CN109715584A

CN109715584A - Centrifugal forming hydraulic-composition

Info

Publication number: CN109715584A
Application number: CN201780057087.8A
Authority: CN
Inventors: 田中骏也; 吉浪雄亮; 下田政朗; 齐田和哉; 岛田恒平; 中村圭介
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2016-09-16
Filing date: 2017-09-15
Publication date: 2019-05-03
Anticipated expiration: 2037-09-15
Also published as: JP6741635B2; JP2018048068A; WO2018052112A1; MY191784A; CN109715584B

Abstract

The present invention is a kind of centrifugal forming hydraulic-composition, it contains: the hydraulic powder dispersing agent of (A) comprising the high-molecular compound containing aromatic rings, (B) are selected from the compound, hydraulic powder, aggregate and water of one or more of specific compound shown in general formula (B1)~(B4), and the ratio between water/hydraulic powder of the hydraulic-composition is more than 25 mass % and is 35 mass % or less.

Description

Centrifugal forming hydraulic-composition

Technical field

The present invention relates to the manufacturing methods of centrifugal forming hydraulic-composition and the hardenite of hydraulic-composition.Into And the present invention relates to the purposes as centrifugal forming hydraulic-composition of particular composition.

Background technique

The dispersing agent of hydraulic-composition is necessary in order to by dispersing cement granules, make to obtain required slump institute Unit discharge reduction, and workability for improving hydraulic-composition etc. and use chemistry mix agent.As dispersing agent, past The polycarboxylic acids such as the naphthalenes such as known naphthalene sulfonic acid-formaldehyde condensation product system dispersing agent, carboxylic acid and the copolymer of monomer with alkylene glycol chain It is melamine series dispersing agents such as dispersing agent, melamine sulfonic formaldehyde condensation compound etc..

Naphthalene system dispersing agent etc, hydraulic powder dispersing agent comprising the high-molecular compound containing aromatic rings and more carboxylics Acid system dispersing agent is compared, and has the feature that the variation for material, temperature, and the variation for flowing the effect of sex expression is less, separately The viscosity of outer gained hydraulic-composition is relatively low, is easy to use in the manufacture of hydraulic-composition.

Naphthalene system dispersing agent etc, hydraulic powder comprising the high-molecular compound containing aromatic rings has such as with dispersing agent Lower feature: for material, temperature change, the variation for flowing the effect of sex expression is less, and in addition gained hydraulic-composition is viscous Property it is lower, in the manufacture of hydraulic-composition be easy use.Especially centrifugal forming is good (no slag and honeycomb (junk)), therefore it is suitable for centrifugal forming purposes.

It is described in Japanese Unexamined Patent Application 61-281054 bulletin and cement dispersants and specific is contained with specific weight ratio The concrete of nonionic surfactant mixes agent.

It is described in Japanese Unexamined Patent Publication 2003-165755 bulletin and contains specific polyalkylene oxide derivatives for improveing And/or the machinability modifying agent of the machinability of the cement composition of specific hydrocarbon derivative.In addition, Japanese Unexamined Patent Publication 2003- The cement water reducing agent containing above-mentioned machinability modifying agent and water-reducing agent is also described in No. 165755 bulletins.

It is described in Japanese Unexamined Patent Application 60-011255 bulletin comprising beta-naphthalenesulfonic-acid formaldehyde condensation compound and there is oxygen ethylidene The slurry that the hydraulic-composition and water of the nonionic surfactants of chain are constituted.

Described in Japanese Unexamined Patent Application 55-023047 bulletin the formaline condensates comprising naphthalene sulfonic acids metal salt and The cement additive of polyoxy Asia vinyl compound.

Described in Japanese Unexamined Patent Application 48-028525 bulletin by add anionic surfactant concrete come Concrete product needed for molding, and the manufacturing method of the concrete product of atmospheric steam curing is carried out to the molded product.

On the other hand, it has also been suggested in the past and is used surfactant as cement mixing agent.Japanese Unexamined Patent Application 50- The anionic surfactant containing sulfuric acid ester type and polyalkylene oxide hydrocarbon system or polyalcohol system are described in No. 150724 bulletins Cement made of nonionic surfactant mixes agent.

Summary of the invention

As the method for the hollow cylinders type concrete formation product such as tubing, stake, the bar manufactured in concrete formation product, Knowing has centrifugal casting.The centrifugal casting is the concrete material that investment was kneaded into molding box, and by making molding box high speed The centrifugal force of rotation and generation, the method that concrete is pressed on into molding box inner face to mold.

In Japan, usually when manufacture requires high-intensitive concrete-pile, in order to ensure that can deliver behind from mixing 7 days Intensity, high-intensitive mixed material is added into concrete, and implement steam curing.

In concrete-pile, the stake for building of the basis stake of structure is existed that serve as.With the gigantism of structure, high level Change, it is desirable that stake high intensity for building, in recent years, the design basis intensity for having also appeared concrete is more than 100N/mm²It is high-strength Spend stake.And, it is believed that more high-intensitive moulded products can also it is expected from now on, for example, the design basis intensity of concrete is super Cross 123N/mm²Moulded products.

It but is more than 123N/mm with regard to the design basis intensity of concrete²Moulded products for, even if increase contain The additive amount of the hydraulic powder dispersing agent of the high-molecular compound of aromatic rings, the raising of the intensity of centrifugal forming product also reach The limit is arrived.

