JPH03141142A - Water reducing agent for cement - Google Patents
Water reducing agent for cementInfo
- Publication number
- JPH03141142A JPH03141142A JP27922989A JP27922989A JPH03141142A JP H03141142 A JPH03141142 A JP H03141142A JP 27922989 A JP27922989 A JP 27922989A JP 27922989 A JP27922989 A JP 27922989A JP H03141142 A JPH03141142 A JP H03141142A
- Authority
- JP
- Japan
- Prior art keywords
- cement
- water reducing
- reducing agent
- weight
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000004568 cement Substances 0.000 title claims abstract description 55
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 45
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 34
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 229950000244 sulfanilic acid Drugs 0.000 claims abstract description 26
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 22
- -1 bisphenol compound Chemical class 0.000 claims abstract description 19
- 230000001603 reducing effect Effects 0.000 claims abstract description 19
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 13
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 7
- 235000000346 sugar Nutrition 0.000 claims description 6
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 16
- 239000000178 monomer Substances 0.000 abstract description 10
- 125000001174 sulfone group Chemical group 0.000 abstract description 6
- 239000002699 waste material Substances 0.000 abstract description 5
- 150000001720 carbohydrates Chemical class 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 description 30
- 230000000694 effects Effects 0.000 description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 11
- 229940126062 Compound A Drugs 0.000 description 10
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 229920001218 Pullulan Polymers 0.000 description 2
- 239000004373 Pullulan Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011400 blast furnace cement Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003631 expected effect Effects 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920005646 polycarboxylate Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000019423 pullulan Nutrition 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000008054 sulfonate salts Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔童業上の利用分野〕
本発明は、セメントペースト、モルタル、コンクリート
などセメント組成物に用いられる減水剤に関するもので
あり、特に減水性が高く、また流動性の経時的低下が少
なく、施工性２作業性の改善されたセメント用減水剤に
関するものである。[Detailed Description of the Invention] [Field of industrial application] The present invention relates to a water reducing agent used in cement compositions such as cement paste, mortar, and concrete. The present invention relates to a water reducing agent for cement that has little deterioration in performance and improved workability.
近年、モルタル工事やコンクリート工事等においてその
作業性の改善２強度や耐久性の向上。In recent years, workability has been improved in mortar work, concrete work, etc.2 Strength and durability have been improved.
ひび割れ性の減少等諸物性の向上を目的として各種の減
水剤が用いられているが、高性能のＡＥ減水剤が尚要求
されている。Although various water reducing agents have been used for the purpose of improving various physical properties such as reducing cracking properties, a high performance AE water reducing agent is still required.
従来、セメント用減水剤としてスルホン化メラミン樹脂
塩、ポリカルボン酸塩、ナフタレンスルホン酸ホルムア
ルデヒド高縮合物塩、リグニンスルホン酸塩等が利用さ
れているが、スルホン化メラミン樹脂塩は、減水効果が
低く、多量の添加を必要とし、ポリカルボン酸塩は、減
水効果が低い上に、添加量を増大すると著しい凝結遅延
を起こし、場合によっては硬化不足となる。ナフタレン
スルホン酸ホルムアルデヒド高縮合物塩は、減水効果が
大きく、凝結遅延も少なく、空気連行性も小さいが、モ
ルタル、コンクリートの流動性の経時的低下が著しい。Conventionally, sulfonated melamine resin salts, polycarboxylate salts, naphthalene sulfonic acid formaldehyde high condensate salts, lignin sulfonate salts, etc. have been used as water reducing agents for cement, but sulfonated melamine resin salts have a low water reducing effect. Polycarboxylic acid salts require addition in large amounts, and not only have a low water-reducing effect, but increasing the amount added causes significant setting delay, resulting in insufficient curing in some cases. Naphthalenesulfonic acid formaldehyde high condensate salts have a large water-reducing effect, little delay in setting, and low air entrainment, but the fluidity of mortar and concrete decreases significantly over time.
リグニンスルホン酸塩は、減水効果は大きいが、空気混
入量が大きく、モルタルやコンクリートの物性に悪影響
を与える等の問題点があった。Although lignin sulfonate has a large water-reducing effect, there are problems such as a large amount of air being mixed in, which adversely affects the physical properties of mortar and concrete.
最近、芳香族アミノスルホン酸・フェノール・ホルムア
ルデヒド縮合物を含有するコンクリート混和剤が開発さ
れている（特開平１１１３４１９号）。この混和剤はセ
メント組成物のコンシスチンシーを改良し、かつ時間の
経過によるスランプロスのような流動性変化を低減する
とされているが、なお縮合時の残モノマーが多く一層の
改良が望まれている。Recently, a concrete admixture containing an aromatic aminosulfonic acid/phenol/formaldehyde condensate has been developed (Japanese Unexamined Patent Publication No. 1113419). Although this admixture is said to improve the consistency of cement compositions and reduce fluidity changes such as slump loss over time, there is still a large amount of residual monomer during condensation, and further improvements are desired. ing.
本発明は芳香族アミノスルホン酸系の混和剤の残モノマ
ー（アミノスルホン酸）を減少させ、その流動性の経時
的低下防止効果は損わず、セメント組成物の流動性を更
に改善することを１」的とし、鋭意研究した結果到達し
たものである。The present invention aims to further improve the fluidity of cement compositions by reducing the residual monomer (aminosulfonic acid) of an aromatic aminosulfonic acid-based admixture without impairing its effect of preventing the fluidity from decreasing over time. 1, and was arrived at after intensive research.
本発明のセメント用減水剤はビスフェノール・４−アミ
ンベンゼンスルホン酸のホルムアルデヒド縮合物及び特
定のリグニンスルホン酸塩を主成分とするもので、具体
的には
（ａ）４−アミノベンゼンスルホン酸（スルファニル酸
）またはその塩 １００重量部（ｂ）ビス
フェノール類化合物またはその塩２０〜１５０重量部
（Ｃ）ホルムアルデヒド ２０〜６５重量部を
水性条件下で加熱し、縮合させて有利に製造することが
できるビスフェノール・４−アミノベンゼンスルホン酸
のホルムアルデヒド縮合物８０〜２０重量部と、還元性
糖類が５％以下になるまで亜硫酸パルプ排液を限外濾過
処理したリグニンスルホン酸塩およびまたはフェニルプ
ロパン単位当り０．２゛モル以上のカルボキシル基と０
１０モル以上のスルホン基とを含有するリグニンスルホ
ン酸塩を２０〜８０重量部とを主成分とするセメント用
減水剤に係わるものである。The water reducing agent for cement of the present invention is mainly composed of a formaldehyde condensate of bisphenol/4-aminebenzenesulfonic acid and a specific ligninsulfonate, and specifically contains (a) 4-aminobenzenesulfonic acid (sulfanyl bisphenol which can be advantageously produced by heating and condensing 100 parts by weight of (b) 20 to 150 parts by weight of bisphenol compounds or salts thereof (C) 20 to 65 parts by weight of formaldehyde under aqueous conditions - 80 to 20 parts by weight of a formaldehyde condensate of 4-aminobenzenesulfonic acid and ligninsulfonate obtained by ultrafiltering sulfite pulp effluent until the reducing sugar content is 5% or less, and or 0.0% per unit of phenylpropane. 2 mmol or more carboxyl group and 0
The present invention relates to a water reducing agent for cement, the main component of which is 20 to 80 parts by weight of a lignin sulfonate containing 10 moles or more of sulfone groups.
