TW202021928A - Additive for hydraulic compositions, and hydraulic composition - Google Patents
Additive for hydraulic compositions, and hydraulic composition Download PDFInfo
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- TW202021928A TW202021928A TW108100093A TW108100093A TW202021928A TW 202021928 A TW202021928 A TW 202021928A TW 108100093 A TW108100093 A TW 108100093A TW 108100093 A TW108100093 A TW 108100093A TW 202021928 A TW202021928 A TW 202021928A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
Description
本發明係關於一種水硬性組成物用添加劑。更詳細而言，係關於一種緩和粒料所含微粒成分或黏土質之影響，且同時可降低水硬性組成物之黏性，可適用於水泥組合物等之水硬性組成物用添加劑。 The present invention relates to an additive for hydraulic composition. In more detail, it relates to an additive for reducing the impact of the particulate components or clay properties contained in the pellets, and at the same time reducing the viscosity of the hydraulic composition, which can be applied to the hydraulic composition such as cement composition.
傳統上，為使砂漿或混凝土等水硬性組成物賦予流動性，其調製之際，會使用木質磺酸類分散劑、萘磺酸類分散劑、三聚氰胺磺酸類分散劑或聚羧酸類分散劑等作為分散劑。近年來，為提升填充性及省力化，並提升施工性，使用進一步提高流動性之水硬性組成物的機會增多，使這般水硬性組成物之需求漸增。 Traditionally, in order to impart fluidity to hydraulic compositions such as mortar or concrete, lignosulfonic acid-based dispersants, naphthalenesulfonic acid-based dispersants, melamine sulfonic acid-based dispersants, or polycarboxylic acid-based dispersants have been used as dispersion agents when preparing them. Agent. In recent years, in order to improve fillability, labor saving, and workability, there have been more opportunities to use hydraulic compositions that further improve fluidity, and the demand for such hydraulic compositions has gradually increased.
為獲得這般水硬性組成物，提出各種技術。例如，在專利文獻1中，藉由使用一種混和劑，其中混合了特定之聚羧酸類分散劑、羧酸單體與(間)丙烯酸類酯之共聚物，可賦予混凝土流動性及材料分離抗性。並且，在專利文獻1中，公開將作為原料成分之特定之聚羧酸類分散劑、羧酸單體與(間)丙烯酸類酯之共聚物組合，作為一液型混和劑供給之方法。 In order to obtain such a hydraulic composition, various techniques have been proposed. For example, in Patent Document 1, by using a mixing agent in which a specific polycarboxylic acid dispersant, a copolymer of a carboxylic acid monomer and (meta) acrylic ester is mixed, it can give concrete fluidity and material separation resistance. Sex. In addition, Patent Document 1 discloses a method of combining a specific polycarboxylic acid dispersant as a raw material component, a copolymer of a carboxylic acid monomer and an (meta)acrylic ester, and supplying it as a one-component mixing agent.
此外，在專利文獻2中，提出藉由使用特定之低取代羥丙甲纖維素，獲得高填充性及高流動性之混凝土。 In addition, Patent Document 2 proposes to obtain concrete with high filling properties and high fluidity by using specific low-substituted hypromellose.
專利文獻 Patent Literature
專利文獻1：日本專利特開2001-89212號公報 Patent Document 1: Japanese Patent Laid-Open No. 2001-89212
專利文獻2：日本專利特開平4-139047號公報 Patent Document 2: Japanese Patent Laid-open No. 4-139047
作為混合至水硬性組成物之粒料，係使用粗粒料與細粒料等。作為諸等粗粒料與細粒料，係使用透過自然作用由岩石形成，自河、山、海、陸產出之砂礫、沙子等天然粒料，以及透過碎石機等人工粉碎岩石而獲得之碎石及碎砂。 As the pellets mixed into the hydraulic composition, coarse pellets and fine pellets are used. As various coarse and fine aggregates, they are obtained by using natural aggregates such as gravel and sand from rivers, mountains, seas, and land that are formed from rocks through natural action, and are obtained by manually crushing rocks through stone crushers. The gravel and crushed sand.
由於優質之天然粒料資源日益枯竭，且考量到資源保護之觀點，及清洗時對環境造成之影響，在作為品質允許之範圍內，有時會在不洗掉附著於天然粒料上之微粒成分或黏土質之情況下使用。 Due to the depletion of high-quality natural pellet resources, and considering the viewpoint of resource protection and the impact on the environment during cleaning, within the range allowed by quality, sometimes the particles attached to the natural pellets are not washed away Use in the case of ingredients or clay.
此外，亦有使用附著有微粒成分或黏土質之碎石及碎砂等情況，而諸等微粒成分或黏土質，係人工粉碎岩石製造碎石及碎砂時所產生。 In addition, there are also cases where crushed stone and sand with particles or clay attached to it are used, and these particles or clays are produced by artificially crushing rocks to make gravel and sand.
若粒料附著有諸等微粒成分或黏土質，則存在分散劑添加量變多之問題。此外，亦存在混合有粒料、膠合劑、分散劑及消泡劑等成分之水硬性組成物之黏性提高之問題。 If various particulate components or clay properties adhere to the pellets, there is a problem that the amount of dispersant added increases. In addition, there is also the problem of increased viscosity of hydraulic compositions mixed with pellets, binders, dispersants, and defoamers.
以專利文獻1、2所公開之技術，無法解決諸等問題。因此，本發明欲解決之問題為提供一種水硬性組成物用添加劑，使得即便不洗掉附著於粒料之微粒成分或黏土質，亦可緩和粒料所含微粒成分或黏土質之影響，且同時可降低水硬性組成物之黏性。 The technologies disclosed in Patent Documents 1 and 2 cannot solve these problems. Therefore, the problem to be solved by the present invention is to provide an additive for a hydraulic composition, so that even if the particulate component or clay attached to the pellet is not washed off, the impact of the particulate component or the clay contained in the pellet can be alleviated, and At the same time, it can reduce the viscosity of hydraulic composition.
本發明者等為達成上述課題，經潛心研究結果，發現使用具特定聚合物之水硬性組成物用添加劑者為適當首選。根據本發明，提供以下水硬性組成物用添加劑。 In order to achieve the above-mentioned problem, the inventors of the present invention, after intensive research, found that the use of additives for hydraulic compositions with specific polymers is the appropriate first choice. According to the present invention, the following additives for hydraulic compositions are provided.
[1]一種水硬性組成物用添加劑，其中包含下述A成分與下述B成分：A成分：一聚合物，其中具備由丙烯酸及/或其鹽類所形成之結構單元，其質量平均分子量為1000以上且未滿100000；B成分：一乙烯基共聚物，其中分子中具備下述結構單元1及結構單元2，且包含1~99質量%之結構單元1，及包含1~99質量%之結構單元2：結構單元1：下述單體1由所形成之結構單元；結構單元2：由分子中具乙烯基之羧酸單體所形成之結構單元；單體1：下述結構式(1)所示不飽和(聚)烷二醇：
結構式(1)中、R1、R2及R3係表示相同或互異基團，且自氫原子、甲基及-(CH2)RCOOM所示之有機基當中選擇至少一基團，唯，R1、R2及R3當中的至少一個表示氫原子或甲基，R4表示氫原子或碳數為1~20之碳化氫基，R5O表示一或兩個以上碳數為2~4之氧伸烷基，p表示0~5之整數，q表示0或1，m表示1~300之整數，R表示0~2之整數，M表示氫原子或金屬原子。 In the structural formula (1), R 1 , R 2 and R 3 represent the same or different groups, and at least one group is selected from a hydrogen atom, a methyl group and an organic group represented by -(CH 2 )RCOOM, However, at least one of R 1 , R 2 and R 3 represents a hydrogen atom or a methyl group, R 4 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms, and R 5 O represents one or more carbon atoms 2~4 oxyalkylene groups, p represents an integer from 0 to 5, q represents 0 or 1, m represents an integer from 1 to 300, R represents an integer from 0 to 2, and M represents a hydrogen atom or a metal atom.