In addition, if increasing the additive amount of the hydraulic powder dispersing agent comprising the high-molecular compound containing aromatic rings, Uncured hydraulic-composition is high dispersion state, in the case that such hydraulic-composition is used for centrifugal forming, is melted The generation of slag, which becomes significant, hardenite surface property, to be reduced.

The present invention provide the hardenite based on centrifugal forming intensity is high and mouldability also excellent centrifugal forming hydraulic Property composition.

The present invention relates to a kind of centrifugal forming hydraulic-compositions, contain: (A) includes the producing high-molecular containing aromatic rings Close the hydraulic powder dispersing agent of object；(B) it is selected from shown in the following general formula (B1) compound represented, the following general formula (B2) and changes Close the compound of one or more of object, the following general formula (B3) compound represented and the following general formula (B4) compound represented；Water Rigid powder；Aggregate；And water, the ratio between water/hydraulic powder of the centrifugal forming hydraulic-composition is more than 25 matter It measures % and is 35 mass % or less.

[chemical formula 1]

R¹¹-O-(AO)_n1-SO₃M (B1)

R²¹-X-(AO)_n2-R²² (B2)

(in formula,

R¹¹、R²¹、R³¹、R⁴¹Each independently represent the alkyl below of carbon number 4 or more and 27；

R²²Indicate hydrogen atom or the alkyl below of carbon number 1 or more and 3；

R³²、R³³It is identical or different, respectively indicate hydrogen atom or the alkyl below of carbon number 1 or more and 3；

X indicates O or COO；

AO indicates the alkylene oxide group below of carbon number 2 or more and 4；

n₁For the average addition molal quantity of AO, 1 or more and 200 numbers below are indicated；

n₂For the average addition molal quantity of AO, 1 or more and 200 numbers below are indicated；

n₃、n₄Identical or different, the average addition molal quantity of respectively AO, is 0 or more number, n₃With n₄Total expression 1 Above and 200 numbers below；

Y¹、Y²It is identical or different, respectively hydrogen atom or SO₃M, Y¹、Y²At least one be SO₃M；

n₅、n₆Identical or different, the average addition molal quantity of respectively AO, is 0 or more number, n₅With n₆Add up to 1 with Upper and 200 numbers below, n₅When being 0, Y¹For hydrogen atom, n₆When being 0, Y²For hydrogen atom,

M indicates counter ion counterionsl gegenions.〕

Moreover, it relates to which a kind of centrifugal forming hydraulic-composition, contains: (A) includes the height containing aromatic rings The hydraulic powder dispersing agent of molecular compound；(B) above-mentioned general formula (B1) compound represented, above-mentioned general formula (B2) institute are selected from The change of one or more of compound, above-mentioned general formula (B3) compound represented and above-mentioned general formula (B4) compound represented for showing Close object；Hydraulic powder；Aggregate；And water, centrifugal forming hydraulic-composition are free of high-intensitive admixture.

Moreover, it relates to which a kind of centrifugal forming hydraulic-composition, contains: (A) includes the height containing aromatic rings The hydraulic powder dispersing agent of molecular compound；(B) above-mentioned general formula (B1) compound represented, above-mentioned general formula (B2) institute are selected from The change of one or more of compound, above-mentioned general formula (B3) compound represented and above-mentioned general formula (B4) compound represented for showing Close object；Hydraulic powder；Aggregate；And water, centrifugal forming hydraulic-composition are free of high-intensitive admixture, and water/ The ratio between hydraulic powder is more than 25 mass % and is 35 mass % or less.

Moreover, it relates to a kind of manufacturing method of the hardenite of hydraulic-composition, wherein by hydraulic-composition Mixed with material, prepare the centrifugal forming hydraulic-composition of aforementioned present invention, by the hydraulic-composition fill to After in molding box, apply centrifugal force and molded, it includes the high score containing aromatic rings that hydraulic-composition material, which includes (A), The hydraulic powder dispersing agent of sub- compound；(B) selected from shown in above-mentioned general formula (B1) compound represented, above-mentioned general formula (B2) One or more of compound, above-mentioned general formula (B3) compound represented and above-mentioned general formula (B4) compound represented chemical combination Object；Hydraulic powder；Aggregate；And water.

In addition, the present invention provides a kind of purposes as centrifugal forming hydraulic-composition of composition, the combination Object contains: (A) includes the hydraulic powder dispersing agent of the high-molecular compound containing aromatic rings；(B) it is selected from above-mentioned general formula (B1) Compound represented, above-mentioned general formula (B2) compound represented, above-mentioned general formula (B3) compound represented and above-mentioned general formula (B4) The compound of one or more of compound represented；Hydraulic powder；Aggregate；And water, water/hydraulicity of the composition The ratio between powder is more than 25 mass % and is 35 mass % or less.

In addition, the present invention provides a kind of purposes as centrifugal forming hydraulic-composition of composition, the combination Object contains: (A) includes the hydraulic powder dispersing agent of the high-molecular compound containing aromatic rings；(B) it is selected from above-mentioned general formula (B1) Compound represented, above-mentioned general formula (B2) compound represented, above-mentioned general formula (B3) compound represented and above-mentioned general formula (B4) The compound of one or more of compound represented；Hydraulic powder；Aggregate；And water, the composition are mixed without high intensity Close material.

