JP2006240950A - Corrosion prevention method for concrete structure - Google Patents
Corrosion prevention method for concrete structure Download PDFInfo
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本発明は、コンクリート構造物の防食を目的とした樹脂ライニングを行う施工において、ピンホールによる表面欠落のない塗膜を得る方法に関する。 The present invention relates to a method for obtaining a coating film having no surface loss due to pinholes in construction for performing resin lining for the purpose of preventing corrosion of concrete structures.
下水施設や上水施設の防食工事などに代表される、コンクリート構造物の腐食防止を目的とした樹脂ライニングにおいて、防食被膜のピンホールによる表面欠落は、その目的を著しく阻害する要因として知られており、ピンホールの発生防止について盛んに研究がなされている。 In resin linings intended to prevent corrosion of concrete structures, such as sewage facilities and anti-corrosion works for water supply facilities, surface loss due to anti-corrosion coating pinholes is known to be a significant impediment to that purpose. Therefore, active research has been conducted on the prevention of pinholes.
特に下水施設の防食においては、下地調整時にピンホールの原因となるコンクリート表面の凹凸や巣穴を完全に埋めることが重要とされてきた。このような状況を踏まえ、平成１４年度版下水道コンクリート構造物の腐蝕抑制技術及びライニング技術指針・同マニュアル（日本下水道事業団）において、下水の特に厳しい腐食環境にさらされると考えられる施設の防食工事終了後に、ピンホール試験機を用いた試験を施工面の全面において行うことが義務づけられるに至った。また、上水施設やその他コンクリート構造物においても、ピンホールなど防食被覆層の欠損は長期耐食性の面から問題とされ、ピンホールの発生が少ない工法が求められている。
一方、防食被膜形成樹脂としては現在、エポキシ樹脂、ビニルエステル樹脂、無溶剤型ポリウレタンエラストマー樹脂、不飽和ポリエステル樹脂、ノンスチレン型ビニルエステル樹脂、ポリウレア樹脂、変性シリコーン樹脂、アクロイル変性アクリル樹脂等又はその他耐酸性樹脂が使用されている。これらの耐酸性樹脂の中でも、ビニルエステル樹脂はその高い耐食性能から多く用いられてきた。しかしながら、ビニルエステル樹脂は一般に樹脂粘度が低いため施工は容易でガラスマットへの含浸性も良好であるが、低い樹脂粘度のため垂直面で垂れが生じやすく、ピンホール発生要因となるため大きな問題となっている。
ビニルエステル樹脂とは、末端不飽和の主鎖化合物に重合性モノマーを配合したもので、重合反応開始剤や重合促進剤を作用させ硬化させる樹脂である。主鎖化合物としてはエピクロルヒドリン・ビスフェノールＡ型グリシジルエーテル、ノボラック型グリシジルエーテル、臭素化グリシジルエーテル等のエポキシ樹脂と、アクリル酸、メタクリル酸、クロトン酸、桂皮酸、ソルビン酸等の不飽和一塩基酸類から合成されるエステル化合物が挙げられる。重合性モノマーとしてはスチレン、ビニルトルエン、メタクリル酸メチル、メタクリル酸イソブチル、ジアリルフタレート、ジアリルイソフタレート等が挙げられる。重合反応開始剤としては過酸化ベンゾイル、キュメンパーオキシド、メチルエチルケトンパーオキシド、アセト酢酸エステルパーオキシド等の過酸化物が挙げられる。さらに重合促進剤としてナフテン酸コバルト、オクテン酸コバルト等の有機酸のコバルト塩やジメチルアニリン等の芳香族第３級アミンが挙げられる。
In particular, in the prevention of sewage facilities, it has been important to completely fill in the irregularities and burrows on the concrete surface that cause pinholes during base adjustment. Based on this situation, the anti-corrosion work for facilities considered to be exposed to the particularly severe corrosive environment of sewage in the 2002 edition of the sewerage concrete structure corrosion control technology and lining technical guidelines and manual (Japan Sewerage Corporation). After the completion, it was obliged to conduct a test using a pinhole tester on the entire construction surface. Also, in water supply facilities and other concrete structures, loss of anticorrosion coating layers such as pinholes is a problem in terms of long-term corrosion resistance, and a construction method with less pinholes is required.
