃での加速保存試験を実施したが、１０日目にゲル化してしまった。
(Chemical Formula 26)
SiO 0.8 (OCH 3 ) 2.4 + H 2 O + C 2 H 5 OH
→ SiO a (OH) b (OCH 3 ) c (OC 2 H 5 ) d + (2.4-c) CH 3 OH
By using this method, the formula of the siloxane compound-6 is obtained. SiO 1.15 (OH) 0.68 (OCH 3 ) 0.37 (OC 2 H 5 ) 0.65
Met.
Further, this siloxane compound-6 was subjected to an accelerated storage test at 50 ° C. in a sealed state, but gelled on the 10th day.
比較例２
〔シロキサン化合物−６の溶媒置換〕
ガラス製２００ｍｌ四ツ口丸底フラスコに攪拌器、温度計、リービッヒコンデンサーを取り付けた簡単な単蒸留装置に、比較例１で得られたシロキサン化合物−６、５０．０ｇとキシレン４０．０ｇを仕込み攪拌しながら徐々に加熱して、留出温度が約６５℃でメタノールを留去させていたところ、内液が白濁すると共に全体がゲル化してしまった。
Comparative Example 2
[Solvent substitution of siloxane compound-6]
A simple single distillation apparatus equipped with a glass 200 ml four-necked round bottom flask equipped with a stirrer, thermometer and Liebig condenser was charged with 50.0 g of siloxane compound-6 obtained in Comparative Example 1 and 40.0 g of xylene. When methanol was distilled off at a distillation temperature of about 65 ° C. while gradually heating with stirring, the internal solution became cloudy and the whole gelled.
実施例６〜１１
実施例１〜５及び比較例１で得られたシロキサン化合物−１〜６と、有機高分子化合物とを配合した各々の硬化性組成物の相溶性を表１に、またそれらの塗膜物性を表２に示す。
Examples 6-11
Table 1 shows the compatibility of each of the curable compositions containing the siloxane compounds -1 to 6 obtained in Examples 1 to 5 and Comparative Example 1 and the organic polymer compound. It shows in Table 2.
（塗膜作製条件）
・基板・・・・ガラス及びアルミニウム
・塗工・・・・１５０μｍアプリケーター
・硬化条件・・１５０℃、２時間硬化
（塗膜物性評価方法）
・外 観 ：目視観察及びヘイズメータによる△Ｈ値測定（ガラス基板使用
・鉛筆硬度：ＪＩＳ Ｋ ５４００塗料一般試験方法参照
・耐溶剤性：キシレンを含浸させた綿布で、塗膜表面を往復１００回ラビングした後 、キズ又は溶出等を目視評価。
○：変化なし △：若干のキズ ×：キズ又は溶出
・耐屈曲性：ＪＩＳ Ｋ ５４００塗料一般試験方法参照
(Coating film preparation conditions)
・ Substrate ・ ・ ・ ・ Glass and aluminum
・ Coating ... 150μm applicator
・ Curing conditions ・ ・ Curing at 150 ℃ for 2 hours
(Method for evaluating physical properties of coating film)
・ Appearance: Visual observation and △ H value measurement with haze meter (use of glass substrate ・ Pencil hardness: Refer to JIS K 5400 paint general test method
-Solvent resistance: After rubbing the coating film surface 100 times with a cotton cloth impregnated with xylene, the scratches or elution are visually evaluated.
○: No change △: Slight scratch ×: Scratch or elution ・ Bending resistance: Refer to JIS K 5400 General Test Methods for Paints
（発明の効果）
本発明のシロキサン化合物は、高重合度でありながら貯蔵安定性は１年以上、透明且つ組成変化のない液状態を保つことが可能である。例えば加水分解溶液としてハードコートに用いたり、樹脂等の各種の有機化合物との相溶性に優れるため、これと配合して得られる液状組成物を硬化して得られる塗膜に、親水性付与、耐汚染性、耐酸性、耐薬品性、耐候性、耐熱性等の向上、あるいは鋳物用砂型等のバインダー用途等、様々な用途への適用が可能であり、極めて有用な液状組成物を供することのできる新規なシロキサン化合物である。
(The invention's effect)
Although the siloxane compound of the present invention has a high degree of polymerization, it has a storage stability of 1 year or more, and can maintain a liquid state that is transparent and has no composition change. For example, because it is used for a hard coat as a hydrolyzed solution, or is excellent in compatibility with various organic compounds such as resins, imparting hydrophilicity to a coating film obtained by curing a liquid composition obtained by blending with this, To provide a very useful liquid composition that can be applied to various applications such as contamination resistance, acid resistance, chemical resistance, weather resistance, heat resistance, etc., or binder applications such as sand molds for castings. It is a novel siloxane compound that can be produced.