In addition, the present invention provides a kind of purposes as centrifugal forming hydraulic-composition of composition, the combination Object contains: (A) includes the hydraulic powder dispersing agent of the high-molecular compound containing aromatic rings；(B) it is selected from above-mentioned general formula (B1) Compound represented, above-mentioned general formula (B2) compound represented, above-mentioned general formula (B3) compound represented and above-mentioned general formula (B4) The compound of one or more of compound represented；Hydraulic powder；Aggregate；And water, the composition are mixed without high intensity Material is closed, and the ratio between water/hydraulic powder more than 25 mass % and is 35 mass % or less.

Hereinafter, by (A) include the high-molecular compound containing aromatic rings hydraulic powder use dispersing agent as (A) ingredient into Row explanation.

In addition, using above-mentioned general formula (B1) compound represented as compound (B1), will change shown in above-mentioned general formula (B2) Close object as compound (B2), using above-mentioned general formula (B3) compound represented as compound (B3), by above-mentioned general formula (B4) institute The compound shown is illustrated as compound (B4).

In turn, compound (B1), compound (B2), compound (B3) and compound (B4) (B) ingredient is referred to as to carry out Explanation.

According to the present invention, it is possible to provide the intensity of the hardenite based on centrifugal forming is high and mouldability also excellent centrifugal forming Use hydraulic-composition.

Specific embodiment

(centrifugal forming hydraulic-composition)

The present invention provides a kind of centrifugal forming hydraulic-composition 1 side, contain (A) ingredient, (B) ingredient, Hydraulic powder, aggregate and water, and the ratio between water/hydraulic powder more than 25 mass % and is 35 mass % or less.

In addition, the present invention provides a kind of centrifugal forming hydraulic-composition in other sides, contain (A) ingredient, (B) Ingredient, hydraulic powder, aggregate and water, but without high-intensitive admixture.

In addition, the present invention provides a kind of centrifugal forming hydraulic-composition in other sides, contain (A) ingredient, (B) Ingredient, hydraulic powder, aggregate and water, but without high-intensitive admixture, the ratio between water/hydraulic powder is more than 25 mass % and is 35 mass % or less.

When centrifugal forming hydraulic-composition hereinafter referred to as of the invention, it is no especially record in the case where, refer to These three centrifugal forming compositions.

Centrifugal forming hydraulic-composition can be loaded by centrifugal force bring load-carrying, therefore, not for growing concrete etc. The composition of hardening seek high yield value (identical as initiating stress) and mild method (with reach a certain speed institute from initiating Need stress it is identical) property.In the present invention, by assigning high yield value to aromatic ring dispersing agent, and then greatly improve point It dissipates property (roughly the same with viscosity), so that making the slurry character of hydraulic-composition itself is improved, is used as centrifugal forming Way is more useful.

In addition, by centrifugal forming to manufacture hardenite, the ratio between water/hydraulic powder be 25 mass % with When lower, because workability reduce due to exists molding box be packed into operation when expend a large amount of labours and time the case where, to shape until compared with The cob webbings such as honeycomb, cavity therefore occur sometimes for time-consuming.Although there are this problems, in the art, make To be set as 25 mass % the following method using by the ratio between water/hydraulic powder for obtaining high-intensitive short-cut method.Separately It is on the one hand, more time-consuming until showing certain strength in region of the ratio between the water/hydraulic powder more than 35 mass %, The reason of purposes period as molding box reduces.This is directly related to productivity.In addition, for long-term strength, in water/water In the case that the ratio between rigid powder is more than 35 mass %, there is also be 35 mass % feelings below with the ratio between water/hydraulic powder Condition compares the tendency that long-term strength is lower.In the present invention, in the region of the ratio between the water/hydraulic powder for being not susceptible to this problem In, it can be improved the intensity and mouldability of the hardenite based on centrifugal forming.

In addition, high-intensitive admixture is received sometimes for improving concrete strength, but when use silicon ash system admixture Contracting, in addition, the expansion of sulfate occurs because of sulfate ion sometimes when using gypsum system admixture.Without using high intensity This problem is difficult to happen in the case where admixture.In the present invention, even if reducing the dosage of high-intensitive admixture or not using High-intensitive admixture, the intensity of hardenite can also improve.

The details of effect expression mechanisms of the invention are unknown, but can speculate as follows.

As the naphthalene system dispersing agent of (A) ingredient of the invention etc, water comprising the high-molecular compound containing aromatic rings Rigid powder has electrostatic repulsion with dispersing agent, compared with the dispersing agent with strong steric repulsion, has very excellent centrifugation Mouldability.

In the present invention, by and use (A) ingredient and as the specific compound of (B) ingredient, can control adsorption rate (has The cement of effect adsorbs), thus, it is possible to realize the inhibition of high water reduction effect (reduction of additive amount) and delay.It can speculate: by this The hydration activity point of the inhibition of reduction and the delay of additive amount, cement increases, and thus, it is possible to assign the effect for improving intensity.

In the low region of the ratio between water/hydraulic powder, ionic strength is got higher, and therefore, is usually existed and is difficult to show (A) Ingredient is to the tendency of the dispersibility of hydraulic powder, but in the present invention, it is believed that: pass through high water reduction effect as described above The approach inhibited with delay, can be dramatically improved performance.