On the other hand, as an anticorrosion film forming resin, epoxy resin, vinyl ester resin, solventless polyurethane elastomer resin, unsaturated polyester resin, non-styrene vinyl ester resin, polyurea resin, modified silicone resin, acroyl modified acrylic resin, etc. Acid-resistant resin is used. Among these acid resistant resins, vinyl ester resins have been frequently used because of their high corrosion resistance. However, vinyl ester resins generally have a low resin viscosity and are easy to install and have good impregnation into glass mats. However, the low resin viscosity tends to cause drooping on the vertical surface, which can cause pinholes. It has become.
The vinyl ester resin is a resin in which a polymerizable monomer is blended with a terminal unsaturated main chain compound, and is cured by acting a polymerization reaction initiator or a polymerization accelerator. Main chain compounds include epichlorohydrin, bisphenol A glycidyl ether, novolac glycidyl ether, brominated glycidyl ether, and other epoxy resins, and unsaturated monobasic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, and sorbic acid. Examples include ester compounds to be synthesized. Examples of the polymerizable monomer include styrene, vinyl toluene, methyl methacrylate, isobutyl methacrylate, diallyl phthalate, and diallyl isophthalate. Examples of the polymerization reaction initiator include peroxides such as benzoyl peroxide, cumene peroxide, methyl ethyl ketone peroxide, and acetoacetate peroxide. Furthermore, examples of the polymerization accelerator include cobalt salts of organic acids such as cobalt naphthenate and cobalt octenoate, and aromatic tertiary amines such as dimethylaniline.
これまでにピンホール発生防止を目的とした防食被膜として、コンクリート構造物の表面に、多孔質薄膜シートに液状プライマー樹脂をスプレー塗布して含浸させたシート層を設けることによりピンホールの発生を防止する方法が記載されている。この方法のように多孔質なシートを適応することは、巨視的なピンホール防止には効果的であるが、微視的なピンホールを防止するには十分な方法ではない。さらに、樹脂の塗布方法がスプレーに限定されているので、樹脂のミストによる作業環境の汚染も難点となっている。 To prevent pinholes by providing a sheet layer that has been impregnated by spraying a liquid primer resin on a porous thin film sheet on the surface of a concrete structure as an anticorrosive coating for the purpose of preventing pinholes. How to do is described. Applying a porous sheet like this method is effective for preventing macroscopic pinholes, but is not a sufficient method for preventing microscopic pinholes. Furthermore, since the resin application method is limited to spraying, contamination of the work environment by resin mist is also a problem.
また、特定の目付け量を有する無機質紙に中・高粘度の樹脂組成物を含浸させた層を形成することで、微視的なピンホールを防止する方法も見いだされているが、低粘度では、含浸性には優れるものの、樹脂組成物が硬化するまでに垂れるなどの保持に欠ける問題がある。
本発明は、上記の実情に鑑みなされたものであり、その目的は、ビニルエステル樹脂などの低粘度樹脂で垂直面に施工しても、樹脂の垂れがなく、ピンホールの出来ない、コンクリート構造物の防食被膜形成法を提供することにある。 The present invention has been made in view of the above circumstances, and the purpose thereof is a concrete structure in which a resin does not sag and a pinhole cannot be formed even when applied to a vertical surface with a low viscosity resin such as a vinyl ester resin. An object of the present invention is to provide a method for forming an anticorrosive film on an object.