Claims (6)
ＳｉＯａ（ＯＨ）ｂ（ＯＲ１）ｃ（ＯＲ２）ｄ
（ただし、１．０≦ａ≦１．６、０≦ｂ＜０．３、ｂ＝４−（２ａ＋ｃ＋ｄ）、０≦ｃ≦２．０、０＜ｄ≦２．０、Ｒ１はメチル基又はエチル基、Ｒ２はＲ１と相異なる有機基） A cured product obtained by curing a liquid composition containing a siloxane compound represented by the following formula.
SiO a (OH) b (OR 1 ) c (OR 2 ) d
(However, 1.0 ≦ a ≦ 1.6, 0 ≦ b <0.3, b = 4- (2a + c + d), 0 ≦ c ≦ 2.0, 0 <d ≦ 2.0, R 1 is a methyl group Or an ethyl group, R 2 is an organic group different from R 1 )
The cured product according to claim 4, wherein a liquid composition obtained by blending the siloxane compound with an organic compound compatible with the siloxane compound and further blending powder is cured.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006237719A JP2006328424A (en) | 1996-03-25 | 2006-09-01 | Siloxane compound and liquid composition using the same |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6789796 | 1996-03-25 | ||
| JP2006237719A JP2006328424A (en) | 1996-03-25 | 2006-09-01 | Siloxane compound and liquid composition using the same |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29014896A Division JP3881071B2 (en) | 1996-03-25 | 1996-10-31 | Siloxane compound and liquid composition using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006328424A true JP2006328424A (en) | 2006-12-07 |
Family
ID=37550429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2006237719A Pending JP2006328424A (en) | 1996-03-25 | 2006-09-01 | Siloxane compound and liquid composition using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2006328424A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0477506A (en) * | 1990-07-16 | 1992-03-11 | Toagosei Chem Ind Co Ltd | Production of silane addition polymer |
| JPH04236266A (en) * | 1991-01-14 | 1992-08-25 | Toagosei Chem Ind Co Ltd | Resin composition and its production |
| JPH06340848A (en) * | 1993-04-07 | 1994-12-13 | Mitsubishi Kasei Corp | Coating film of organic substance |
| JPH0734034A (en) * | 1993-05-17 | 1995-02-03 | Mitsubishi Chem Corp | Electrical insulating film material |
| JPH0768217A (en) * | 1993-05-17 | 1995-03-14 | Mitsubishi Chem Corp | Coating method of metal surface |
| JPH07150102A (en) * | 1993-11-26 | 1995-06-13 | Nippon Synthetic Chem Ind Co Ltd:The | Film-forming composition |
| JPH0912583A (en) * | 1995-06-23 | 1997-01-14 | Mitsubishi Chem Corp | Siloxane compound, its production and curable composition |
| JPH09110984A (en) * | 1995-10-13 | 1997-04-28 | Mitsubishi Chem Corp | Cured silicate product and its production |
| JPH09165451A (en) * | 1995-10-06 | 1997-06-24 | Mitsubishi Chem Corp | Silicate oligomer its production, and curable composition prepared using the same |
| JPH09165452A (en) * | 1995-10-11 | 1997-06-24 | Mitsubishi Chem Corp | Polymethoxypolysiloxane, its production, and curable composition prepared using the same |
| JPH09169847A (en) * | 1995-10-20 | 1997-06-30 | Mitsubishi Chem Corp | Polyalkoxypolysiloxane, its production, and curable composition prepared using the same |
| JPH09169848A (en) * | 1995-10-20 | 1997-06-30 | Mitsubishi Chem Corp | Polysiloxane compound, its production, and curable composition prepared therefrom |
-
2006
- 2006-09-01 JP JP2006237719A patent/JP2006328424A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0477506A (en) * | 1990-07-16 | 1992-03-11 | Toagosei Chem Ind Co Ltd | Production of silane addition polymer |
| JPH04236266A (en) * | 1991-01-14 | 1992-08-25 | Toagosei Chem Ind Co Ltd | Resin composition and its production |
| JPH06340848A (en) * | 1993-04-07 | 1994-12-13 | Mitsubishi Kasei Corp | Coating film of organic substance |
| JPH0734034A (en) * | 1993-05-17 | 1995-02-03 | Mitsubishi Chem Corp | Electrical insulating film material |