< (A) ingredient >

(A) ingredient is the hydraulic powder dispersing agent comprising the high-molecular compound containing aromatic rings.It, can as aromatic rings Enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, triazine ring.

(A) ingredient is preferably the hydraulic powder use for including the high-molecular compound with the monomeric unit containing aromatic rings Dispersing agent.

As the monomeric unit containing aromatic rings, it can enumerate and be selected from the monomeric unit containing phenyl ring, the list containing naphthalene nucleus The monomeric unit of one or more of body unit and monomeric unit containing triazine ring.

From the viewpoint of the intensity of performance centrifugal forming and/or hardenite, (A) ingredient includes preferably producing high-molecular The hydraulic powder dispersing agent of object is closed, the high-molecular compound, which has, wraps naphthalene-ring containing monomeric unit.

As (A) ingredient, it may be more preferable to enumerate naphthalene sulfonic acid-formaldehyde condensation product or its salt.Naphthalene sulfonic acid-formaldehyde condensation product or its salt It is the condensation product or its salt of naphthalene sulfonic acids and formaldehyde.As long as not damaging energy, naphthalene sulfonic acid-formaldehyde condensation product can also be with such as methyl Naphthalene, ethylnaphthalene, dibutyl naphthalene, hydroxyl naphthalene, naphthalene-carboxylic acid, anthracene, phenol, cresols, creasote, tar, melamine, urea, to amino Benzene sulfonic acid and/or their derivative or the like as monomer, can be with the aromatic compound cocondensation of naphthalene sulfonic acids cocondensation.

Naphthalene sulfonic acid-formaldehyde condensation product or its salt can be used for example, Mighty150, DEMOL N, DEMOL RN, DEMOL MS, DEMOL SN-B, DEMOL SS-L (being Kao Corp's system), Celluflow 120, Ravelin FD-40, Commercially available product as Ravelin FM-45 (being first Industrial Co., Ltd's system) etc..

The sight that the mobility of viewpoint and hydraulic-composition from the intensity of centrifugal forming and/or case-hardening(drying) body improves Point set out, the weight average molecular weight of naphthalene sulfonic acid-formaldehyde condensation product or its salt is preferably 200,000 or less, more preferably 100,000 with Under, further preferably 80,000 or less, still more preferably for 50,000 or less, be still more preferably 30,000 or less. Also, the viewpoint improved from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and the mobility of hydraulic-composition Set out, the weight average molecular weight of naphthalene sulfonic acid-formaldehyde condensation product or its salt is preferably 1,000 or more, more preferably 3,000 or more, into one Step preferably 4,000 or more is still more preferably 5,000 or more.Naphthalene sulfonic acid-formaldehyde condensation product can be acid state or It is corrective.

The molecular weight of naphthalene sulfonic acid-formaldehyde condensation product or its salt can be carried out with gel permeation chromatography (GPC) under the following conditions Measurement.

[GPC condition]

Chromatographic column: G4000SWXL+G2000SWXL (TOSOH Co., Ltd)

Eluent: 30mM CH₃COONa/CH₃CN=6/4

Flow: 0.7ml/min

Detection wavelength: UV280nm

Sample size: 0.2mg/ml

Standard substance: western tail industrial (strain) kayexalate conversion (monodisperse polystyrene sodium sulfonate: molecule processed Amount: 206,1,800,4,000,8,000,18,000,35,000,88,000,780,000)

Detector: TOSOH Co., Ltd UV-8020

The manufacturing method of naphthalene sulfonic acid-formaldehyde condensation product or its salt can enumerate for example, by the way that naphthalene sulfonic acids and formaldehyde contract Close the method that reaction obtains condensation product.It can carry out the neutralization of above-mentioned condensation product.Alternatively, it is also possible to remove by-product by neutralizing Water-insoluble.Specifically, naphthalene sulfonic acids using 1.2~1.4 moles of sulfuric acid, and is allowed to relative to 1 mole of naphthalene in order to obtain 2~5 hours are reacted at 150~165 DEG C to obtain sulfonated bodies.Then, relative to 1 mole of the sulfonated bodies, so that formaldehyde is 0.93~0.99 mole of mode lasts 3~6 hours dropwise addition formalin at 85~105 DEG C, after dropwise addition at 95~105 DEG C Carry out condensation reaction.In addition, from the viewpoint for inhibiting the metal erosion such as the storage tank as caused by the aqueous acidity height of gained condensation product It sets out, water and neutralizer can be added to gained condensation product, and carry out neutralization step at 80~95 DEG C.Neutralizer preferably with respect to Naphthalene sulfonic acids and unreacted sulfuric acid add 1.0~1.1 moles times respectively.Furthermore it is possible to remove by neutralizing the water-insoluble generated, make It preferably enumerates for its method and is separated using filtering.By these processes, available naphthalene sulfonic acid-formaldehyde condensation product is water-soluble The aqueous solution of property salt.The aqueous solution can be used directly as the aqueous solution of (A) ingredient.It as needed can be further by the water Solution is dried, powdered is to obtain the salt of powdered naphthalene sulfonic acid-formaldehyde condensation product, and can be as powder (A) ingredient of shape uses.

Dry, powdered can be carried out by spray drying, roller drying, freeze-drying etc..

Phenol system dispersing agent, lignin can be enumerated other than naphthalene sulfonic acid-formaldehyde condensation product or its salt as (A) ingredient It is dispersing agent, melamine series dispersing agent, styrene sulfonic acid system dispersing agent.