[2]如第[1]項所述之水硬性組成物用添加劑，其中該B成分係更含有0~30質量%之下述結構單元3之乙烯基共聚物：結構單元3：由可與該單體1及該羧酸單體進行共聚反應之單體3所形 成之結構單元。 [2] The additive for hydraulic composition according to item [1], wherein the component B is a vinyl copolymer containing 0-30% by mass of the following structural unit 3: structural unit 3: The monomer 1 and the carboxylic acid monomer are copolymerized by the monomer 3 Into the structural unit.
[3]如第[1]或[2]項所述之水硬性組成物用添加劑，其中相對於該B成分，該A成分之質量%係0.1~5質量%。 [3] The additive for hydraulic composition according to [1] or [2], wherein the mass% of the A component relative to the B component is 0.1 to 5 mass%.
[4]如第[1]~[3]項之任一項所述之水硬性組成物用添加劑，其中該A成分之質量平均分子量為1000以上且未滿10000。 [4] The additive for hydraulic composition according to any one of [1] to [3], wherein the mass average molecular weight of the component A is 1,000 or more and less than 10,000.
[5]一種水硬性組成物，其中含有第[1]~[4]項之任一項所述之水硬性組成物用添加劑。 [5] A hydraulic composition containing the additive for hydraulic composition according to any one of [1] to [4].
[6]如第[5]項所述之水硬性組成物，其中更含有膠合劑。 [6] The hydraulic composition according to item [5], which further contains a binder.
[7]如第[6]項所述之水硬性組成物，其中相對於該膠合劑100質量份，該A成分與該B成分之總質量份為0.1~2質量份。 [7] The hydraulic composition according to item [6], wherein the total mass parts of the A component and the B component is 0.1 to 2 parts by mass relative to 100 parts by mass of the adhesive.
根據本發明之水硬性組成物用添加劑可獲如下效果：即便不洗掉附著於粒料之微粒成分或黏土質，亦可緩和粒料所含微粒成分或黏土質之影響，且同時可降低水硬性組成物之黏性。 According to the additive for hydraulic composition of the present invention, the following effects can be obtained: even if the particulate component or clay attached to the pellet is not washed off, the impact of the particulate component or clay content in the pellet can be alleviated, and the water can be reduced at the same time. The viscosity of rigid components.
以下說明本發明之實施方式，唯應理解本發明並不限定於以下實施方式，本發明所屬技術領域中具有通常知識者可在不背離本發明之趣旨範圍內，對以下實施方式進行適當變更及修改，而仍屬於本發明之範圍。另，以下實施例等當中，若無特別記載，“%”係表示質量%，而“份”係表示質量份。 The following describes the embodiments of the present invention, but it should be understood that the present invention is not limited to the following embodiments. Those with ordinary knowledge in the technical field to which the present invention belongs can make appropriate changes and modifications to the following embodiments without departing from the scope of the present invention. Modifications still belong to the scope of the present invention. In addition, in the following examples and the like, unless otherwise stated, "%" means mass %, and "parts" means mass parts.
本實施方式之水硬性組成物用添加劑，係包含A成分與B成分之水硬性組成物用添加劑。 The additive for hydraulic composition of this embodiment is an additive for hydraulic composition containing A component and B component.
供於本實施方式之水硬性組成物用添加劑之A成分，係具備由丙烯酸及/或其鹽類所形成之結構單元之聚合物。在此，丙烯酸鹽之種類無特殊限制，例如可列舉：鈉鹽或鉀鹽等鹼金屬鹽、鈣鹽或鎂鹽等鹼土族金屬鹽、銨鹽、二乙醇胺鹽或三乙醇胺鹽等胺鹽等。若以易於處理或易取得之觀點考量，較佳為鈉鹽、銨鹽，更佳為鈉鹽。此外，丙烯酸及/或其鹽類可以僅為一種，亦可為兩種以上。 The A component used as the additive for the hydraulic composition of the present embodiment is a polymer having a structural unit formed of acrylic acid and/or its salts. Here, the type of acrylate is not particularly limited, and examples include alkali metal salts such as sodium salt or potassium salt, alkaline earth metal salts such as calcium salt or magnesium salt, amine salts such as ammonium salt, diethanolamine salt, or triethanolamine salt, etc. . From the viewpoint of easy handling or availability, sodium salt and ammonium salt are preferred, and sodium salt is more preferred. In addition, acrylic acid and/or its salts may be only one type, or two or more types.
供於本實施方式之水硬性組成物用添加劑之A成分之聚合物，其質量平均分子量係1000以上且未滿100000，較佳為1000以上且未滿70000，更佳為1000以上且未滿50000，尤佳為1000以上且未滿30000。甚至更佳為1000以上且未滿10000。 The polymer of component A used in the additive for hydraulic composition of this embodiment has a mass average molecular weight of 1,000 or more and less than 100,000, preferably 1,000 or more and less than 70,000, more preferably 1,000 or more and less than 50,000 , Especially preferably above 1,000 and less than 30,000. Even more preferably, it is 1,000 or more and less than 10,000.
供於本實施方式之水硬性組成物用添加劑之B成分，係分子中具備結構單元1及結構單元2之乙烯基共聚物。 The component B used in the additive for the hydraulic composition of the present embodiment is a vinyl copolymer having structural unit 1 and structural unit 2 in the molecule.
結構單元1由單體1所形成。單體1係由下述結構式(1)所表示之不飽和(聚)烷二醇。 Structural unit 1 is formed by monomer 1. Monomer 1 is an unsaturated (poly)alkylene glycol represented by the following structural formula (1).
結構式(1)中，R1、R2及R3係表示相同或互異基團，且自氫原子、甲基及-(CH2)RCOOM所示之有機基當中選擇至少一基團，唯，R1、R2及R3當中的至少一個表示氫原子或甲基。R4表示氫原子或碳數為1~20之碳化氫基。作為這樣的碳化氫基，可列舉甲基、乙基、丙基及丁基等。R5O表示一或兩個以上碳數為2~4之氧伸烷基。作為這樣的氧伸 烷基，可列舉氧化乙烯基、氧化丙烯基等。若為兩種以上之氧伸烷基，亦可為隨機加成、嵌段加成、交替加成等任一加成形態。p表示0~5之整數，q表示0或1，m表示1~300之整數，R表示0~2之整數，M表示氫原子或金屬原子。 In the structural formula (1), R 1 , R 2 and R 3 represent the same or different groups, and at least one group is selected from hydrogen atom, methyl group and organic group represented by -(CH 2 )RCOOM, However, at least one of R 1 , R 2 and R 3 represents a hydrogen atom or a methyl group. R 4 represents a hydrogen atom or a hydrocarbon group with 1 to 20 carbon atoms. Examples of such hydrocarbon groups include methyl, ethyl, propyl, and butyl. R 5 O represents one or more oxyalkylene groups with a carbon number of 2 to 4. As such an oxyalkylene group, an oxyethylene group, an oxypropylene group, etc. are mentioned. If it is two or more oxyalkylene groups, it can also be in any addition form such as random addition, block addition, and alternate addition. p represents an integer from 0 to 5, q represents 0 or 1, m represents an integer from 1 to 300, R represents an integer from 0 to 2, and M represents a hydrogen atom or a metal atom.