本発明でビスフェノール・４−アミノベンゼンスルホン
酸のホルムアルデヒド縮合物の製造に用いられるビスフ
ェノール類は一般式
［式中Ｘは
０ＯＩ−１
で示される化合物、すなわち
ＣＨ。The bisphenols used in the present invention to produce the formaldehyde condensate of bisphenol/4-aminobenzenesulfonic acid are compounds represented by the general formula [wherein X is 0OI-1], ie, CH.
が用いられる。is used.
本発明の減水剤の主成分の１つである縮合化合物を製造
するには前記した特定の比率で縮合を行わせることが望
ましく、これを外れると減水性や流動性、経時変化特性
が低下する。In order to produce the condensation compound, which is one of the main components of the water reducing agent of the present invention, it is desirable to perform the condensation at the specific ratio described above, and if it deviates from this, water reducing properties, fluidity, and aging properties will deteriorate. .
この縮合反応においてアルカリの影響は極めて大きく、
アルカリの添加率はビスフェノール類化合物／４−アミ
ノベンゼンスルホン酸＝１／１の場合に、対アミノスル
ポン酸モル比で０．９５〜１．０５であることが好まし
い。これをはずれるト残モノマー（未反応アミノスルポ
ン酸）の量が急激に多（なる。In this condensation reaction, the influence of alkali is extremely large.
The addition rate of alkali is preferably 0.95 to 1.05 in molar ratio to aminosulfonic acid when bisphenol compound/4-aminobenzenesulfonic acid=1/1. The amount of residual monomer (unreacted aminosulfonic acid) that is removed from this increases rapidly.
縮合化合物の分子量はゲルパーメーションクロマトグ−
７７イー （Ｇ、 Ｐ、 Ｃ，）テ測定すると１０．０
００〜５０．０００の範囲であり、この範囲を逸脱する
と流動性改善効果が低下する。The molecular weight of the condensed compound is determined by gel permeation chromatography.
77E (G, P, C,) Te measurement is 10.0
It is in the range of 00 to 50.000, and if it deviates from this range, the fluidity improving effect decreases.
本発明の減水剤の他の成分である限外濾過処理したリグ
ニンスルホン酸塩は亜硫酸パルプ排液中の還元性糖類が
５％以下になるまで精製したものである。限外処理での
分画膜は５．００Ｑ〜３０．０００好ましくは１０，０
００〜２０．０００が良い。The ultrafiltered lignin sulfonate, which is another component of the water reducing agent of the present invention, is purified until the reducing sugar content in the sulfite pulp effluent is 5% or less. The fractionation membrane in ultra treatment is 5.00Q to 30.000, preferably 10.0
00-20.000 is good.
またフェニルプロパン単位当り０．２０モル以上のカル
ボキシル基と０．１０モル以上のスルホン基とを含有す
るリグニンスルホン酸塩は特公昭５６−４０１０６に示
される様に亜硫酸パルプ排液をアルカリ酸化しスルホン
基を低下させるか、クラフトパルプ排液のチオリグニン
をスルホメチル化してスルホン基を導入して製造するこ
とができる。In addition, lignin sulfonate containing 0.20 mole or more of carboxyl group and 0.10 mole or more of sulfone group per phenylpropane unit can be produced by alkali oxidation of sulfite pulp waste liquid as shown in Japanese Patent Publication No. 40106/1983. It can be produced by reducing the number of groups or by sulfomethylating thiolignin of kraft pulp wastewater to introduce a sulfone group.
ここで、ビスフェノール−４アミノベンゼンスルホン酸
のホルムアルデヒド縮合物単独では長期の流動性がまだ
充分でなく、前出の特定のリグニンスルホン酸塩を併用
することによって、はじめて満足する効果が得られる。Here, the formaldehyde condensate of bisphenol-4-aminobenzenesulfonic acid alone does not have sufficient long-term fluidity, and a satisfactory effect can only be obtained by using the above-mentioned specific ligninsulfonate in combination.
その割合は前者：後者＝８０〜２０ ： ２０〜８０（
重量部）でこの範囲を外れるとその効果は著しく低下す
る。The ratio is former: latter = 80-20: 20-80 (
If the amount (parts by weight) is outside this range, the effect will be significantly reduced.
本発明に用いられる縮合化合物は特開平１〜１１３４１
９号公報に示される４−アミノベンゼンスルホン酸とフ
ェノールとのホルムアルデヒド縮合物（以下Ａ化合物と
略記）に比して流動性改善効果が著しいが、これは次の
理由に基づくものである。The condensation compound used in the present invention is disclosed in JP-A-1-11341.
The fluidity improvement effect is remarkable compared to the formaldehyde condensate of 4-aminobenzenesulfonic acid and phenol (hereinafter abbreviated as compound A) shown in Publication No. 9, and this is based on the following reason.
Ａ化合物の縮合生成時にはアミノスルホン酸が残モノマ
ーとして約１０％残存するが、これはフェノールがアル
カリ性下でホルムアルデヒドと反応し、フェノールホモ
ポリマー（レゾールタイプ）が増加し、その結果未反応
のアミノスルホン酸が増加するからである。Approximately 10% aminosulfonic acid remains as a residual monomer during condensation of compound A, but this is because phenol reacts with formaldehyde under alkaline conditions, increasing phenol homopolymer (resol type), and as a result, unreacted aminosulfone This is because acid increases.
このようにフェノールを用いるＡ化合物の縮合反応の場
合は副反応を伴うため、第１工程（弱アルカリでの反応
）、第２工程（強アルカリでの反応）という繁雑な手段
を用いる必要がある。In this way, the condensation reaction of compound A using phenol involves side reactions, so it is necessary to use complicated means such as the first step (reaction with a weak alkali) and the second step (reaction with a strong alkali). .