< (B) ingredient >

< compound (B1) >

Compound (B1) is compound represented by the general formula (B1).

R in general formula (B1)¹¹For the alkyl below of carbon number 4 or more and 27.The alkyl includes the alkyl comprising substituent group.

In this specification, substituent group is the hydrogen atom instead of most basic organic compound and the atom or atomic group that import (chemical dictionary, the first edition, the 7th printing, the same people of (strain) Tokyo chemistry, on April 1st, 2003).

Hydrocarbon comprising substituent group can be the derivative of hydrocarbon.Derivative refers to, when certain hydrocarbon is considered as parent, through function Importing, oxidation, reduction, substitution of atom of group etc. are formed without substantially changing the change of the construction of parent and the degree of property Compound.

As R¹¹Alkyl, can enumerate selected from alkyl, alkenyl, aralkyl, aryl and with substituent group aryl (with Under, referred to as substituted aryl) in group.From the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming It sets out, R¹¹Alkyl be preferably selected from the group in alkyl, alkenyl and substituted aryl, more preferably be selected from alkenyl and substituted aryl In group.

From the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming, R¹¹Alkyl it is preferred For aliphatic alkyl, more preferably straight-chain aliphatic alkyl.

From the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming, R¹¹Alkenyl it is preferred For aliphatic alkenyl, more preferably straight-chain aliphatic alkenyl.

R¹¹Substituted aryl be aromatic rings the aryl that is substituted with a substituent of hydrogen atom, the hydrogen atom of aromatic rings can be enumerated The aryl replaced by alkyl.The carbon number of substituted aryl comprising substituent group is 4 or more and 27 or less.As substituted aryl, can arrange Enumerate 1,2 or 3 aryl replaced the substituent groups such as alkyl of the hydrogen atom of aromatic rings.The aryl of substituted aryl is preferred For phenyl.As substituted aryl, the substituted aryl below of carbon number 13 or more and 27 can be enumerated.The substituent group of substituted aryl can arrange Enumerate the alkyl below of carbon number 1 or more and 10.

As substituted aryl, can enumerate selected from carbon number is preferably 1 or more, further preferably 2 or more, also, preferably For 10 or less, in the phenyl of further preferably 8 alkyl-substituted phenyl below, the phenyl that benzyl replaces and styrol Group.Substituted aryl can enumerate the group in the phenyl selected from phenyl and styrol that benzyl replaces.

Substituted aryl is preferably selected from monobenzyl phenyl, dibenzylphenyl, tribenzyl phenyl, single styrenated phenyl and two Group in styrenated phenyl, the more preferably group in tribenzyl phenyl and distyrenated phenyl.

From the viewpoint of the viewpoint and economy of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming, R¹¹Preferably alkyl.

It is easy from the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming and dissolution in water From the perspective of, R¹¹Preferably alkenyl.

From the viewpoint and inhibition hydraulic-composition of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming Blistering from the perspective of, R¹¹Preferably substituted aryl.

From the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming, R¹¹Carbon number it is preferred For 8 or more, more preferably 12 or more, further preferably 16 or more, also, preferably 22 or less, more preferably 20 or less, into One step is preferably 18 or less.

If enumerating R¹¹Concrete example, then from centrifugal forming and/or performance centrifugal forming after hardenite intensity sight Point sets out, can enumerate selected from carbon number be preferably 8 or more, further preferably 10 or more, be still more preferably 16 or more, and And in the alkyl that is substituted with a substituent of hydrogen atom of preferably 22 or less, further preferably 20 alkyl and the alkyl below Group.

If enumerating R¹¹Other concrete examples, then from centrifugal forming and/or performance centrifugal forming after hardenite intensity From the perspective of, can enumerate selected from carbon number be preferably 8 or more, further preferably 10 or more, still more preferably for 16 with On, also, the hydrogen atom of preferably 22 or less, further preferably 20 alkyl or alkenyls below and the alkyl or the alkenyl The group in group being substituted with a substituent.

If enumerating R¹¹Other concrete examples, then from centrifugal forming and/or performance centrifugal forming after hardenite intensity From the perspective of, can enumerate selected from carbon number be preferably 8 or more, further preferably 10 or more, still more preferably for 16 with On, also, preferably 22 or less, further preferably 20 alkyl, preferably aliphatic alkyl, more preferably straight chain rouge below Fat race alkyl, and preferably 8 or more carbon number, further preferably 10 or more, be still more preferably 16 or more, also, it is excellent Be selected as 22 or less, further preferably 20 alkenyls below, preferably aliphatic alkenyl, more preferably in straight-chain aliphatic alkenyl Group.

In addition, from the viewpoint and the inhibition hydraulicity of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming From the perspective of the blistering of composition, R¹¹Preferably substituted aryl, more preferably distyrenated phenyl.

As R¹¹Alkyl, as described above, can enumerate selected from alkyl, alkenyl, aralkyl, aryl and with substituent group Group in aryl (hereinafter referred to as substituted aryl).From the viewpoint of the intensity for showing the hardenite after steam curing, R¹¹'s Alkyl is preferably selected from the group in alkyl, alkenyl and substituted aryl, the group more preferably in alkenyl and substituted aryl.

From the viewpoint of the intensity for showing the hardenite after steam curing, R¹¹Alkenyl be preferably aliphatic alkenyl, more Preferably straight-chain aliphatic alkenyl.