作為這樣的單體1，例如可列舉：α-乙烯基-ω-羥(聚)氧丁烯(聚)氧化乙烯、α-烯丙-ω-甲氧-(聚)氧化乙烯、α-烯丙-ω-甲氧-(聚)氧化乙烯(聚)氧化丙烯、α-烯丙-ω-羥-(聚)氧化乙烯、α-烯丙-ω-羥-(聚)氧化乙烯(聚)氧化丙烯、α-甲烯丙-ω-羥-(聚)氧化乙烯、α-甲烯丙-ω-甲氧-(聚)氧化乙烯、α-甲烯丙-ω-羥-(聚)氧化乙烯(聚)氧化丙烯、α-甲烯丙-ω-乙醯-(聚)氧化乙烯、α-(3-甲-3-丁烯)-ω-羥-(聚)氧化乙烯、α-(3-甲-3-丁烯)-ω-丁氧-(聚)氧化乙烯、α-(3-甲-3-丁烯)-ω-羥-(聚)氧化乙烯(聚)氧化丙烯、α-(3-甲-3-丁烯)-ω-乙醯-(聚)氧化乙烯(聚)氧化丙烯、α-丙烯醯-ω-羥-(聚)氧化乙烯、α-丙烯醯-ω-甲氧-(聚)氧化乙烯、α-丙烯醯-ω-丁氧-(聚)氧化乙烯、α-丙烯醯-ω-甲氧-(聚)氧化乙烯(聚)氧化丙烯、α-甲基丙烯醯-ω-羥-(聚)氧化乙烯、α-甲基丙烯醯-ω-甲氧-(聚)氧化乙烯、α-甲基丙烯醯-ω-丁氧-(聚)氧化乙烯、α-丙烯醯-ω-甲氧-(聚)氧化乙烯(聚)氧化丙烯、α-甲基丙烯醯-ω-羥-(聚)氧化乙烯(聚)氧化丙烯、α-甲基丙烯醯-ω-乙醯-(聚)氧化乙烯(聚)氧化丙烯、順丁烯二酸或反丁烯二酸、伊康酸等不飽和二羧酸與(聚)氧化乙烯所形成之單酯、順丁烯二酸或反丁烯二酸、伊康酸等不飽和二羧酸與(聚)氧化乙烯(聚)氧化丙烯所形成之單酯。 As such monomer 1, for example, α-vinyl-ω-hydroxy(poly)oxybutylene (poly)ethylene oxide, α-allyl-ω-methoxy-(poly)ethylene oxide, α-ene Propylene-ω-methoxy-(poly)ethylene oxide (poly)propylene oxide, α-allyl-ω-hydroxy-(poly)ethylene oxide, α-allyl-ω-hydroxy-(poly)ethylene oxide (poly) Propylene oxide, α-methallyl-ω-hydroxy-(poly)oxyethylene, α-methallyl-ω-methoxy-(poly)oxyethylene, α-methallyl-ω-hydroxy-(poly)oxy Ethylene (poly)propylene oxide, α-methallyl-ω-acetyl-(poly)ethylene oxide, α-(3-methyl-3-butene)-ω-hydroxy-(poly)ethylene oxide, α-( 3-methyl-3-butene)-ω-butoxy-(poly)ethylene oxide, α-(3-methyl-3-butene)-ω-hydroxy-(poly)ethylene oxide (poly)propylene oxide, α -(3-Methyl-3-butene)-ω-acetylene-(poly)ethylene oxide (poly)propylene oxide, α-propylene oxide-ω-hydroxy-(poly)ethylene oxide, α-propylene oxide-ω- Methoxy-(poly)ethylene oxide, α-propylene-ω-butoxy-(poly)oxyethylene, α-propylene-ω-methoxy-(poly)oxyethylene (poly)propylene oxide, α-methyl Acrylic acid-ω-hydroxy-(poly)ethylene oxide, α-methacrylic acid-ω-methoxy-(poly)ethylene oxide, α-methacrylic acid-ω-butoxy-(poly)ethylene oxide, α -Propylene oxide-ω-Methoxy-(poly)ethylene oxide (poly)propylene oxide, α-methacrylic acid-ω-hydroxy-(poly)ethylene oxide (poly)propylene oxide, α-methacrylic acid-ω -Acetyl-(poly)ethylene oxide (poly)propylene oxide, maleic acid or fumaric acid, itaconic acid and other unsaturated dicarboxylic acids and (poly)ethylene oxide monoester, maleic acid Monoester formed by unsaturated dicarboxylic acid such as alkene acid, fumaric acid and itaconic acid and (poly)oxyethylene (poly)oxypropylene.
結構單元2由羧酸單體所形成。在此，羧酸單體係指不具有酯基或醯胺基之單體。羧酸單體之分子中具有乙烯基。作為這樣的羧酸單體，例如可列舉：(間)丙烯酸、巴豆酸、(無水)順丁烯二酸、(無水)伊康酸、反丁烯二酸及其鹽類等。作為鹽，並無特殊限制，例如可列舉：鈉鹽、鉀鹽等鹼金屬鹽、鈣鹽、鎂鹽等鹼土族金屬鹽、銨鹽、二乙醇胺鹽、三乙醇胺鹽等胺鹽等。其中較佳為鈉鹽與鈣鹽。 The structural unit 2 is formed by a carboxylic acid monomer. Here, the carboxylic acid monosystem refers to a monomer having no ester group or amide group. The carboxylic acid monomer has a vinyl group in its molecule. Examples of such carboxylic acid monomers include (meta) acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, and salts thereof. The salt is not particularly limited, and examples thereof include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, and amine salts such as ammonium salt, diethanolamine salt, and triethanolamine salt. Among them, sodium salt and calcium salt are preferred.
供於本實施方式之水硬性組成物用添加劑之B成分之乙烯基共聚物，可進一步在分子中含有結構單元3作為任意之結構單元。結構單元3可以由可與單體1及羧酸單體進行共聚反應的單體3所形成。 The vinyl copolymer of component B used as the additive for hydraulic composition of this embodiment may further contain structural unit 3 as an arbitrary structural unit in the molecule. The structural unit 3 may be formed of a monomer 3 that can be copolymerized with the monomer 1 and the carboxylic acid monomer.