一方本発明の減水剤の一方の主成分であるアミノスルホ
ン酸−ビスフェノール類化合物のホルムアルデヒド縮合
物の場合には、残モノマーはＡ化合物の場合に比べ１７
３程度に低下する。On the other hand, in the case of a formaldehyde condensate of an aminosulfonic acid-bisphenol compound, which is one of the main components of the water reducing agent of the present invention, the residual monomer is 17
It drops to about 3.
これはＡ化合物の場合フェノールがアルカリ性下でホル
ムアルデヒドと反応し易いのに対し、本発明の場合ビス
フェノール類化合物が水やアルカリに難溶であり反応性
が低く、フェノールに比べて副反応が起りにくいためと
考えられる。This is because in the case of compound A, phenol easily reacts with formaldehyde under alkaline conditions, whereas in the case of the present invention, bisphenol compounds are poorly soluble in water and alkali, have low reactivity, and are less likely to cause side reactions than phenol. It is thought that this is because of this.
またビスフェノール類化合物を用いる本発明の場合には
フェノールを用いたＡ化合物の場合の如く複雑な反応手
段を用いなくてもよいという特徴もある。In addition, the present invention using bisphenol compounds is characterized in that it is not necessary to use complicated reaction means as in the case of compound A using phenol.
本発明のセメント用減水剤は、セメントの０．０１〜２
．０％好ましくは０．１〜０．６％の割合で使用される
。配合量が少なすぎると期待した効果は得られず、多す
ぎるとセメントが過度に分赦し、分離現象を起こし、好
ましくない。The water reducing agent for cement of the present invention has a water reducing agent of 0.01 to 2
．． 0%, preferably 0.1-0.6%. If the amount is too small, the expected effect will not be obtained, and if it is too large, the cement will become too loose and a separation phenomenon will occur, which is undesirable.
本発明の適用されるセメントは、普通ポルトランドセメ
ント、早強セメント、超早強セメント高炉セメント中庸
熱セメント、フライアッシュセメント耐硫酸塩セメント
などが用いられる。また本発明のセメント用減水剤は他
のセメント用添加剤、例えば空気連行剤、凝結遅延剤、
防水剤、膨張剤、シリカヒユーム、石粉等と併用するこ
ともできる。The cement to which the present invention is applied includes ordinary Portland cement, early strength cement, ultra early strength cement, blast furnace cement, moderate heat cement, fly ash cement, and sulfate-resistant cement. The cement water reducing agent of the present invention may also be used with other cement additives, such as air entraining agents, setting retarders,
It can also be used in combination with waterproofing agents, swelling agents, silica hume, stone powder, etc.
以下実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
製造例１ 反応容器に下記の物質を所定量仕込んだ。Manufacturing example 1 A predetermined amount of the following substances was charged into a reaction vessel.
（Ｉ）４−アミノベンゼンスルホン酸
２０７．８４ｇ （１モル）
（ＩＩ）ビスフェノールＡ １３６．９８ｇ（０，
５モル）（ｍ）９５％ＮａＯＨ５０，５２ｇ （１モル
）水 ９２２．４６ ｇ次にこ
の固液懸濁液に３５％（ＶＯｊりホルムアルデヒド水溶
液（ＴＶ） ２０５．７２ｇ （２モル）を還流下に滴
下し、生成した反応混合物を１０時間攪拌し、透明な縮
合水溶液を得た。(I) 4-aminobenzenesulfonic acid 207.84g (1 mol) (II) Bisphenol A 136.98g (0,
5 mol) (m) 95% NaOH 50.52 g (1 mol) Water 922.46 g Next, to this solid suspension, 205.72 g (2 mol) of 35% (VOj) formaldehyde aqueous solution (TV) was added under reflux. The reaction mixture was added dropwise and the resulting reaction mixture was stirred for 10 hours to obtain a clear aqueous condensate solution.
得られた縮合物の重量平均分子ｆｆｉ（ＭＷ）と未反応
アミノスルホン酸量はそれぞれ２４．９５０と２．８％
（対固形分）であった。The weight average molecular ffi (MW) of the obtained condensate and the amount of unreacted aminosulfonic acid are 24.950 and 2.8%, respectively.
(based on solid content).
なお重量平均分子量はゲルパーメーションクロマトグラ
フィー（Ｇ Ｐ Ｃ）で測定、プルラン標阜で換算した
。未反応アミノスルホン酸はＧＰＣの示差屈折計での面
積比より求めた。The weight average molecular weight was measured by gel permeation chromatography (GPC) and converted using a pullulan standard. Unreacted aminosulfonic acid was determined from the area ratio using a GPC differential refractometer.
製造例２〜４
ビスフェノール類化合物を変化させ製造例１と同様にし
て縮合物を得た。Production Examples 2 to 4 Condensates were obtained in the same manner as Production Example 1 except that the bisphenol compounds were changed.
これらの結果を第１表に示す。These results are shown in Table 1.
製造例５
亜硫酸パルプ排液をアルカリ性下に空気酸化し、硫酸で
沈殿させ水洗し、水酸化ナトリウムで中和し、フェニル
プロパン単位当たり（１，３モルのスルホン基及び０．
４モルのカルボキシル基を含有したリグニンスルホン酸
塩を得た。Production Example 5 Sulfite pulp effluent was air oxidized under alkaline conditions, precipitated with sulfuric acid, washed with water, neutralized with sodium hydroxide, and phenylpropane units (1.3 moles of sulfonic groups and 0.5 moles) were obtained.
A lignin sulfonate containing 4 moles of carboxyl groups was obtained.
製造例６
亜硫酸バルブ排液を限外濾過膜（バイオエンジニアリン
グＫ Ｋ製、商品名ＧＯ５Ｔ （分画分子量）で濃縮精
製した。このようにして得られたリグニンスルホン酸塩
の還元性糖類は３．２％（対固形分）であった。Production Example 6 The sulfite valve effluent was concentrated and purified using an ultrafiltration membrane (manufactured by Bio Engineering K.K., trade name: GO5T (molecular weight cut off). The reducing saccharide of the lignin sulfonate thus obtained was 3. It was 2% (based on solid content).
実施例１
製造例５により製造したリグニンスルホン酸塩と製造例
１により製造した縮合物とをｓｏ ： ｓ。Example 1 The lignin sulfonate produced in Production Example 5 and the condensate produced in Production Example 1 were mixed in a so:s solution.
（固形分比）に混合し、本発明品１を得た。(solid content ratio) to obtain product 1 of the present invention.
実施例２
製造例６により製造したリグニンスルホン酸塩と製造例
１により製造した縮合物とを５０ ： ５０（固形分比
）に混合し、本発明品２を得た。Example 2 The lignin sulfonate produced in Production Example 6 and the condensate produced in Production Example 1 were mixed at a ratio of 50:50 (solid content ratio) to obtain Inventive Product 2.