本発明者は、ビニルエステル樹脂などの低粘度含浸用樹脂を用いた時のピンホール発生原因につき種々検討を重ねた結果、次のような知見を得た。すなわち、ビニルエステル樹脂など低粘度樹脂を用いた防食工法のピンホール発生の原因は、垂直面で施工したときガラスマットに樹脂を含浸しても使用したガラスマットに樹脂の保持力がなく、樹脂が下に流れ出しピンホールが出来やすい為、その樹脂を保持するシートを挟み込むことで樹脂の流れを防止し、また下地の影響を軽減することができること、さらに、樹脂の保持には、含浸させる繊維シートが、ランダムで緻密な空孔を有する不織シートでヨレの生じない紙状になっているものがもっとも効果的であることを見出した。目付け量や空孔の径平均が適切である繊維紙に、樹脂組成物をコテ、ヘラ、刷毛またはローラーで塗布すると、樹脂の垂れが防止され、防食被膜における微視的なピンホールの発生を防止することができ、素地調整、防食被覆の中塗りや上塗りなどのいずれの工程段階においても適応することができる。 The present inventor has made various studies on the cause of pinholes when using a low-viscosity impregnation resin such as a vinyl ester resin, and as a result, has obtained the following knowledge. In other words, the cause of pinholes in the anticorrosion method using a low viscosity resin such as vinyl ester resin is that even if the glass mat is impregnated with the resin when it is installed on the vertical surface, the glass mat used does not have the resin holding power, and the resin Since the resin flows out downward and pinholes are easily formed, the resin flow can be prevented by sandwiching the sheet holding the resin, and the influence of the base can be reduced. It has been found that the most effective sheet is a non-woven sheet having random and dense pores, which is in the form of paper that does not twist. If the resin composition is applied to a fiber paper with an appropriate weight per unit and average pore diameter with a trowel, spatula, brush or roller, the dripping of the resin is prevented and microscopic pinholes are generated in the anticorrosion coating. It can be applied to any process step such as substrate preparation, intermediate coating or top coating of anticorrosion coating.
本発明によれば、コンクリート構造物の樹脂ライニング施工において、垂直面の樹脂垂れ、ピンホールの発生がない防食被覆層が得られ、下水道施設内で生成する硫化水素に起因する硫酸によるコンクリート構造物の腐食を完全に抑えることができ、また上水施設やその他コンクリート構造物においても長期の防食性が期待できる。
以下に本発明の実施例を挙げて説明する。
According to the present invention, in a resin lining construction of a concrete structure, an anticorrosion coating layer free from the occurrence of resin dripping and pinholes on the vertical surface is obtained, and the concrete structure with sulfuric acid caused by hydrogen sulfide generated in a sewerage facility Corrosion of water can be completely suppressed, and long-term corrosion resistance can be expected in water supply facilities and other concrete structures.
Examples of the present invention will be described below.
本発明で使用する無機繊維紙は、目付量が１５〜１００ｇ／ｍ２の範囲、空孔の平均直径が５〜１００μｍであり、繊維を紙状に固定したものが使用できる。目付量が１５ｇ／ｍ２未満であったり、１５０ｇ／ｍ２ を超えるとハンドリングがし辛く施工面への貼り付けが困難となる。また、前記無機繊維紙の空孔の平均直径が１００μｍを超えると、樹脂の保持が不十分で垂れが生じやすく、ピンホールの発生を防止できない。逆に、空孔の平均直径が５μｍ未満であると、含浸性が劣り樹脂との一体化が不十分なためピンホールの発生を防止できない。繊維が紙状に固定されていないと、樹脂の含浸過程において空孔径が変化するため、垂れが生じやすくピンホールの発生を防止できない。なお、前記無機繊維紙の含浸施工の前工程に、ガラス繊維や炭素繊維等からマット、不織布、織布等を貼り付けておいてもよい。
前記無機繊維紙の例としてはガラス繊維を水中に均一に分散させ湿式抄法によりペーパー化したもの、または湿式でなくてもガラス繊維をペーパー化したものであればいい。また鉱物、無機物の粉体またはその微細繊維物を主成分としてつくられたミネラルペーパー、具体的には炭酸カルシウム、水酸化アルミニウム、タルク、活性炭粉末、珪酸カルシウム、炭酸マグネシウム等の高機能を持つ粉体をペーパー化したものや炭素繊維紙やセラミック繊維紙、ロックウール繊維紙等があげられる。
ライニング層の施工方法としては、コテ、スプレー、ヘラ、ローラー等いずれでも良いが、作業性の良好なローラーで施工するのがより好ましい。ローラーの種類は、短毛、中毛、長毛どの種類でも問題ないが、特に無泡ローラーが好ましい。
本発明で使用する樹脂組成物は、上記にあげた防食被膜形成樹脂で、樹脂組成物として粘度が１００〜１，５００ｍＰａ・ｓ（２５℃、ＢＭ型回転粘度計２号ローター）のものが使用できる。粘度が、１００ｍＰａ・ｓ未満では前記の無機繊維紙であっても樹脂垂れが生じ、１，５００ｍＰａ・ｓを超えると含浸性に劣り、ピンホールの発生を防止できない。