單體3只要能夠與單體1及羧酸單體共聚即可，並無特殊限制，例如可列舉：丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸丁酯等烷基(間)丙烯酸酯類單體；(間)丙烯醯胺、N,N-二甲(間)丙烯醯胺等不飽和醯胺類、(間)丙烯腈等不飽和氰類；順丁烯二酸或反丁烯二酸等不飽和二羧酸與碳數為1~22之烷基或烯基之醇所形成之單酯；順丁烯二酸或反丁烯二酸等不飽和二羧酸與(聚)烷二醇或碳數為1~22之烷基或烯基之醇所形成之二酯等不飽和二羧酸二酯類；不飽和羧酸或不飽和二羧酸與碳數為1~22之胺所形成之單醯胺或二醯胺等醯胺單體類；不飽和羧酸或不飽和二羧酸與碳數為1~22之胺所形成之單醯胺或二醯胺等醯胺單體類；將烷基二羧酸與聚乙烯聚胺進行縮合反應後，在具有活性氫之氮原子上加成環氧乙烷或環氧丙烷後，再與(間)丙烯酸反應形成之反應物；不飽和羧酸或不飽和二羧酸與碳數為1~22之胺所形成之單醯胺或二醯胺等醯胺單體類；將烷基二羧酸與聚乙烯聚胺進行縮合反應後，在具有活性氫之氮原子上加成環氧乙烷或環氧丙烷後，再與環氧丙基(間)丙烯酸酯反應形成之反應物；聚醯胺聚胺單體類；由(間)烯丙磺酸或乙烯基磺酸及諸等鹽 類等所形成之磺酸類單體類；由磷酸2-(甲基丙烯醯氧)乙基或磷酸-雙[2-(甲基丙烯醯氧)乙基]及諸等鹽類等所形成之磷酸類單體類等。 Monomer 3 is not particularly limited as long as it can be copolymerized with monomer 1 and a carboxylic acid monomer. Examples include alkyl (meta)acrylate monomers such as methyl acrylate, methyl methacrylate, and butyl acrylate. Body; (m) acrylamide, N,N-dimethyl (m) acrylamide and other unsaturated amides, (m) acrylonitrile and other unsaturated cyanogens; maleic acid or fumaric acid Monoesters formed by unsaturated dicarboxylic acids and alkyl or alkenyl alcohols with carbon number of 1-22; unsaturated dicarboxylic acids such as maleic acid or fumaric acid and (poly)alkane Unsaturated dicarboxylic acid diesters such as diesters formed by alcohols or alkyl or alkenyl alcohols with 1-22 carbons; unsaturated carboxylic acids or unsaturated dicarboxylic acids and amines with 1-22 carbons Amine monomers such as monoamide or diamide; unsaturated carboxylic acid or unsaturated dicarboxylic acid and amine with carbon number of 1 to 22 formed monoamide or diamide and other amide monomers Body type; after the condensation reaction of alkyl dicarboxylic acid and polyethylene polyamine, ethylene oxide or propylene oxide is added to the nitrogen atom with active hydrogen, and then reacted with (m) acrylic acid. ; Amine monomers such as mono-amine or di-amide formed by unsaturated carboxylic acid or unsaturated dicarboxylic acid and amine with carbon number of 1-22; condensation of alkyl dicarboxylic acid and polyethylene polyamine After the reaction, ethylene oxide or propylene oxide is added to the nitrogen atom with active hydrogen, and then reacted with glycidyl (m) acrylate to form a reactant; polyamide polyamine monomers; (M) Allyl sulfonic acid or vinyl sulfonic acid and other salts Sulfonic acid monomers formed by the like; formed by phosphoric acid 2-(methacryloxy)ethyl or phosphoric acid-bis[2-(methacryloxy)ethyl] and other salts, etc. Phosphoric acid monomers, etc.
在供於本實施方式之水硬性組成物用添加劑之B成分中，含有1~99質量%之結構單元1，較佳為含有70~99質量%，更佳為含有75~99質量%，尤佳為含有80~99質量%；B成分中，含有1~99質量%之結構單元2，較佳為含有1~30質量%，更佳為含有25~99質量%，尤佳為含有1~20質量%。此外，供於本實施方式之水硬性組成物用添加劑之B成分中，較佳為含有0~30質量%之結構單元3，更佳為含有0~20質量%，尤佳為含有0~10質量%，甚至更佳為含有0~5質量%。 The component B of the additive for hydraulic composition of this embodiment contains 1 to 99% by mass of structural unit 1, preferably 70 to 99% by mass, more preferably 75 to 99% by mass, especially Preferably, it contains 80~99% by mass; in component B, 1~99% by mass of structural unit 2 is contained, preferably 1~30% by mass, more preferably 25~99% by mass, and particularly preferably 1~ 20% by mass. In addition, the component B of the additive for hydraulic composition of the present embodiment preferably contains 0-30% by mass of structural unit 3, more preferably contains 0-20% by mass, and particularly preferably contains 0-10 % By mass, and even more preferably 0-5% by mass.
供於本實施方式之水硬性組成物用添加劑之B成分中，結構單元1、結構單元2之總量較佳為80質量%以上，更佳為85質量%以上，尤佳為90質量%以上，甚至更佳為95質量%以上。 In the component B of the additive for hydraulic composition of this embodiment, the total amount of structural unit 1 and structural unit 2 is preferably 80% by mass or more, more preferably 85% by mass or more, and particularly preferably 90% by mass or more , And even more preferably 95% by mass or more.
供於本實施方式之水硬性組成物用添加劑之B成分之質量平均分子量，可藉由凝膠滲透層析術測得，若以聚乙二醇換算，較佳為2000~500000，更佳為5000~200000，尤佳為10000~100000。 The mass average molecular weight of component B of the additive for hydraulic composition of this embodiment can be measured by gel permeation chromatography. If it is converted to polyethylene glycol, it is preferably 2000 to 500,000, more preferably 5000~200000, especially 10000~100000.
這樣的B成分，可透過眾所周知之自由基聚合反應取得。例如可透過各種方法進行製備。其中可列舉：在溶媒中使用水之自由基聚合、在溶媒中使用有機溶媒之自由基聚合、無溶媒之自由基聚合等方法。自由基聚合時之反應溫度，較佳為0~120℃，更佳為20~100℃，尤佳為50~90℃。用於自由基聚合反應之自由基聚合起始劑，可列舉：過氧化氫、過硫酸銨、過硫酸鈉、過硫酸鉀等過氧化物；2,2-偶氮雙(2-甲脒基丙烷)二鹽酸鹽、2,2-偶氮雙(異丁腈)等偶氮類化合物。只要是在聚合反應溫度下分解，且產生自由基之物質，其種類並無特殊限制。諸等亦可與亞硫酸鹽或L-抗壞血酸等還原性物質，進而與胺等物質組合，作為氧化還原 起始劑使用。為了使得到的B成分之質量平均分子量為所期望之範圍，亦可使用2-巰基乙醇、2-巰基丙酸、3-巰基丙酸、氫硫基乙酸、硫甘油、硫代蘋果酸等鏈轉移劑。諸等自由基聚合起始劑、還原性物質及鏈轉移劑可分別單獨使用，亦可併用兩種以上。對於反應系統內之壓力並無特殊限制，唯較佳為常壓。 Such B component can be obtained through the well-known radical polymerization reaction. For example, it can be prepared by various methods. Among them, methods such as radical polymerization using water in a solvent, radical polymerization using an organic solvent in a solvent, and free radical polymerization without a solvent can be mentioned. The reaction temperature during radical polymerization is preferably 0 to 120°C, more preferably 20 to 100°C, and particularly preferably 50 to 90°C. Radical polymerization initiators used in radical polymerization reactions include peroxides such as hydrogen peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, etc.; 2,2-azobis(2-carboxamidino Azo compounds such as propane) dihydrochloride and 2,2-azobis(isobutyronitrile). As long as it is a substance that decomposes at the polymerization temperature and generates free radicals, there are no special restrictions on its type. These can also be combined with reducing substances such as sulfite or L-ascorbic acid, and then combined with substances such as amines as redox The initiator is used. In order to make the mass average molecular weight of component B within the desired range, 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, hydrothioglycolic acid, thioglycerin, thiomalic acid and other chains can also be used. Transfer agent. The radical polymerization initiators, reducing substances, and chain transfer agents may be used individually, or two or more of them may be used in combination. There are no special restrictions on the pressure in the reaction system, but normal pressure is preferred.