実施例３
製造例２により製造した縮合物と製造例５で製造したリ
グニンスルホン酸塩とを６Ｑ ： ４０ （Ｊｌｌｒ形
分比身分比合し、本発明品３を得た。Example 3 The condensate produced in Production Example 2 and the lignin sulfonate produced in Production Example 5 were subjected to a 6Q:40 (Jllr fraction ratio) to obtain product 3 of the present invention.
実施例４
製造例２により製造した縮合物と製造例６で製造したリ
グニンスルホン酸塩とを４０ ＋ ６０ （固形分比）
に混合し、本発明品４を得た。Example 4 The condensate produced in Production Example 2 and the lignin sulfonate produced in Production Example 6 were mixed at a ratio of 40 + 60 (solid content ratio).
Inventive product 4 was obtained.
試験例
コンクリートの使用材料および配合は次ぎの通りである
。The materials and composition of the test example concrete are as follows.
セメント（Ｃ）：普通ポルトランドセメント細骨材（Ｓ
）：木更津産陸砂（比重２．５９． Ｆ！、１２．４０
）粗肯材（Ｇ）、山口産砕石（比重２．７０． ＦＭ６
．７５１水 （Ｗ）・水道水
第２表 配 合
１００１ミキサーにて第２表の配合に夫々実施例１〜４
の減水剤を添加して夫々３分間混練し、直後、３１６Ｇ
、 ９Ｌ １２［１分電後に各スランプの空気量を測定
した。尚、コンクリートのスランプと空気量の測定はＪ
ＩＳに準拠して行なった。Cement (C): Ordinary Portland cement fine aggregate (S
): Land sand from Kisarazu (specific gravity 2.59. F!, 12.40
) Crushed stone from Yamaguchi (specific gravity 2.70. FM6)
．． 751 water (W)/tap water Table 2 Mixture 1001 Mix the formulations in Table 2 with Examples 1 to 4, respectively.
of water reducing agent was added and kneaded for 3 minutes, and immediately after, 316G
, 9L 12 [The amount of air in each slump was measured after one minute of electricity. In addition, the measurement of concrete slump and air volume is carried out by J.
This was done in accordance with IS.
また比較のため製造例１〜４で得られた縮合物よりなる
減水剤を用いて同様に実施し、比較例１〜４の結果を得
た。For comparison, the same procedure was carried out using a water reducing agent made of the condensate obtained in Production Examples 1 to 4, and the results of Comparative Examples 1 to 4 were obtained.
測定結果は第３表の通りであるが、本発明品は従来品よ
り流動性保持性の良いことがわかる。The measurement results are shown in Table 3, and it can be seen that the product of the present invention has better fluidity retention than the conventional product.
本発明品を用いることにより、従来のセメント添加剤よ
り流動性の経時変化の少ないセメント組成物を得ること
が出来る。By using the product of the present invention, it is possible to obtain a cement composition whose fluidity changes less over time than with conventional cement additives.
手続補正ｖｊＦ（白部
明 細 書
１、事件の表示
平成１年 特許願 第２７９２２９号
２、発明の名称
セメント用減水剤
３、補正をする者
事件との関係 特許出願人
住 所 東京都千代ｔｎ区丸の内−丁［１４番５号
名 称 （２３４）山陽国策バルブ株式会社４、代
理人
住 所 東京都千代ＦＴＪ区神田北乗物町１６番地
〒１０１ 英ビル３階
１、発明の名称
セメント用減水剤
２、特許請求の範囲
（１）４−アミノベンゼンスルホン酸またはその塩及び
ビスフェノール類化合物またはその塩のホルムアルデヒ
ド縮合物の８０〜２０重量部と、還元性糖類が５％以下
になるまで亜硫酸パルプ排液を限外濾過処理したリグニ
ンスルホン酸塩またはフェニルプロパン単位当り０．２
０モル以上のカルボキシル基と０．１０モル以上のスル
ホン基とを含有するリグニンスルホン酸塩の２０〜８０
重量部とを主成分とするセメント用減水剤。Procedural amendment vjF (Shirabe Specification 1, Indication of the case 1999 Patent Application No. 279229 2, Name of the invention Water reducing agent for cement 3, Relationship with the case by the person making the amendment Patent applicant address Chiyo tn, Tokyo) Marunouchi-cho, Ward 14-5 Name (234) Sanyo Kokusaku Valve Co., Ltd. 4, Agent address 16 Kanda Kita Jorimono-cho, Chiyo FTJ-ku, Tokyo 101 Ei Building 3rd floor 1 Name of invention: Water reduction for cement Agent 2, Claims (1) 80 to 20 parts by weight of a formaldehyde condensate of 4-aminobenzenesulfonic acid or its salt and a bisphenol compound or its salt, and sulfite pulp until the reducing sugar content is 5% or less. 0.2 per unit of lignin sulfonate or phenylpropane after ultrafiltration of wastewater
20 to 80 lignin sulfonate containing 0 mol or more carboxyl group and 0.10 mol or more sulfonic group
A water reducing agent for cement whose main ingredients are parts by weight.
（２）ビスフェノール類化合物が下記一般式５、補正の
対象
明細書全文
［但し式中Ｘは
ＯＯＨ
で示されるビスフェノール類化合物またはその塩である
請求項１記載のセメント用減水剤。(2) The water reducing agent for cement according to claim 1, wherein the bisphenol compound is a bisphenol compound represented by the following general formula 5, the entire text of the specification to be amended, where X is a bisphenol compound represented by OOH or a salt thereof.
（３）４−アミノベンゼンスルホン酸またはその塩１０
０重量部とビスフェノール類化合物またはその塩２０〜
１５０重量部およびホルムアルデヒド２０〜６５重機部
とを縮合させて製造したビスフェノール・４−アミノベ
ンゼンスルホン酸縮合物を含有する請求項１または２記
載のセメント用減水剤。(3) 4-aminobenzenesulfonic acid or its salt 10
0 parts by weight and 20 to 20 parts of bisphenol compound or its salt
The water reducing agent for cement according to claim 1 or 2, containing a bisphenol/4-aminobenzenesulfonic acid condensate produced by condensing 150 parts by weight of formaldehyde and 20 to 65 parts of formaldehyde.
（４）縮合物の重量平均分子量力月０．０００〜５００
００である請求項１〜３のいずれか１項記載のセメント
用減水剤。(4) Weight average molecular weight of condensate: 0.000 to 500
The water reducing agent for cement according to any one of claims 1 to 3, wherein the water reducing agent is 00.