前記樹脂組成物には必要に応じて顔料、骨材等の固体成分を含むことができる。前記固体成分としては硅砂、砕石、カオリン、タルク、炭酸カルシウム、硫酸バリウム、シリカ、酸化チタン、珪酸アルミニウム、酸化マグネシウム、酸化亜鉛、酸化鉄、ウルトラマリーン、カドミウムレット、コバルトグリーン、コバルトバイオレット、コバルトブルー、酸化クロムグリーン、セルリアンブルー、チタニウムイエロー、ベンガラ、カーボンブラック等が挙げられる。
As the inorganic fiber paper used in the present invention, those having a basis weight of 15 to 100 g / m 2 , an average pore diameter of 5 to 100 μm, and fibers fixed in a paper shape can be used. When the weight per unit area is less than 15 g / m 2 or exceeds 150 g / m 2 , handling is difficult, and it is difficult to attach to the construction surface. On the other hand, if the average diameter of the pores of the inorganic fiber paper exceeds 100 μm, the resin is not sufficiently retained and is likely to sag, and the occurrence of pinholes cannot be prevented. On the contrary, if the average diameter of the pores is less than 5 μm, the impregnation property is inferior and the integration with the resin is insufficient, so that the generation of pinholes cannot be prevented. If the fibers are not fixed in a paper shape, the pore diameter changes during the resin impregnation process, and therefore, drooping easily occurs and pinholes cannot be prevented. In addition, a mat, a nonwoven fabric, a woven fabric, or the like may be pasted from glass fiber, carbon fiber, or the like in the pre-process of impregnation with the inorganic fiber paper.
Examples of the inorganic fiber paper may be those in which glass fibers are uniformly dispersed in water and made into paper by a wet papermaking method, or glass fibers made into paper even if not wet. Mineral paper made of minerals, inorganic powders, or fine fiber materials, such as calcium carbonate, aluminum hydroxide, talc, activated carbon powder, calcium silicate, magnesium carbonate, etc. Examples include paper made bodies, carbon fiber paper, ceramic fiber paper, rock wool fiber paper, and the like.
As a method for applying the lining layer, any of a trowel, a spray, a spatula, a roller, and the like may be used. The type of roller may be any kind of short hair, medium hair, and long hair, but a non-foam roller is particularly preferable.
The resin composition used in the present invention is the above-described anticorrosion film-forming resin, and the resin composition having a viscosity of 100 to 1,500 mPa · s (25 ° C., BM type rotational viscometer No. 2 rotor) is used. it can. If the viscosity is less than 100 mPa · s, resin dripping occurs even in the case of the inorganic fiber paper, and if it exceeds 1,500 mPa · s, the impregnation property is inferior and the generation of pinholes cannot be prevented.
The resin composition may contain solid components such as pigments and aggregates as necessary. The solid components include cinnabar, crushed stone, kaolin, talc, calcium carbonate, barium sulfate, silica, titanium oxide, aluminum silicate, magnesium oxide, zinc oxide, iron oxide, ultramarine, cadmium let, cobalt green, cobalt violet, cobalt blue. Chrome oxide green, cerulean blue, titanium yellow, bengara, carbon black and the like.
以下、実施例、比較例を挙げて詳細に説明する。 Hereinafter, examples and comparative examples will be described in detail.