本實施方式之水硬性組成物用添加劑中，A成分與B成分之濃度並無特殊限制，唯相對於B成分，A成分之質量%較佳為0.1~5質量%，更佳為0.5~4質量%。 In the additive for hydraulic composition of the present embodiment, the concentration of the A component and the B component is not particularly limited, but the mass% of the A component is preferably 0.1 to 5 mass%, more preferably 0.5 to 4 relative to the B component quality%.
接著，針對本實施方式之水硬性組成物進行說明。本實施方式之水硬性組成物，含有本實施方式之水硬性組成物用添加劑。 Next, the hydraulic composition of this embodiment will be described. The hydraulic composition of this embodiment contains the additive for hydraulic composition of this embodiment.
水硬性組成物用添加劑相對於水硬性組成物之添加方法，可分別獨立添加A成分與B成分，亦可同時添加。A成分及B成分可作為粉末添加於水硬性組成物漿料中，此外，亦可將A成分及B成分以分散或溶解於液態收縮抑制劑或液態消泡劑等狀態下，添加至水硬性組成物漿料，甚至，亦可將A成分及B成分以溶解於水的狀態下添加至水硬性組成物漿料。 With respect to the method of adding the hydraulic composition additive to the hydraulic composition, the A component and the B component may be added separately or simultaneously. The A component and B component can be added as powder to the hydraulic composition slurry. In addition, the A component and B component can be dispersed or dissolved in a liquid shrinkage inhibitor or liquid defoamer to add to the hydraulic composition In the composition slurry, even the A component and the B component may be added to the hydraulic composition slurry in a state of being dissolved in water.
另，使用作為B成分之乙烯基共聚物作為水溶液時，以A成分與B成分之相溶性觀點考量，B成分之1質量%水溶液之pH值較佳為2~7，更佳為2~6，尤佳為2~5。 In addition, when using the vinyl copolymer as component B as an aqueous solution, considering the compatibility of component A and component B, the pH of a 1% by mass aqueous solution of component B is preferably 2-7, more preferably 2-6 , Preferably 2~5.
本實施方式之水硬性組成物，係使用如上說明之本實施方式之水硬性組成物用添加劑調製而成，其中較佳為水泥漿、砂漿、混凝土等水泥組合物。該水泥組合物，係至少使用水泥一種物質作為膠合劑者，其中，可單獨使用水泥，此外，亦可併用水泥、卜作嵐材料或具潛在水硬性之細粉混和材料。作為這樣的水泥，可列舉：普通卜特蘭水泥、早強卜特 蘭水泥、中庸熱卜特蘭水泥、低熱卜特蘭水泥等各種卜特蘭水泥、高爐水泥、飛灰水泥、矽灰水泥等各種混合水泥。此外，作為細粉混和材料，可列舉高爐爐碴細粉、矽灰、飛灰等。 The hydraulic composition of this embodiment is prepared using the additive for the hydraulic composition of this embodiment described above, and among them, cement compositions such as cement paste, mortar, and concrete are preferred. The cement composition is one that uses at least one kind of cement as the cement. Among them, the cement can be used alone, and in addition, it can also be used in combination with cement, a sturdy material or a fine powder mixed material with potential hydraulic properties. Examples of such cements include: ordinary portland cement, early strength port Various mixed cements such as blue cement, moderate heat portland cement, low heat portland cement, blast furnace cement, fly ash cement, and silica fume cement. In addition, as fine powder mixing materials, blast furnace ballast fine powder, silica fume, fly ash, etc. can be cited.
本實施方式之水硬性組成物，較佳為含有粒料。作為粒料，可採用細粒料或粗粒料等任意之適當粒料。這樣的粒料當中，作為細粒料，可列舉：河砂、山砂、陸砂、矽砂、碎砂、高爐爐碴細粒料等；作為粗粒料，可列舉：河礫、山礫、陸礫、碎石、高爐爐碴粗粒料等。 The hydraulic composition of this embodiment preferably contains pellets. As the pellets, any suitable pellets such as fine pellets and coarse pellets can be used. Among such aggregates, fine aggregates include river sand, mountain sand, land sand, silica sand, crushed sand, blast furnace ballast fine aggregates, etc.; coarse aggregates include river gravel, mountain gravel , Land gravel, crushed stone, blast furnace ballast coarse-grained materials
在粒料上附著有微粒成分或黏土質，在不洗掉微粒成分或黏土質之情況下使用時，水硬性組成物中會含有微粒成分或黏土質，唯本實施方式之水硬性組成物，除了諸等微粒成分或黏土質之影響被緩和，且可降低水硬性組成物之黏性。 Particles or clay are attached to the pellets. When used without washing off the particles or clay, the hydraulic composition will contain the particulates or clay. Only the hydraulic composition of this embodiment is the hydraulic composition. In addition to the effects of particulate components or clay properties are alleviated, and the viscosity of the hydraulic composition can be reduced.
本實施方式之水硬性組成物中，相對於膠合劑100質量份，A成分與B成分之總質量份較佳為0.1~2質量份，更佳為0.1~1.5質量份，尤佳為0.1~1質量份。 In the hydraulic composition of this embodiment, relative to 100 parts by mass of the adhesive, the total mass parts of component A and component B is preferably 0.1-2 parts by mass, more preferably 0.1-1.5 parts by mass, and particularly preferably 0.1~ 1 part by mass.
本實施方式之水硬性組成物中，較佳為使用易受黏土質流動性影響的水膠比30~60%。另，水膠比係指水硬性組成物中的水相對於100質量份水泥等膠合劑之質量份，若水為50質量份，則水膠比為50%。 In the hydraulic composition of this embodiment, it is preferable to use a water-to-gel ratio of 30 to 60%, which is easily affected by the fluidity of the clay. In addition, the water-binder ratio refers to the mass parts of water in the hydraulic composition relative to 100 parts by mass of cement and other cements. If the water is 50 parts by mass, the water-binder ratio is 50%.
本實施方式之水硬性組成物，在不損及其效果之範圍內，可適當地包含：例如由陰離子界面活性劑組成的AE調整劑、例如氧伸烷類消泡劑、例如由氧羧酸鹽組成之緩凝劑、例如由烷醇胺組成之硬化促進劑、例如由聚氧乙烯烷基醚組成之乾燥收縮抑制劑、例如由異噻唑啉類化合物組成之防腐劑、例如由高級脂肪酸衍生物組成之防水劑、例如由亞硝酸鹽組成之防鏽劑等。 The hydraulic composition of the present embodiment may suitably contain, within a range that does not impair its effects, for example, an AE modifier composed of an anionic surfactant, such as an oxyalkylene-based defoaming agent, such as an oxycarboxylic acid Retarders composed of salts, such as hardening accelerators composed of alkanolamines, such as drying shrinkage inhibitors composed of polyoxyethylene alkyl ethers, such as preservatives composed of isothiazoline compounds, such as derived from higher fatty acids Water-proofing agent composed of materials, such as rust inhibitor composed of nitrite.
試驗分類1(作為A成分之丙烯酸及/或其鹽類之聚合物)使用的丙烯酸及/或其鹽類之聚合物彙整如表1所示。 Test category 1 (polymer of acrylic acid and/or its salt as component A) is summarized in Table 1 for the polymer of acrylic acid and/or its salt used.
表1當中， In Table 1,
A-1：聚丙烯酸鈉(東亞合成株式會社製ARON T-210) A-1: Sodium polyacrylate (ARON T-210 manufactured by Toagosei Co., Ltd.)