３、発明の詳細な説明
〔産業上の利用分野〕
本発明は、セメントペースト、モルタル コンクリート
などセメント組成物に用いられる減水剤に関するもので
あり、特に減水性が高く、また流動性の経時的低下が少
なく、施工性９作業性の改善されたセメント用減水剤に
関するものである。3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a water reducing agent used in cement compositions such as cement paste and mortar concrete, which has particularly high water reducing properties and also reduces fluidity over time. This invention relates to a water reducing agent for cement that has improved workability and reduced workability.
近年、モルタル工事やコンクリート工事等においてその
作業性の改善２強度や耐久性の向上。In recent years, workability has been improved in mortar work, concrete work, etc.2 Strength and durability have been improved.
ひび割れ性の減少等諸物性の向上を目的として各種の減
水剤が用いられているが、高性能のＡＥ減水剤が尚要求
されている。Although various water reducing agents have been used for the purpose of improving various physical properties such as reducing cracking properties, a high performance AE water reducing agent is still required.
従来、セメント用減水剤としてスルホン化メラミン樹脂
塩、ポリカルボン酸塩、ナフタレンスルホン酸ホルムア
ルデヒド高縮合物塩、リグニンスルホン酸塩等が利用さ
れているが、スルホン化メラミン樹脂塩は、減水効果が
小さく、多量の添加を必要とし、ポリカルボン酸塩は、
減水効果が大きいが、添加量を増大すると著しい凝結遅
延を起こし、場合によっては硬化不足となる。ナフタレ
ンスルホン酸ホルムアルデヒド高縮合物塩は、減水効果
が大きく、凝結遅延も少なく、空気連行性も小さいが、
モルタル。Conventionally, sulfonated melamine resin salts, polycarboxylic acid salts, naphthalene sulfonic acid formaldehyde high condensate salts, lignin sulfonate salts, etc. have been used as water reducing agents for cement, but sulfonated melamine resin salts have a small water reducing effect. , a large amount of addition is required, and polycarboxylate is
Although it has a large water-reducing effect, increasing the amount added causes a significant setting delay, resulting in insufficient curing in some cases. Naphthalenesulfonic acid formaldehyde high condensate salt has a large water reduction effect, little condensation delay, and low air entrainment, but
mortar.
コンクリートの流動性の経時的低下が著しい。The fluidity of concrete decreases significantly over time.
リグニンスルホン酸塩は、減水効果は大きいが、空気混
入量が大きく、モルタルやコンクリートの物性に悪影響
を与える等の問題点があった。Although lignin sulfonate has a large water-reducing effect, there are problems such as a large amount of air being mixed in, which adversely affects the physical properties of mortar and concrete.
最近、芳香族アミノスルホン酸・フェノール・ホルムア
ルデヒド縮合物を含有するコンクリート混和剤が開発さ
れている（特開平１−１１３４１９号）。この混和剤は
セメント組成物のコンシスチンシーを改良し、かつ時間
の経過によるスランプロスのような流動性変化を低減す
るとされているが、縮合時の残モノマーが多い等、−層
の改良が望まれている。Recently, a concrete admixture containing an aromatic aminosulfonic acid/phenol/formaldehyde condensate has been developed (Japanese Unexamined Patent Publication No. 1-113419). This admixture is said to improve the consistency of cement compositions and reduce fluidity changes such as slump loss over time, but it does not improve the -layer, such as a large amount of monomer remaining during condensation. desired.
本発明は芳香族アミノスルホン酸系の混和剤ノ残モノマ
ー（芳香族アミノスルホン酸）を減少させ、その流動性
の経時的低下防止効果は損わず、セメント組成物の流動
性を更に改善することを目的とし、鋭意研究した結果到
達したものである。本発明のセメント用減水剤はビスフ
ェノール類化合物・４−アミノベンゼンスルホン酸のホ
ルムアルデヒド縮合物及び特定のリグニンスルホン酸塩
を主成分とするもので、具体的には
（ａ）４−アミノベンゼンスルホン酸（スルファニル酸
）またはその塩 １００重量部（ｂ）
ビスフェノール類化合物またはその塩２０−１５０重量
部
（Ｃ）ホルムアルデヒド ２０〜６５重量部を
水性条件下で加熱し、縮合させて製造するビスフェノー
ル類化合物・４−アミノベンゼンスルホン酸のホルムア
ルデヒド縮合物８０〜２０重量部と、還元性糖類が５％
以下になるまで亜硫酸パルプ排液を限外濾過処理したリ
グニンスルホン酸塩またはフェニルプロパン単位当り０
．２モル以上のカルボキシル基と０，１０モル以上のス
ルホン基とを含有するリグニンスルホン酸塩を２０〜８
０重量部とを主成分とするセメント用減水剤に係わるも
のである。The present invention reduces the residual monomer (aromatic aminosulfonic acid) of an aromatic aminosulfonic acid-based admixture, and further improves the fluidity of cement compositions without impairing the effect of preventing the fluidity from decreasing over time. This is what we arrived at as a result of intensive research. The water reducing agent for cement of the present invention is mainly composed of a bisphenol compound, a formaldehyde condensate of 4-aminobenzenesulfonic acid, and a specific ligninsulfonate, and specifically contains (a) 4-aminobenzenesulfonic acid. (sulfanilic acid) or its salt 100 parts by weight (b)
Bisphenol compound or its salt 20-150 parts by weight (C) Formaldehyde 20-65 parts by weight are heated and condensed under aqueous conditions to produce a bisphenol compound/formaldehyde condensate of 4-aminobenzenesulfonic acid 80-20 parts by weight and reducing sugars 5%
0 per unit of lignin sulfonate or phenylpropane by ultrafiltration of sulfite pulp effluent until
．． 20 to 8 lignin sulfonate containing 2 moles or more of carboxyl groups and 0.10 moles or more of sulfonic groups
This relates to a water reducing agent for cement containing 0 parts by weight as a main component.
本発明でビスフェノール類化合物・ドアミノベンゼンス
ルホン酸のホルムアルデヒド縮合物の製造に用いられる
ビスフェノール類化合物は一般式
［式中Ｘは
ＯＯＨ
ＯＯＨ
で示される化合物、すなわち
が用いられる。The bisphenol compound used in the present invention to produce the formaldehyde condensate of bisphenol compound/doaminobenzenesulfonic acid is a compound represented by the general formula [wherein X is OOH OOH].
本発明の減水剤の主成分の１つである縮合物を製造する
には前記した特定の比率で縮合を行わせることが望まし
く、これを外れると減水性や流動性、経時変化特性が低
Ｆする。In order to produce the condensate, which is one of the main components of the water reducing agent of the present invention, it is desirable to carry out the condensation at the specific ratio mentioned above. do.