From the viewpoint and the easy viewpoint of dissolution in water of the intensity of the hardenite of the hardenite after performance steam curing It sets out, R¹¹Preferably alkenyl.

From the viewpoint of the intensity of the hardenite of the hardenite after performance steam curing and the blistering of inhibition hydraulic-composition From the perspective of, R¹¹Preferably substituted aryl.

From the viewpoint of showing the intensity of hardenite of the hardenite after steam curing, R¹¹Carbon number be preferably 8 or more, It more preferably 12 or more, is more preferably 16 or more, also, preferably 22 or less.

If enumerating R¹¹Concrete example, then from the intensity of the hardenite of the hardenite of the hardenite after steam curing find sight Point sets out, can enumerate selected from carbon number be preferably 8 or more, further preferably 10 or more, be still more preferably 16 or more, and And preferably 22 or less, the further preferably hydrogen atom of 20 alkyl or alkenyls below and the alkyl or the alkenyl is substituted The group in group that base replaces.

If enumerating R¹¹Other concrete examples, then go out from the viewpoint of intensity of the hardenite of the hardenite after performance steam curing Hair, can enumerate selected from carbon number be preferably 8 or more, further preferably 10 or more, be still more preferably 16 or more, also, It preferably 22 or less, is more preferably 20 alkyl, preferably aliphatic alkyl, more preferably straight-chain aliphatic alkane below Base, and preferably 8 or more carbon number, further preferably 10 or more, be still more preferably 16 or more, also, preferably 22 It below, is more preferably 20 alkenyl, preferably aliphatic alkenyls, the base being more preferably in straight-chain aliphatic alkenyl below Group.

In addition, going out from the viewpoint of the blistering of the intensity and inhibition hydraulic-composition of the hardenite after performance steam curing Hair, R¹¹Preferably substituted aryl, the group more preferably in tribenzyl phenyl and distyrenated phenyl.

More specifically, as R¹¹, can enumerate selected from decyl, lauryl, myristyl, palmityl, stearyl, Group in behenyl base, iso stearyl, oil base, tribenzyl phenyl and distyrenated phenyl, preferably enumerate selected from lauryl, Base in myristyl, palmityl, stearyl, behenyl base, iso stearyl, oil base, tribenzyl phenyl and distyrenated phenyl Group, it may be more preferable to enumerate selected from lauryl, myristyl, palmityl, stearyl, oil base, tribenzyl phenyl and distyrenated Group in phenyl can be enumerated still more preferably in oil base, stearyl, distyrenated phenyl and tribenzyl phenyl Group.From the viewpoint of showing the viewpoint of intensity of the hardenite after steam curing and mobility and improving, preferred these groups. In addition, from the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming, preferred these groups.

In general formula (B1), AO is the alkylene oxide group below of carbon number 2 or more and 4, from centrifugal forming and/or case-hardening(drying) body Intensity from the perspective of, be preferably selected from the group of one or more of the alkylene oxide group of carbon number 2 and the alkylene oxide group of carbon number 3. From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, AO preferably comprises the alkylene oxide group of carbon number 2.

In general formula (B1), n₁For the average addition molal quantity of AO, from the intensity of centrifugal forming and/or case-hardening(drying) body It is 1 or more and 200 numbers below from the perspective of viewpoint and cement dispersibility.From centrifugal forming and/or performance centrifugal forming From the perspective of the viewpoint and mobility of the intensity of hardenite afterwards improve, n₁Preferably 10 or more, more preferably 20 or more, and And from the easy and economic viewpoint of the interaction with (A) ingredient and after centrifugal forming and/or performance centrifugal forming From the perspective of the intensity of hardenite, preferably 60 or less, more preferably 40 numbers below.

R¹¹In the case where for substituted aryl, from the viewpoint of the intensity for showing the hardenite after steam curing, n₁It is preferred that For 10 or more, more preferably 15 or more, further preferably 25 or more, also, preferably 65 or less, more preferably 50 or less, It further preferably 40 or less, is still more preferably 35 or less.

R¹¹In the case where for alkenyl, from the viewpoint of the intensity for showing the hardenite after steam curing, n₁Preferably 5 with Above, 8 or more, further preferably 9 or more, also, preferably 65 or less are more preferably, 50 or less is more preferably, is further excellent It is selected as 40 or less, is still more preferably 35 or less, is still more preferably 25 or less, is still more preferably 20 or less, more Further preferably 12 or less.

R¹¹In the case where for alkyl, from the viewpoint of the intensity for showing the hardenite after steam curing, n₁Preferably 15 Above, 20 or more, also, preferably 55 or less, more preferably 30 or less are more preferably.

In general formula (B1), M is counter ion counterionsl gegenions, can be enumerated selected from hydrogen ion, alkali metal ion, alkaline-earth metal ion Ion in (1/2 ion) and ammonium ion.

From the viewpoint of being easy the manufacture of the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and compound, M Preferably ammonium ion.

From the viewpoint of the peculiar smell of the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and compound, M is preferred For alkali metal ion, the alkali metal ion more preferably in sodium ion and potassium ion.

As compound (B1), the polyoxyethylene alkene ether of polyoxyethylene oleyl ether sulfuric ester compound etc. can be enumerated The polyoxyethylene of sulfuric ester compound or its salt and the distyrenated phenyl ether sulfuric ester compound of polyoxyethylene etc. replaces virtue Base ether sulfuric ester compound or its salt.