A-2：聚丙烯酸(和光純藥工業株式會社製聚丙烯酸5,000) A-2: Polyacrylic acid (Polyacrylic acid 5,000 manufactured by Wako Pure Chemical Industries, Ltd.)
A-3：聚丙烯酸(和光純藥工業株式會社製聚丙烯酸25,000) A-3: Polyacrylic acid (Polyacrylic acid 25,000 manufactured by Wako Pure Chemical Industries, Ltd.)
Ar-1：聚丙烯酸(和光純藥工業株式會社製聚丙烯酸1,000,000) Ar-1: Polyacrylic acid (Polyacrylic acid 1,000,000 manufactured by Wako Pure Chemical Industries, Ltd.)
Ar-2：聚丙烯酸鈉(東亞合成株式會社製ARON A-20P-X) Ar-2: Sodium polyacrylate (ARON A-20P-X manufactured by Toagosei Co., Ltd.)
Ar-3：羥丙甲纖維素(信越化學工業社製METOLOSE Hi90SH100000) Ar-3: Hypromellose (METOLOSE Hi90SH100000 manufactured by Shin-Etsu Chemical Co., Ltd.)
d-1：由丙烯酸鈉所形成之結構單元 d-1: The structural unit formed by sodium acrylate
d-2：由丙烯酸所形成之結構單元 d-2: Structural unit formed by acrylic acid
d-3：由丙烯酸所形成之結構單元 d-3: Structural unit formed by acrylic acid
d-4：由丙烯酸所形成之結構單元 d-4: Structural unit formed by acrylic acid
d-5：由丙烯酸鈉所形成之結構單元 d-5: The structural unit formed by sodium acrylate
試驗分類2(製備作為B成分之乙烯基共聚物) Test category 2 (preparation of vinyl copolymer as component B)
製備例1{製備乙烯基共聚物(B-1)} Preparation Example 1 {Preparation of vinyl copolymer (B-1)}
將蒸餾水250g、α-(3-甲-3-丁烯)-ω-羥-聚(n=50)氧 化乙烯330g倒入備有溫度計、攪拌器、滴液漏斗、氮氣導管之反應容器(以下，使用相同儀器)，邊攪拌邊均勻溶解後，將環境氣體置換為氮氣，並以溫水浴使反應系統之溫度維持在65℃。接著，以3小時滴定1%過氧化氫水16g，與此同時，以3小時滴定將丙烯酸30g均勻溶解至離子交換水80g之水溶液，與此同時，以4小時滴定將L-抗壞血酸2g與氫硫基乙酸3g溶解至離子交換水14g之水溶液。之後的2小時，將反應系統之溫度維持在65℃，結束聚合反應。之後，將30%氫氧化鈉水溶液加入反應系統內，調整至pH3，並以離子交換水調整濃度至40%，獲得反應混合物。以凝膠滲透層析術(GPC)分析該反應混合物，得其質量平均分子量為35000。將該反應物作為乙烯基共聚物(B-1)。 Distilled water 250g, α-(3-methyl-3-butene)-ω-hydroxy-poly(n=50) oxygen Pour 330g of ethylene glycol into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen pipe (hereafter, using the same equipment). After stirring and uniformly dissolving, replace the ambient gas with nitrogen and use a warm water bath to make the reaction system The temperature is maintained at 65°C. Next, 16 g of 1% hydrogen peroxide water was titrated in 3 hours. At the same time, 30 g of acrylic acid was uniformly dissolved in an aqueous solution of 80 g of ion-exchanged water in 3 hours of titration. At the same time, 2 g of L-ascorbic acid and hydrogen were titrated in 4 hours. An aqueous solution of 3 g of thioacetic acid dissolved in 14 g of ion exchange water. For the next 2 hours, the temperature of the reaction system was maintained at 65°C to complete the polymerization reaction. After that, a 30% sodium hydroxide aqueous solution was added to the reaction system, adjusted to pH 3, and the concentration was adjusted to 40% with ion exchange water to obtain a reaction mixture. The reaction mixture was analyzed by gel permeation chromatography (GPC), and the mass average molecular weight was 35,000. This reactant is referred to as a vinyl copolymer (B-1).
製備例2{製備乙烯基共聚物(B-2)} Preparation Example 2 {Preparation of vinyl copolymer (B-2)}
反應容器內倒入蒸餾水150g，將環境氣體置換為氮氣，於氮氣環境氣體下使反應系統溫度維持在60℃。接著將蒸餾水150g、甲基丙烯酸20g、α-羥-ω-甲基丙烯醯-聚(n=2)丙烯聚(n=113)氧化乙烯320g、羥乙丙烯酸酯10g及3-巰基丙酸3.5g均勻混合，調整單體混合物水溶液。將該單體混合物水溶液與10%過硫酸鈉水溶液24g以4小時間同時滴定至反應容器，進行自由基共聚反應，進而，將10%過硫酸鈉水溶液6g以1小時滴定進行反應。之後的1小時，讓反應系統溫度維持在60℃，進行自由基共聚反應。接著，將反應系統冷卻至室溫後，加入氫氧化鈉水溶液，調整至pH5，並以蒸餾水調整濃度至40%，獲得反應混合物。以凝膠滲透層析術(GPC)分析該反應混合物，得其質量平均分子量為43000。將該反應物作為乙烯基共聚物(B-2)。 Pour 150 g of distilled water into the reaction vessel, replace the ambient gas with nitrogen, and maintain the temperature of the reaction system at 60° C. under the nitrogen atmosphere. Then, distilled water 150g, methacrylic acid 20g, α-hydroxy-ω-methacrylic acid-poly(n=2) propylene poly(n=113) ethylene oxide 320g, hydroxyethyl acrylate 10g and 3-mercaptopropionic acid 3.5 g Mix uniformly and adjust the monomer mixture aqueous solution. This monomer mixture aqueous solution and 24 g of a 10% sodium persulfate aqueous solution were simultaneously titrated to a reaction vessel for 4 hours to perform a radical copolymerization reaction, and further, 6 g of a 10% sodium persulfate aqueous solution was reacted by titration for 1 hour. In the next hour, the temperature of the reaction system was maintained at 60°C to proceed with the radical copolymerization reaction. Then, after cooling the reaction system to room temperature, an aqueous sodium hydroxide solution was added to adjust the pH to 5, and the concentration was adjusted to 40% with distilled water to obtain a reaction mixture. The reaction mixture was analyzed by gel permeation chromatography (GPC), and the mass average molecular weight was 43,000. This reactant is referred to as a vinyl copolymer (B-2).