縮合化合物の重量平均分子量はゲルパーミエイシ３ンク
ロマトグラフィー（Ｇ、Ｐ、 Ｃ，ｌで測定すると１０
． ＯＯＱ〜５０．０００の範囲であり、この範囲を逸
脱すると流動性改善効果が低下する。The weight average molecular weight of the condensed compound is 10 when measured by gel permeability chromatography (G, P, C, l).
．． It is in the range of OOQ to 50,000, and if it deviates from this range, the fluidity improving effect decreases.
本発明の減水剤の他の成分である限外濾過処理したリグ
ニンスルホン酸塩は亜硫酸パルプ排液中の還元性糖類が
５％以下になるまで精製したものである。限外処理での
分画膜は１０００〜３０．０００好ましくは５．０００
〜２０．０００が良い。The ultrafiltered lignin sulfonate, which is another component of the water reducing agent of the present invention, is purified until the reducing sugar content in the sulfite pulp effluent is 5% or less. The fractionation membrane in ultra treatment is 1000 to 30,000, preferably 5,000
~20,000 is good.
またフェニルプロパン単位当り０．２０モル以上のカル
ボキシル基と０．１０モル以上のスルホン基とを含有す
るリグニンスルホン酸塩は特公昭５６−４０１０６に示
される様に亜硫酸パルプ排液をアルカリ酸化しスルホン
基を低下させるか、クラフトパルプ排液のチオリグニン
をスルホメチル化してスルホン基を導入して製造するこ
とができる。In addition, lignin sulfonate containing 0.20 mole or more of carboxyl group and 0.10 mole or more of sulfone group per phenylpropane unit can be produced by alkali oxidation of sulfite pulp waste liquid as shown in Japanese Patent Publication No. 40106/1983. It can be produced by reducing the number of groups or by sulfomethylating thiolignin of kraft pulp wastewater to introduce a sulfone group.
ここで、ビスフェノール類化合物・４−アミノベンゼン
スルホン酸のホルムアルデヒド縮合物単独では長期の流
動性がまだ充分でなく、前出の特定のリグニンスルホン
酸塩を併用することによって、はじめて満足する効果が
得られる。Here, the long-term fluidity of the formaldehyde condensate of bisphenol compounds and 4-aminobenzenesulfonic acid alone is still insufficient, and a satisfactory effect can only be achieved by using the above-mentioned specific ligninsulfonate in combination. It will be done.
その割合は前者：後者＝８０〜２０ ： ２Ｑ〜８０（
重量部）でこの範囲を外れるとその効果は著しく低下す
る。The ratio is former: latter = 80~20: 2Q~80 (
If the amount (parts by weight) is outside this range, the effect will be significantly reduced.
本発明に用いられる縮合物は特開平１−１１３４１９号
公報に示される４−アミノベンゼンスルホン酸とフェノ
ールとのホルムアルデヒド縮合物（以下Ａ化合物と略記
）に比して流動性改善効果が著しいが、これは次の理由
に基づくものである。The condensate used in the present invention has a remarkable fluidity improvement effect compared to the formaldehyde condensate of 4-aminobenzenesulfonic acid and phenol (hereinafter abbreviated as compound A) shown in JP-A-1-113419. This is based on the following reasons.
Ａ化合物の縮合反応後には４−アミノベンゼンスルホン
酸が残モノマーとして約１０％残存するが、これはフェ
ノールがホモポリマーを生成しやすく、その結果未反応
の４−アミノベンゼンスルホン酸が残存しやすいためと
思われる。After the condensation reaction of compound A, about 10% of 4-aminobenzenesulfonic acid remains as a residual monomer, but this is because phenol tends to form a homopolymer, and as a result, unreacted 4-aminobenzenesulfonic acid tends to remain. It seems to be for a reason.
このようにフェノールを用いるＡ化合物の縮合反応の場
合は副反応を伴うことや、フェノール自体の性状のため
ため、第１工程（弱アルカリでの反応）、第２工程（強
アルカリでの反応）・という繁雑な手段を用いる必要が
ある。In this way, in the case of condensation reaction of compound A using phenol, there are side reactions and due to the properties of phenol itself, the first step (reaction with a weak alkali) and the second step (reaction with a strong alkali) are required.・It is necessary to use complicated means.
−古本発明の減水剤の主成分である４−アミノベンゼン
スルホン酸−ビスフェノール類化合物のホルムアルデヒ
ド縮合物の場合には、残モノマーはＡ化合物の場合に比
べｌ／３程度に低下する。これは本発明のビスフェノー
ル類化合物が水やアルカリに難溶であり、またフェノー
ルに比べて副反応のホモポリマーの生成が起りにくいた
めと考えられる。またビスフェノール類化合物を用いる
本発明の場合にはフェノールを用いたＡ化合物の場合の
如く曳雑な反応手段を用いなくてもよいという特徴もあ
る。- In the case of the formaldehyde condensate of 4-aminobenzenesulfonic acid-bisphenol compound, which is the main component of the water reducing agent of the old invention, the residual monomer is reduced to about 1/3 compared to the case of compound A. This is thought to be because the bisphenol compound of the present invention is poorly soluble in water or alkali, and is less likely to produce a homopolymer as a side reaction than phenol. In addition, the present invention using bisphenol compounds is characterized in that it is not necessary to use complicated reaction means as in the case of compound A using phenol.
本発明のセメント用減水剤は、セメントの０．０１〜２
０％好ましくは０．１〜０６％の割合で使用される。配
合量が少なすぎると期待した効果は得られず、多すぎる
とセメントが過度に分散し、分離現象を起こし、好まし
くない。The water reducing agent for cement of the present invention has a water reducing agent of 0.01 to 2
It is used in a proportion of 0%, preferably 0.1 to 0.6%. If the amount is too small, the expected effect will not be obtained, and if it is too large, the cement will be excessively dispersed, causing a separation phenomenon, which is not preferable.
本発明の適用されるセメントは、普通ポルトランドセメ
ント、早強セメント、超早強セメント、高炉セメント中
庸熱セメント、フライアッシュセメント、耐硫酸塩セメ
ントなどが用いられる。また本発明のセメント用減水剤
は他のセメント用添加剤、例えば減水剤、空気連行剤。As the cement to which the present invention is applied, ordinary Portland cement, early strength cement, ultra early strength cement, blast furnace cement, medium heat cement, fly ash cement, sulfate resistant cement, etc. are used. The cement water reducing agent of the present invention may also be used as other cement additives, such as water reducing agents and air entraining agents.