| JPH0768217A (en) * | 1993-05-17 | 1995-03-14 | Mitsubishi Chem Corp | Coating method of metal surface |
| JPH07150102A (en) * | 1993-11-26 | 1995-06-13 | Nippon Synthetic Chem Ind Co Ltd:The | Film-forming composition |
| JPH0912583A (en) * | 1995-06-23 | 1997-01-14 | Mitsubishi Chem Corp | Siloxane compound, its production and curable composition |
| JPH09165451A (en) * | 1995-10-06 | 1997-06-24 | Mitsubishi Chem Corp | Silicate oligomer its production, and curable composition prepared using the same |
| JPH09165452A (en) * | 1995-10-11 | 1997-06-24 | Mitsubishi Chem Corp | Polymethoxypolysiloxane, its production, and curable composition prepared using the same |
| JPH09110984A (en) * | 1995-10-13 | 1997-04-28 | Mitsubishi Chem Corp | Cured silicate product and its production |
| JPH09169847A (en) * | 1995-10-20 | 1997-06-30 | Mitsubishi Chem Corp | Polyalkoxypolysiloxane, its production, and curable composition prepared using the same |
| JPH09169848A (en) * | 1995-10-20 | 1997-06-30 | Mitsubishi Chem Corp | Polysiloxane compound, its production, and curable composition prepared therefrom |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3949175B2 (en) | Polyalkoxysiloxane compound, method for producing the same, and coating composition containing the same | |
| KR100363126B1 (en) | An epoxy-functional organopolysiloxane resin and An epoxy-functional organopoly silioxane coating composition | |
| EP0771835B1 (en) | Polyalkoxysiloxane and process for its production | |
| WO1995028445A1 (en) | Curable composition and process for producing the same | |
| US5633311A (en) | Method of producing organopolysiloxanes containing hydrolyzable functional groups, and curable resin composition using said organopolysiloxanes | |
| KR900007878B1 (en) | Ungelled resins and process for the preparation of thereof | |
| US6291697B1 (en) | Siloxane compounds, process for preparing the same, and liquid composition containing the same | |
| JP2009235238A (en) | Aqueous coating composition, organic-inorganic composite coating film, metal alkoxide condensate dispersion, and production method thereof | |
| JPS62252456A (en) | Room temperature-curable organopolysiloxane composition | |
| JP3881076B2 (en) | Silicate compound and liquid composition containing the same | |
| JPH0786183B2 (en) | Coating composition for coating | |
| JPH10251516A (en) | Silane oligomer composition | |
| JP3881071B2 (en) | Siloxane compound and liquid composition using the same | |
| JP3279015B2 (en) | Composition for coating | |
| JPH029633B2 (en) | ||
| JPH09165450A (en) | Curabale composition, its production, and its cured item | |
| JP2006328424A (en) | Siloxane compound and liquid composition using the same | |
| JPH09169847A (en) | Polyalkoxypolysiloxane, its production, and curable composition prepared using the same | |
| JP3361779B2 (en) | Coating composition | |
| JPH09165451A (en) | Silicate oligomer its production, and curable composition prepared using the same | |
| JP4352568B2 (en) | Inorganic paint | |
| JP4009837B2 (en) | Silicone coating agent, method for producing the same, and cured product | |
| JP7093663B2 (en) | Curable resin composition and its manufacturing method | |
| KR20190105914A (en) | Room temperature curing coating materials containing silan oligomer | |
| JPH10212354A (en) | Polyalkoxypolysiloxane, its production and curable composition containing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060901 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100706 |
|
| A02 | Decision of refusal |
Effective date: 20101104 Free format text: JAPANESE INTERMEDIATE CODE: A02 |