製備例3{製備乙烯基共聚物(B-3)} Preparation Example 3 {Preparation of vinyl copolymer (B-3)}
反應容器內倒入蒸餾水150g，將環境氣體置換為氮氣，於氮氣環境氣 體下使反應系統溫度維持在60℃。接著將蒸餾水150g、甲基丙烯酸35g、α-甲氧-ω-甲基丙烯醯-聚(n=23)氧化乙烯300g、丙烯酸甲5g及3-巰基丙酸3.5g均勻混合，調整單體混合物水溶液。將該單體混合物水溶液與10%過硫酸鈉水溶液24g以4小時間同時滴定至反應容器，進行自由基共聚反應，進而，將10%過硫酸鈉水溶液6g以1小時滴定進行反應。之後的1小時，讓反應系統溫度維持在60℃，進行自由基共聚反應。接著，將反應系統冷卻至室溫後，加入氫氧化鈉水溶液，調整至pH4，並以蒸餾水調整濃度至40%，獲得反應混合物。以凝膠滲透層析術(GPC)分析該反應混合物，得其質量平均分子量為43000。將該反應物作為乙烯基共聚物(B-3)。以上製備之乙烯基共聚物，彙整顯示於表2。 Pour 150g of distilled water into the reaction vessel and replace the ambient gas with nitrogen. The temperature of the reaction system was maintained at 60°C. Then, 150 g of distilled water, 35 g of methacrylic acid, 300 g of α-methoxy-ω-methacrylic acid-poly(n=23) ethylene oxide, 5 g of methyl acrylate and 3.5 g of 3-mercaptopropionic acid were uniformly mixed to adjust the monomer mixture Aqueous solution. This monomer mixture aqueous solution and 24 g of a 10% sodium persulfate aqueous solution were simultaneously titrated to a reaction vessel for 4 hours to perform a radical copolymerization reaction, and further, 6 g of a 10% sodium persulfate aqueous solution was reacted by titration for 1 hour. In the next hour, the temperature of the reaction system was maintained at 60°C to proceed with the radical copolymerization reaction. Next, after cooling the reaction system to room temperature, an aqueous sodium hydroxide solution was added to adjust the pH to 4, and the concentration was adjusted to 40% with distilled water to obtain a reaction mixture. The reaction mixture was analyzed by gel permeation chromatography (GPC), and the mass average molecular weight was 43,000. This reactant is referred to as a vinyl copolymer (B-3). The vinyl copolymers prepared above are collectively shown in Table 2.
表2當中， In Table 2,
＊1：作為B成分之乙烯基共聚物之種類 *1: Type of vinyl copolymer as component B
＊2：形成結構單元1之單體1之種類 *2: Type of monomer 1 forming structural unit 1
＊3：形成結構單元2之羧酸單體之種類 *3: The type of carboxylic acid monomer forming structural unit 2
＊4：形成結構單元3之單體3之種類 ＊4: Types of monomer 3 forming structural unit 3
比例：單位為質量% Proportion: The unit is mass%
單體(e-1)~(e-4)：彙整如下述表3之結構式(1)所示單體 Monomers (e-1)~(e-4): aggregated as the monomers shown in the structural formula (1) in Table 3 below
單體(f-1)：丙烯酸 Monomer (f-1): acrylic acid
單體(f-2)：甲基丙烯酸 Monomer (f-2): methacrylic acid
單體(g-1)：丙烯酸甲酯 Monomer (g-1): methyl acrylate
表3當中， In Table 3,
EO：氧化乙烯基 EO: oxyethylene
PO：氧化丙烯基 PO: Propylene oxide
EO(113)+PO(2)：EO 113mol與PO 2mol總計115mol之加成產物 EO(113)+PO(2): the addition product of 115mol of EO 113mol and PO 2mol in total
試驗分類3(A成分、B成分之質量平均分子量之測定) Test category 3 (Determination of the mass average molecular weight of component A and component B)
透過以下方法測定A成分及B成分之質量平均分子量。結果如表1、2所示。 Measure the mass average molecular weight of component A and component B by the following method. The results are shown in Tables 1 and 2.
A成分之質量平均分子量之測定 Determination of the mass average molecular weight of component A
作為A成分之丙烯酸及/或其鹽類之聚合物之質量平均分子量之測定，係藉由凝膠滲透層析術多角度光散射法(GPC-MALS法)及/或凝膠滲透層析術(GPC法)執行，測定條件如下。另，聚丙烯酸之質量平均分子量-旦超過500,000，便無法運用GPC法測定，故針對質量平均分子量超過500,000者，係使用GPC-MALS法。另，在A-3與Ar-1中，GPC-MALS法與GPC法之分子量之差在±3%以內，故視為相同者。 The mass average molecular weight of the polymer of acrylic acid and/or its salt as component A is determined by gel permeation chromatography, multi-angle light scattering method (GPC-MALS method) and/or gel permeation chromatography (GPC method) Executed, and the measurement conditions are as follows. In addition, if the mass average molecular weight of polyacrylic acid exceeds 500,000, it cannot be measured by the GPC method. Therefore, the GPC-MALS method is used for the mass average molecular weight of more than 500,000. In addition, in A-3 and Ar-1, the difference in molecular weight between the GPC-MALS method and the GPC method is within ±3%, so they are considered the same.
測定條件 Measurement conditions
GPC-MALS法 GPC-MALS method
檢測器：示差折射率偵檢器(RI)、多角度光散射檢測器(MALS) Detectors: differential refractive index detector (RI), multi-angle light scattering detector (MALS)
管柱：昭和電工製OHpak SB-807 HQ+SB-806M HQ Column: Showa Denko OHpak SB-807 HQ+SB-806M HQ
溶離液：0.1M Tris緩衝液(pH=0.9、添加0.1M鹽化鉀)/乙腈混合 Eluent: 0.1M Tris buffer (pH=0.9, add 0.1M potassium salt)/acetonitrile mix
溶媒(混合體積比：7/3) Solvent (mixing volume ratio: 7/3)
流速：0.5mL/分 Flow rate: 0.5mL/min
管柱溫度：40℃ Column temperature: 40℃
GPC法 GPC method
檢測器：示差折射率偵檢器(RI) Detector: Differential refractive index detector (RI)
管柱：昭和電工製OHpak SB-G+SB-806M HQ+SB-806M Column: Showa Denko OHpak SB-G+SB-806M HQ+SB-806M
溶離液：50mM硝酸鈉水溶液 Eluent: 50mM sodium nitrate aqueous solution
流速：0.7mL/分 Flow rate: 0.7mL/min
管柱溫度：40℃ Column temperature: 40℃
標準物質：Agilent Technologies Japan,Ltd.製聚丙烯酸鈉 Standard material: Sodium polyacrylate manufactured by Agilent Technologies Japan, Ltd.
B成分之質量平均分子量之測定 Determination of the mass average molecular weight of component B
作為B成分之乙烯基共聚物之質量平均分子量之測定，係藉由凝膠滲透層析術法(GPC)執行，條件如下。 The determination of the mass average molecular weight of the vinyl copolymer as component B is performed by gel permeation chromatography (GPC), and the conditions are as follows.
測定條件 Measurement conditions
檢測器：示差折射率偵檢器(RI) Detector: Differential refractive index detector (RI)
管柱：昭和電工製OHpak SB-G+SB-806M HQ+SB-806M Column: Showa Denko OHpak SB-G+SB-806M HQ+SB-806M
溶離液：50mM硝酸鈉水溶液 Eluent: 50mM sodium nitrate aqueous solution
流速：0.7mL/分 Flow rate: 0.7mL/min
管柱溫度：40℃ Column temperature: 40℃
標準物質：Agilent Technologies Japan,Ltd.製聚乙二醇/氧化物(PEG/PEO) Standard material: Polyethylene glycol/oxide (PEG/PEO) manufactured by Agilent Technologies Japan, Ltd.
試驗分類4(相溶性之確認) Test category 4 (confirmation of compatibility)
溶液之相溶性，係將B成分之乙烯基共聚物設為20%時，以表4所示A成分與B成分之比例充分攪拌混合，透過目視並藉由以下基準進行測定。水溶液之濃度調整係使用蒸餾水。 The compatibility of the solution is that when the vinyl copolymer of component B is set to 20%, the ratio of component A to component B shown in Table 4 is fully stirred and mixed, and the solution is measured by visual observation based on the following criteria. The concentration of the aqueous solution is adjusted using distilled water.