凝結遅延剤、防水剤、膨張剤、シリカヒユーム。Set retardant, waterproofing agent, swelling agent, silica hume.
石粉等と併用することもできる。It can also be used in combination with stone powder, etc.
以下実施例により本発明を説明する。 The present invention will be explained below with reference to Examples.
製造例１ 反応容器に下記の物質を所定量仕込んだ。Manufacturing example 1 A predetermined amount of the following substances was charged into a reaction vessel.
（■）４−アミノベンゼンスルホン酸
１７３．２０ｇ （１モル）
（■）２．２−ビス（４−ヒドロキシフェニル）プロパ
ン １１４．１５ ｇ （０，５モル
）（ｍ）９５％ＮａＯＨ４２，ｌＩｇ （１モル）水
７６８．７４ ｇ次にこの固液
懸濁液に３５％ホルムアルデヒド水溶液（ＩＶ） ２［
１５，７２ｇ （２モル）を還流下に滴下し、生成した
反応混合物を１０時間１豊拌し、縮合物水溶液を得た。(■) 4-Aminobenzenesulfonic acid 173.20 g (1 mol) (■) 2.2-bis(4-hydroxyphenyl)propane 114.15 g (0.5 mol) (m) 95% NaOH42,lIg ( 1 mole) water
768.74 g Next, 35% formaldehyde aqueous solution (IV) 2[
15.72 g (2 mol) was added dropwise under reflux, and the resulting reaction mixture was stirred for 10 hours to obtain an aqueous condensate solution.
得られた縮合物のｆｆｉ戯平均分子ｆｆ１（＋Ｊｙ）と
未反応４−アミノベンゼンスルホン酸量はそれぞれ２４
、９５０と２．８％（対固形分）であった。The ffi average molecule ff1 (+Jy) of the obtained condensate and the amount of unreacted 4-aminobenzenesulfonic acid are each 24
, 950 and 2.8% (based on solid content).
なお重量平均分子量はゲルパーミエイションクロマトグ
ラフィー（Ｇ Ｐ Ｃ）で測定、プルラン標準で換算し
た。未反応４−アミノベンゼンスルホン酸はＧＰＣの示
差屈折計での面積比より求めた。The weight average molecular weight was measured by gel permeation chromatography (GPC) and converted using a pullulan standard. Unreacted 4-aminobenzenesulfonic acid was determined from the area ratio using a GPC differential refractometer.
製造例２〜４
ビスフェノール類化合物を変化させ製造例１と同様にし
て縮合物を得た。Production Examples 2 to 4 Condensates were obtained in the same manner as Production Example 1 except that the bisphenol compounds were changed.
これらの結果を第１表に示す。These results are shown in Table 1.
製造例５
亜硫酸パルプ排液をアルカリ性下に空気酸化し、硫酸で
沈殿させ水洗し、水酸化ナトリウムで中和し、フェニル
プロパン単位当たす０．３モルのスルホン基及び０．４
モルのカルボキシル基を含有したリグニンスルホン酸塩
を得た。Production Example 5 Sulfite pulp waste liquid was air oxidized under alkaline conditions, precipitated with sulfuric acid, washed with water, neutralized with sodium hydroxide, and 0.3 mol of sulfonic group per phenylpropane unit and 0.4
A lignin sulfonate containing molar carboxyl groups was obtained.
製造例６
亜硫酸パルプ排液を限外濾過膜（バイオエンジニアリン
グＫ Ｋ製、商品名ＧＯ５Ｔ （分画分子量５、０００
１で濃縮精製した。このようにして得られたリグニンス
ルホン酸塩の還元性糖類は３２％（対固形分）であった
。Production Example 6 Sulfite pulp waste liquid was filtered using an ultrafiltration membrane (manufactured by Bio Engineering K.K., trade name: GO5T (molecular weight cut off: 5,000
1 and concentrated and purified. The reducing saccharide content of the lignin sulfonate thus obtained was 32% (based on solid content).
実施例１
製造例５により製造したリグニンスルホン酸塩と製造例
１により製造した縮合物とを５０ ： ５０（固形分比
）に混合し、本発明品１を得た。Example 1 The lignin sulfonate produced in Production Example 5 and the condensate produced in Production Example 1 were mixed at a ratio of 50:50 (solid content ratio) to obtain product 1 of the present invention.
実施例２
製造例６により製造したリグニンスルホン酸塩と製造例
１により製造した縮合物とを５［）：５０（固形分比）
に混合し、本発明品２を得た。Example 2 The lignin sulfonate produced in Production Example 6 and the condensate produced in Production Example 1 were mixed in a ratio of 5 [ ): 50 (solid content ratio).
Inventive product 2 was obtained.
実施例３
製造例２により製造した縮合物と製造例５で製造したリ
グニンスルホン酸塩とを６０ ＋ ４０ （固形分比）
に混合し、本発明品３を得た。Example 3 The condensate produced in Production Example 2 and the lignin sulfonate produced in Production Example 5 were mixed at a ratio of 60 + 40 (solid content ratio).
Inventive product 3 was obtained.
実施例４
製造例２により製造した縮合物と製造例６で製造したリ
グニンスルホン酸塩とを４０：６０（固形分比）に混合
し、本発明品４を得た。Example 4 The condensate produced in Production Example 2 and the lignin sulfonate produced in Production Example 6 were mixed at a ratio of 40:60 (solid content ratio) to obtain product 4 of the present invention.
試験例 コンクリートの使用材料および配合は次の通りである。Test example The materials and mix of concrete used are as follows.
セメント（Ｃ）ｌ普通ポルトランドセメント細骨材（Ｓ
）：木更津産陸砂（比重２．５９． ＦＭ２．４０）粗
性材（Ｇ）：山口産砕石（比重２．７０． ＦＭ６．７
５＋水 （Ｗｌ 水道水
第２表 配 合
＋００１ ミキサーにて第２表の配合に夫々実施例１〜
４の減水剤を添加して３分間混練し、直後、３０．６０
．９０． １２０分毎復電各スランプの空気量を測定し
た。尚、コンクリートのスランプと空気量の測定はＪＩ
Ｓに準拠して行なった。Cement (C) Ordinary Portland cement Fine aggregate (S
): Land sand from Kisarazu (specific gravity 2.59. FM 2.40) Rough material (G): Crushed stone from Yamaguchi (specific gravity 2.70. FM 6.7)
5+Water (Wl Tap water Table 2 formulation +001 Use a mixer to add each of Examples 1 to 2 to the formulations in Table 2.
Immediately after adding water reducing agent No. 4 and kneading for 3 minutes, 30.60
．． 90. The amount of air in each slump was measured every 120 minutes. In addition, measurements of concrete slump and air volume are conducted by JI.