Compound (B2) is above-mentioned general formula (B2) compound represented.

The HLB (Davis's method) of compound (B2) is preferably 0 or more.The HLB of compound (B2) is preferably 1 or more, more Preferably 3 or more, it is more preferably 5 or more, also, preferably 150 or less, is more preferably 100 or less, is more preferably It 80 or less, is still more preferably 60 or less.It should be noted that the HLB of compound (B2) can be calculated by structure.

R in general formula (B2)²¹For the alkyl below of carbon number 4 or more and 27.The alkyl includes the alkyl comprising substituent group.It takes Described in Dai Jiru compound (B1).

As R²¹Alkyl, can enumerate selected from alkyl, alkenyl, aralkyl, aryl and with substituent group aryl (with Under, referred to as substituted aryl) in group.From the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming It sets out, R²¹Alkyl be preferably selected from the group in alkyl and alkenyl.

From the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming, R²¹Alkyl it is preferred For aliphatic alkyl, more preferably straight-chain aliphatic alkyl.

From the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming, R²¹Alkenyl it is preferred For aliphatic alkenyl, more preferably straight-chain aliphatic alkenyl.

R²¹Substituted aryl be aromatic rings the aryl that is substituted with a substituent of hydrogen atom, the hydrogen atom of aromatic rings can be enumerated The aryl replaced by alkyl.The carbon number of substituted aryl comprising substituent group is 4 or more and 27 or less.As substituted aryl, can arrange Enumerate 1,2 or 3 aryl replaced the substituent groups such as alkyl of the hydrogen atom of aromatic rings.The aryl of substituted aryl is preferred For phenyl.As substituted aryl, the substituted aryl below of carbon number 13 or more and 27 can be enumerated.The substituent group of substituted aryl can arrange Enumerate the alkyl below of carbon number 1 or more and 10.

From the viewpoint of the viewpoint and economy of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming, R²¹Preferably alkyl.

It is easy from the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming and dissolution in water From the perspective of, R²¹Preferably alkenyl.

The viewpoint upward from the viewpoint and dispersibility of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming It sets out, R²¹Carbon number be preferably 8 or more, more preferably 12 or more, further preferably 16 or more, also, preferably 22 or less, It more preferably 20 or less, is more preferably 18 or less.

If enumerating R²¹Concrete example, then from centrifugal forming and/or performance centrifugal forming after hardenite intensity sight Point sets out, can enumerate selected from carbon number be preferably 10 or more, further preferably 12 or more, also, preferably 22 or less, into one Step is preferably the group in the alkyl that the hydrogen atom of 20 alkyl and the alkyl below is substituted with a substituent.

If enumerating R²¹Other concrete examples, then from centrifugal forming and/or performance centrifugal forming after hardenite intensity From the perspective of, can enumerate selected from carbon number be preferably 10 or more, further preferably 12 or more, also, preferably 22 or less, Group that the hydrogen atom of further preferably 20 alkyl or alkenyls below and the alkyl or the alkenyl is substituted with a substituent, with And the group in the phenyl replaced by alkyl.

If enumerating R²¹Other concrete examples, then from centrifugal forming and/or performance centrifugal forming after hardenite intensity From the perspective of, can enumerate selected from carbon number be preferably 10 or more, further preferably 12 or more, also, preferably 22 or less, Further preferably 20 alkyl below, preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl and carbon number are preferred For 10 or more, further preferably 12 or more, also, preferably 22 or less, further preferably 20 alkenyls below, preferably Aliphatic alkenyl, the group more preferably in straight-chain aliphatic alkenyl.In addition, as R²¹Other concrete examples, carbon can be enumerated Number preferably 1 or more, further preferably 2 or more, also, preferably 10 or less, further preferably 8 alkyl below replace Phenyl, benzyl replace phenyl, styrol phenyl.

More specifically, as R²¹, can enumerate for example selected from decyl, lauryl, myristyl, palmityl, hard Group in aliphatic radical, behenyl base, iso stearyl and oil base, from the hardenite after centrifugal forming and/or performance centrifugal forming From the perspective of the viewpoint and mobility of intensity improve, preferably enumerate selected from lauryl, myristyl, palmityl, stearyl, Group in behenyl base, iso stearyl and oil base, it may be more preferable to enumerate selected from lauryl, myristyl, palmityl, stearyl and Group in oil base.It should be noted that when the X in general formula (B2) is COO, as R²¹, can exemplify and subtract from these groups Remove group obtained by 1 carbon number.For example, nonyl can be exemplified instead of decyl, undecyl can be exemplified instead of lauryl.

As R²¹Alkyl, as described above, alkyl, alkenyl, aralkyl, aryl and the aryl with substituent group can be enumerated (hereinafter referred to as substituted aryl).From the viewpoint of the intensity for showing the hardenite after steam curing, R²¹Alkyl preferably select From the group in substituted aryl and alkenyl.

R²¹Substituted aryl be the aryl replaced by alkyl, the substituted aryl below of carbon number 13 or more and 27 can be enumerated.

From the viewpoint of the blistering of the viewpoint and inhibition hydraulic-composition that show the intensity after steam curing, R²¹It is preferred that For substituted aryl.