相溶性之判定基準 Compatibility criteria
A：無法判定沈澱或沈降的程度 A: Unable to determine the degree of precipitation or sedimentation
B：確認到薄薄的混濁 B: Thin cloudiness is confirmed
C：確認到沈澱或沈降 C: Precipitation or settlement is confirmed
試驗分類5(調製作為水硬性組成物之砂漿) Test category 5 (preparation of mortar as hydraulic composition)
使用根據JIS R 5201水泥之物理試驗方法之砂漿攪拌機。並使用普通卜特蘭水泥(密度3.16g/cm3)作為膠合劑，使用大井川水系產陸砂(密度2.58g/cm3)作為細粒料，使用皂土(bentonite)(試劑和光純藥工業株式會社製)作為黏土質。相對於膠合劑100質量份，以0.005質量份之比例添加消泡劑(竹本油脂社製，商品名稱AFK-2)，並同時將試驗分類4中使用的水硬性組成物用添加劑與攪拌水一起投入，在表5所述之混合條件下攪拌成分240秒，調製砂漿。另，添加劑及消泡劑被視為水的一部份。 Use mortar mixer according to JIS R 5201 cement physical test method. And use ordinary portland cement (density 3.16g/cm 3 ) as a cement, use Oigawa water system land sand (density 2.58g/cm 3 ) as fine aggregate, and use bentonite (reagent Wako Pure Chemical Industries, Ltd.) Co., Ltd.) as clay. Add a defoamer (made by Takemoto Oil Co., Ltd., trade name AFK-2) at a ratio of 0.005 parts by mass to 100 parts by mass of the adhesive, and at the same time add the additive for hydraulic composition used in test category 4 together with stirring water Put in, stir the ingredients for 240 seconds under the mixing conditions described in Table 5 to prepare a mortar. In addition, additives and defoamers are regarded as part of the water.
成分攪拌及以下試驗係在將材料溫度設定為20±3℃，將室溫設定為20±3℃，將濕度設定為60%以上之環境下進行。所得砂漿之砂漿流動性評價，作為無振動砂漿流動性，係以240±5mm為目標進行。黏性評價，係根據填充砂漿流動性試驗方法(JSCE-F 541)，使用J14漏斗進行測定，將流下時間短者評價為黏性低者。結果如表6所示。另，目視皆未確認到任一砂漿中有分離之情況。 The component stirring and the following tests are carried out in an environment where the material temperature is set to 20±3°C, the room temperature is set to 20±3°C, and the humidity is set to 60% or more. The mortar fluidity evaluation of the obtained mortar, as a non-vibration mortar fluidity, was carried out with a target of 240±5mm. Viscosity evaluation is based on the filling mortar fluidity test method (JSCE-F 541), using J 14 funnel to measure, and the short running time is evaluated as the low viscosity. The results are shown in Table 6. In addition, no separation in any mortar was confirmed visually.
表6當中， In Table 6,
※1：相對於膠合劑100質量份，(A)成分與(B)成分之總質量份(固體含量) ※1: Relative to 100 parts by mass of the adhesive, the total mass parts of (A) component and (B) component (solid content)
結果 result
如表6所示，與不含A成分卻僅含B成分之比較例5相較，同時含A成分及B成分之實施例7、實施例10，毋需增加添加劑之添加率，即可觀察到流下時間縮短之情況。而與使用分子量較大之聚丙烯酸之比較例6相較，使用A成分之聚丙烯酸之實施例7，毋需增加添加劑之添加率，即可觀察到流下時間明顯縮短之情況。與使用分子量較大之聚丙烯酸鹽之比較例7相較，使用A成分之聚丙烯酸之實施例10，毋需增加添加劑之添加率，即可觀察到流下時間明顯縮短之情況。與使用羥丙甲纖維素作為増黏劑使用之比較例8相較，使用A成分之聚丙烯酸之實施例8，毋需增加添加劑之添加率，即可觀察到流下時間明顯縮短之情況。 As shown in Table 6, compared with Comparative Example 5 which does not contain A component but only contains B component, Example 7 and Example 10 which contain both A component and B component can be observed without increasing the additive rate. Circumstances where the time to shed is shortened Compared with Comparative Example 6 using polyacrylic acid with a larger molecular weight, Example 7 using polyacrylic acid with component A does not need to increase the additive rate, and the flow time can be observed to be significantly shortened. Compared with Comparative Example 7 using a higher molecular weight polyacrylate, Example 10 using polyacrylic acid of component A does not need to increase the additive rate, and the flow time can be observed to be significantly shortened. Compared with Comparative Example 8 using hypromellose as a viscosity increasing agent, Example 8 using the polyacrylic acid of component A does not need to increase the additive rate, and it can be observed that the flow time is significantly shortened.
[產業上之可用性][Industry Availability]
本發明之水硬性組成物用添加劑，可作為調製水硬性組成物之際的添加劑使用。 The additive for a hydraulic composition of the present invention can be used as an additive when preparing a hydraulic composition.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPPCT/JP2018/044378 | 2018-12-03 | ||
| PCT/JP2018/044378 WO2020115788A1 (en) | 2018-12-03 | 2018-12-03 | Additive for hydraulic compositions, and hydraulic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW202021928A true TW202021928A (en) | 2020-06-16 |
| TWI777016B TWI777016B (en) | 2022-09-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW108100093A TWI777016B (en) | 2018-12-03 | 2019-01-02 | Additive for hydraulic composition and hydraulic composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP7103691B2 (en) |
| TW (1) | TWI777016B (en) |
| WO (1) | WO2020115788A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5268648B2 (en) * | 2006-11-09 | 2013-08-21 | 電気化学工業株式会社 | Quick setting agent and spraying method using the same |
| JP7099767B1 (en) * | 2021-11-04 | 2022-07-12 | 竹本油脂株式会社 | Admixture for hydraulic composition and hydraulic composition |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0931458A (en) * | 1995-07-24 | 1997-02-04 | Fujisawa Pharmaceut Co Ltd | Water reducing agent for clayey soil added with cement |
| KR100562920B1 (en) * | 1997-06-25 | 2006-03-22 | 더블유.알. 그레이스 앤드 캄파니-콘. | Admixture and method for optimizing addition of EO/PO superplasticizer to concrete containing smectite clay-containing aggregates |
| JP4267100B2 (en) * | 1998-09-07 | 2009-05-27 | 花王株式会社 | Additive for cement composition for grout method |
| JP5371457B2 (en) * | 2009-01-16 | 2013-12-18 | 花王株式会社 | Dispersant composition for hydraulic composition |
| JP6339819B2 (en) * | 2013-03-21 | 2018-06-06 | 株式会社日本触媒 | Additives used in hydraulic compositions |
| JP6260037B2 (en) * | 2014-03-24 | 2018-01-17 | 竹本油脂株式会社 | Multifunctional admixture for concrete |
| JP6649811B2 (en) * | 2016-03-09 | 2020-02-19 | 株式会社日本触媒 | Additive for hydraulic composition and concrete composition |
| JP6821250B2 (en) * | 2016-12-16 | 2021-01-27 | 花王株式会社 | Method for producing a cured product of hydraulic composition |
-
2018
- 2018-12-03 WO PCT/JP2018/044378 patent/WO2020115788A1/en active Application Filing
- 2018-12-03 JP JP2020558691A patent/JP7103691B2/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| TWI777016B (en) | 2022-09-11 |
| WO2020115788A1 (en) | 2020-06-11 |
| JP7103691B2 (en) | 2022-07-20 |
| JPWO2020115788A1 (en) | 2021-09-27 |
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