It was conducted in accordance with S.
また比較のため製造例１〜４で得られた縮合物よりなる
減水剤を用いて同様に実施し、比較例１〜４の結果を得
た。For comparison, the same procedure was carried out using a water reducing agent made of the condensate obtained in Production Examples 1 to 4, and the results of Comparative Examples 1 to 4 were obtained.
測定結果は第３表の通りであるが、本発明品は従来品よ
り流動性保持の良いことがわかる。The measurement results are shown in Table 3, and it can be seen that the product of the present invention retains fluidity better than the conventional product.
本発明品を用いることにより、従来のセメント添加剤よ
り流動性の経時変化の少ないセメント組成物を得ること
が出来る。By using the product of the present invention, it is possible to obtain a cement composition whose fluidity changes less over time than with conventional cement additives.
１゜ ２゜ ３゜ ４゜ 手続辛［１７正具＋（自発） 平成２年１０Ｔ］２５−日 事件の表示 平成１年 特許願 第２７９２２９号 発明の名称 セメント用減水剤 補正をする各 事件との関係 特許出願人1゜ 2゜ 3゜ 4゜ Procedure spicy [17 positive tools + (spontaneous) 1990 10T] 25-day Display of incidents 1999 Patent Application No. 279229 name of invention Water reducing agent for cement Each correction Relationship to the incident: Patent applicant
Claims (4)
ビスフェノール類化合物またはその塩のホルムアルデヒ
ド縮合物の８０〜２０重量部と、還元性糖類が５％以下
になるまで亜硫酸パルプ排液を限外濾過処理したリグニ
ンスルホン酸塩およびまたはフェニルプロパン単位当り
０．２０モル以上のカルボキシル基と０．１０モル以上
のスルホン基とを含有するリグニンスルホン酸塩の２０
〜８０重量部とを主成分とするセメント用減水剤。(1) Ultrafiltration treatment of sulfite pulp effluent with 80 to 20 parts by weight of a formaldehyde condensate of 4-aminobenzenesulfonic acid or its salt and a bisphenol compound or its salt until the reducing sugar content is 5% or less. 20 of the lignin sulfonate containing 0.20 mol or more carboxyl group and 0.10 mol or more sulfonic group per phenylpropane unit.
- 80 parts by weight of a water reducing agent for cement.
学式、表等があります▼ ［但し式中Ｘは ▲数式、化学式、表等があります▼，▲数式、化学式、
表等があります▼，▲数式、化学式、表等があります▼
，▲数式、化学式、表等があります▼または−Ｏ−を表
わす］で示されるビスフェノール誘導体またはその塩で
ある請求項１記載のセメント用減水剤。(2) Bisphenol compounds have the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, X in the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas, etc.
There are tables, etc.▼、▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ▲ Numerical formula, chemical formula, table, etc. ▼ or -O-] The water reducing agent for cement according to claim 1, which is a bisphenol derivative or its salt.
０重量部とビスフェノール類化合物またはその塩２０〜
１５０重量部およびホルムアルデヒド２０〜６５重量部
とをアルカリ性下に縮合させて製造したビスフェノール
・４−アミノベンゼンスルホン酸縮合物を含有する請求
項１または２記載のセメント用減水剤。(3) 4-aminobenzenesulfonic acid or its salt 10
0 parts by weight and 20 to 20 parts of bisphenol compound or its salt
3. The water reducing agent for cement according to claim 1, comprising a bisphenol/4-aminobenzenesulfonic acid condensate produced by condensing 150 parts by weight of formaldehyde and 20 to 65 parts by weight of formaldehyde under alkaline conditions.
０００である請求項１〜３のいずれか１項記載のセメン
ト用減水剤。(4) The weight average molecular weight of the condensate is 10,000 to 50,
The water reducing agent for cement according to any one of claims 1 to 3, wherein the water reducing agent is 000.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1279229A JPH0617256B2 (en) | 1989-10-26 | 1989-10-26 | Water reducing agent for cement |
| US07/566,760 US5153299A (en) | 1989-09-01 | 1990-08-14 | Production of novel condensates comprising bisphenols and aromatic aminosulfonic acids, condensates and dispersant, additive and water-reducing agent based thereon |
| GB9018212A GB2236533B (en) | 1989-09-01 | 1990-08-20 | Bisphenol condensates |
| DE4027667A DE4027667C2 (en) | 1989-09-01 | 1990-08-31 | Condensates based on aromatic aminosulfonic acids, bisphenols and formaldehyde, processes for their preparation and color dispersions containing these condensates, additives and water-reducing agents |
| US07/895,133 US5233012A (en) | 1989-09-01 | 1992-06-08 | Production of novel condensates comprising bisphenols and aromatic aminosulfonic acids, condensates and dispersant, additive and water-reducing agent based thereon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1279229A JPH0617256B2 (en) | 1989-10-26 | 1989-10-26 | Water reducing agent for cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03141142A true JPH03141142A (en) | 1991-06-17 |
| JPH0617256B2 JPH0617256B2 (en) | 1994-03-09 |
Family
ID=17608233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1279229A Expired - Fee Related JPH0617256B2 (en) | 1989-09-01 | 1989-10-26 | Water reducing agent for cement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0617256B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881248A (en) * | 1994-09-13 | 1996-03-26 | Nippon Paper Ind Co Ltd | Admixture for concrete |
| JP2013189546A (en) * | 2012-03-14 | 2013-09-26 | Toyo Ink Sc Holdings Co Ltd | Dispersion including diamond fine particle |
| CN117683182A (en) * | 2023-12-14 | 2024-03-12 | 四川嘉兆丰新材料科技有限公司 | Bio-based water reducer with claw-type branched structure and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01113419A (en) * | 1987-09-25 | 1989-05-02 | Fujisawa Pharmaceut Co Ltd | Concrete admixture |
-
1989
- 1989-10-26 JP JP1279229A patent/JPH0617256B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01113419A (en) * | 1987-09-25 | 1989-05-02 | Fujisawa Pharmaceut Co Ltd | Concrete admixture |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881248A (en) * | 1994-09-13 | 1996-03-26 | Nippon Paper Ind Co Ltd | Admixture for concrete |
| JP2013189546A (en) * | 2012-03-14 | 2013-09-26 | Toyo Ink Sc Holdings Co Ltd | Dispersion including diamond fine particle |
| CN117683182A (en) * | 2023-12-14 | 2024-03-12 | 四川嘉兆丰新材料科技有限公司 | Bio-based water reducer with claw-type branched structure and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0617256B2 (en) | 1994-03-09 |
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