実施例１〜５
垂直に保持したコンクリート板（ＪＩＳ板：５０ｍｍ×６００ｍｍ×３６０ｍｍ）に素地調整材（大日本色材工業製：スチレン型ビニルエステル樹脂パテ ＶＥ−９０４）を１．０ｋｇ／ｍ２をコテで塗布し、２３℃×１日硬化後、ライニング層を塗布する。ライニング層として必要に応じてガラスマット（ＪＩＳ Ｒ ３４１１−１９７５に定めるＥＭ４５０）を貼り付け、さらにこれに目付量３０および１００ｇ／ｍ２ のガラス繊維紙を貼り付けた後、含浸用ビニルエステル樹脂（大日本色材工業製：スチレン型ビニルエステル樹脂 ＶＥ−４０３）１．５ｋｇ／ｍ２を含浸し、２３℃×１日硬化後、上塗り用ビニルエステル樹脂（大日本色材工業製：スチレン型ビニルエステル樹脂 ＶＥ−４０８）０．３ｋｇ／ｍ２ をローラーで塗布し２３℃×７日間硬化させた。前記含浸用ビニルエステル樹脂は粘度を１００、４００、７００、１０００ｍＰａ・ｓ （２５℃：ＢＭ型回転粘度計２号ローター）に調製したものをそれぞれ使用した。
Examples 1-5
Concrete plates (JIS plate: 50mm × 600mm × 360mm) held perpendicular to the surface preparation material: the (Dainippon colorant Kogyo styrene type vinyl ester resin putty VE-904) was applied to 1.0 kg / m 2 with iron After curing at 23 ° C. for 1 day, a lining layer is applied. If necessary, a glass mat (EM450 as defined in JIS R 3411-1975) is attached as a lining layer, and further a glass fiber paper having a basis weight of 30 and 100 g / m 2 is attached thereto. Dainippon Color Material Industries: Styrene-type vinyl ester resin VE-403) impregnated with 1.5 kg / m 2 and cured at 23 ° C. for 1 day, then vinyl ester resin for overcoating (Dainippon Color Material Industries: styrene-type vinyl) Ester resin VE-408) 0.3 kg / m 2 was applied with a roller and cured at 23 ° C. for 7 days. As the impregnation vinyl ester resin, those prepared to have a viscosity of 100, 400, 700, 1000 mPa · s (25 ° C .: BM type rotational viscometer No. 2 rotor) were used.
ピンホール試験は、株式会社サンコウ電子研究所製ＴＯ−２５０Ｃピンホール探知機（コンクリート素地用）を使用し、電圧７ＫＶをかけ試験体全体についてピンホールの有無を評価した。（○・・・ピンホールなし、△・・・ピンホールあり（５ヶ以下／試験板）、×・・・多数ピンホールあり（６ヶ以上／試験板））
また、垂れの有無は目視で判定した。（○・・・垂れなし，×・・・垂れあり）
比較例１
垂直に保持したコンクリート板（ＪＩＳ板：５０ｍｍ×６００ｍｍ×３６０ｍｍ）に素地調整材（大日本色材工業製：スチレン型ビニルエステル樹脂パテ ＶＥ−９０４）を１．０ｋｇ／ｍ２をコテで 塗布し、２３℃×１日硬化後、ライニング層を塗布する。比較例１としてライニング層に含浸用ビニルエステル樹脂（大日本色材工業製：スチレン型ビニルエステル樹脂 ＶＥ−４０３）１．５ｋｇ／ｍ２ をガラスマット（ＪＩＳ Ｒ ３４１１−１９７５に定めるＥＭ４５０）に含浸し、２３℃×１日硬化後、上塗り用ビニルエステル樹脂（大日本色材工業製：スチレン型ビニルエステル樹脂 ＶＥ−４０８）０．３ｋｇ／ｍ２ をローラーで塗布し２３℃×７日間硬化させた。
比較例２および３のライニング層としては含浸用ビニルエステル樹脂（大日本色材工業製：スチレン型ビニルエステル樹脂 ＶＥ−４０３）１．５ｋｇ／ｍ２ で、ガラスマット（ＪＩＳ Ｒ ３４１１−１９７５に定めるＥＭ４５０） を貼り付け、さらにこれに、ガラスサーフェイスマット（ＪＩＳ Ｒ ３４１１−１９７５に定める＃３０） および目付量１０ｇ／ｍ２ のガラス繊維紙を貼り付け、２３℃×１日硬化後、上塗り用ビニルエステル樹脂（大日本色材工業製：スチレン型ビニルエステル樹脂 ＶＥ−４０８）０．３ｋｇ／ｍ２ をローラーで塗布し２３℃×７日間硬化させた。
比較例４のライニング層としては含浸用ビニルエステル樹脂（大日本色材工業製：スチレン型ビニルエステル樹脂 ＶＥ−４０３）０．７ｋｇ／ｍ２ で、ガラスクロス（ＪＩＳ Ｒ ３４１４−１９７５に定めるＥＰ１８Ｄ） を貼り付け、２３℃×１日硬化後、上塗り用ビニルエステル樹脂（大日本色材工業製：スチレン型ビニルエステル樹脂 ＶＥ−４０８）０．３ｋｇ／ｍ２ をローラーで塗布し２３℃×７日間硬化させた。
In the pinhole test, a TO-250C pinhole detector (for concrete base) manufactured by Sanko Electronic Laboratory Co., Ltd. was used, and a voltage of 7 KV was applied to evaluate the presence or absence of a pinhole in the entire test specimen. (○ ... No pinhole, △ ... With pinhole (5 or less / test plate), X ... With many pinholes (6 or more / test plate))
The presence or absence of sagging was determined visually. (○ ... No dripping, x ... with dripping)
Comparative Example 1
Concrete plates (JIS plate: 50mm × 600mm × 360mm) held perpendicular to the surface preparation material: the (Dainippon colorant Kogyo styrene type vinyl ester resin putty VE-904) was applied to 1.0 kg / m 2 with iron After curing at 23 ° C. for 1 day, a lining layer is applied. As Comparative Example 1, a glass mat (EM450 as defined in JIS R 3411-1975) was impregnated with 1.5 kg / m 2 of vinyl ester resin for impregnation (Dainippon Color Material Industries: styrene type vinyl ester resin VE-403) in the lining layer. Then, after curing at 23 ° C. for 1 day, a vinyl ester resin for overcoating (Dainippon Color Material Industries: Styrene-type vinyl ester resin VE-408) 0.3 kg / m 2 was applied with a roller and cured at 23 ° C. for 7 days. It was.
The lining layers of Comparative Examples 2 and 3 were impregnated vinyl ester resin (Dainippon Color Material Industries Co., Ltd .: styrene type vinyl ester resin VE-403) 1.5 kg / m 2 and glass mat (as defined in JIS R 3411-1975). EM450) and a glass surface mat (# 30 as defined in JIS R 3411-1975) and a glass fiber paper with a basis weight of 10 g / m 2 were pasted, and after curing at 23 ° C. for 1 day, vinyl for top coating was applied. Ester resin (Dainippon Color Material Industries: Styrene-type vinyl ester resin VE-408) 0.3 kg / m 2 was applied with a roller and cured at 23 ° C. for 7 days.
As a lining layer of Comparative Example 4, impregnation vinyl ester resin (Dainippon Color Material Industries: styrene type vinyl ester resin VE-403) 0.7 kg / m 2 , glass cloth (EP18D defined in JIS R 3414-1975) After being cured at 23 ° C. for 1 day, a vinyl ester resin for overcoating (Dainippon Color Material Industries: Styrene type vinyl ester resin VE-408) 0.3 kg / m 2 was applied with a roller and 23 ° C. for 7 days. Cured.
なお、含浸用ビニルエステル樹脂は粘度が４００ｍＰａ・ｓ （２５℃：ＢＭ型回転粘度計２号ローター）のものを使用した。
The impregnating vinyl ester resin used had a viscosity of 400 mPa · s (25 ° C .: BM type rotational viscometer No. 2 rotor).
実施例においては、樹脂粘度が低い場合でも樹脂の垂れがなく、ピンホール試験において十分性能が発揮されていることが確認された。一方比較例のガラスマット、ガラスクロスや目付け量の小さいガラス繊維紙などでは樹脂の保持が不十分で垂れ、ピンホールの発生が確認された。
In the examples, even when the resin viscosity was low, it was confirmed that the resin did not sag and the performance was sufficiently exhibited in the pinhole test. On the other hand, in the glass mat, glass cloth and glass fiber paper having a small basis weight of the comparative example, the resin was not sufficiently retained and dripped, and the occurrence of pinholes was confirmed.
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| JP2009126762A (en) * | 2007-11-27 | 2009-06-11 | Japan Sewage Works Agency | Acid-resistant composite and repairing method |
| JP2016013956A (en) * | 2014-07-03 | 2016-01-28 | 積水化学工業株式会社 | Surface protective sheet and method for protecting surface of concrete structure using the same |
| JP2016504974A (en) * | 2012-10-16 | 2016-02-18 | オーシーヴィー インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー | Liner for reinforcing a pipe and method for manufacturing the same |
| JP2016150867A (en) * | 2015-02-17 | 2016-08-22 | 積水化学工業株式会社 | Repair material for concrete structure and repairing method of concrete structure |
| JP7066236B1 (en) * | 2021-10-04 | 2022-05-13 | 大泰化工株式会社 | How to protect concrete |
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| JP7066236B1 (en) * | 2021-10-04 | 2022-05-13 | 大泰化工株式会社 | How to protect concrete |
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