From the viewpoint of showing the viewpoint of intensity of the hardenite after steam curing and dissolution in water is easy, R²¹It is excellent It is selected as alkenyl.

From the viewpoint of the intensity for showing the hardenite after steam curing, R²¹Substituted aryl it is preferably distyrenated Phenyl.

From the viewpoint of the intensity for showing the hardenite after steam curing, R²¹Alkenyl be preferably aliphatic alkenyl, more Preferably straight-chain aliphatic alkenyl.

From the viewpoint of showing the viewpoint of intensity of the hardenite after steam curing and dispersibility upwards, R²¹Carbon number it is excellent It is selected as 8 or more, more preferably 12 or more, further preferably 16 or more, also, preferably 22 or less.

If enumerating R²¹Concrete example, then it is upward from the viewpoint and dispersibility of the intensity of the hardenite after performance steam curing Viewpoint is set out, and can enumerate selected from carbon number is preferably 10 or more, further preferably 12 or more, also, preferably 22 is below The group in alkyl that the hydrogen atom of alkyl and the alkyl is substituted with a substituent.

If enumerating R²¹Other concrete examples can be arranged then from the viewpoint of the intensity for showing the hardenite after steam curing Enumerating selected from carbon number is preferably 10 or more, further preferably 12 or more, also, preferably 22 alkenyls below and the alkenyl The group that is substituted with a substituent of hydrogen atom and substituted aryl, the phenyl that is preferably replaced by alkyl in group.

If enumerating R²¹Other concrete examples can be arranged then from the viewpoint of the intensity for showing the hardenite after steam curing Enumerate selected from carbon number be preferably 10 or more, further preferably 12 or more, be still more preferably 16 or more, also, preferably It 22 or less, is more preferably 20 alkenyl, preferably aliphatic alkenyls, the base being more preferably in straight-chain aliphatic alkenyl below Group.In addition, as substituted aryl, preferably distyrenated phenyl.

More specifically, as R²¹, can enumerate selected from decyl, lauryl, myristyl, palmityl, stearyl, Group in behenyl base, iso stearyl, oil base and distyrenated phenyl, the intensity of the hardenite after showing steam curing From the perspective of viewpoint and mobility improve, preferably enumerate selected from lauryl, myristyl, palmityl, stearyl, behenyl Group in base, iso stearyl, oil base and distyrenated phenyl, it may be more preferable to enumerate selected from lauryl, myristyl, palm Group in base, stearyl, oil base and distyrenated phenyl.It should be noted that when the X in general formula (B2) is COO, as R²¹, can exemplify from subtracting group obtained by 1 carbon number in these groups.For example, nonyl can be exemplified instead of decyl, instead of the moon Gui Jike exemplifies undecyl.

In general formula (B2), X is O or COO, preferably O.

In general formula (B2), AO is the alkylene oxide group below of carbon number 2 or more and 4, from centrifugal forming and/or case-hardening(drying) body Intensity from the perspective of, be preferably selected from the group of one or more of the alkylene oxide group of carbon number 2 and the alkylene oxide group of carbon number 3. From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, AO preferably comprises the alkylene oxide group of carbon number 2.

In general formula (B2), n₂For the average addition molal quantity of AO, from the intensity of centrifugal forming and/or case-hardening(drying) body It is 1 or more and 200 numbers below from the perspective of viewpoint and cement dispersibility.From centrifugal forming and/or case-hardening(drying) body From the perspective of the viewpoint and mobility of intensity improve, n₂Preferably 10 or more, be more preferably 20 or more, also, from (A) at The interaction divided is easy with economic viewpoint and from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, Preferably 60 or less, 40 numbers below are more preferably.

R²¹In the case where for substituted aryl, from the viewpoint of the intensity for showing the hardenite after steam curing, n₂It is preferred that It is 10 or more, also, preferably 25 or less, more preferably 15 or less.

R²¹In the case where for alkyl, from the viewpoint of the intensity for showing the hardenite after steam curing, n₂Preferably 1 with On, also, preferably 5 or less.

R²¹In the case where for alkenyl, from the viewpoint of the intensity for showing the hardenite after steam curing, n₂Preferably 5 with Above, 8 or more, further preferably 10 or more, also, preferably 65 or less are more preferably, 50 or less is more preferably, is further excellent It is selected as 40 or less, is still more preferably 35 or less, is still more preferably 25 or less, is still more preferably 15 or less.

In general formula (B2), R²²For hydrogen atom or the alkyl below of carbon number 1 or more and 3, preferably hydrogen atom.

As compound (B2), polyoxyethylene -2- ethylhexyl ether, polyoxyethylene decyl ethers, polyoxy can be enumerated The polyoxyethylene ether and polyoxyethylene alkene ether of ethylidene lauryl ether, polyoxyethylene oleyl ether etc..In addition, can Enumerate the polyoxyethylene ester of polyoxyethylene monostearate etc..In addition, polyoxyethylene hexichol second can be enumerated The polyoxyethylene substituted aryl ether of alkylene phenyl ether etc..

< compound (B3) >

Compound (B3) is compound represented by the general formula (B3).

R in general formula (B3)³¹For the alkyl below of carbon number 4 or more and 27.The alkyl includes the alkyl comprising substituent group.It takes Described in Dai Jiru compound (B1).

As R³¹Alkyl, can enumerate selected from alkyl, alkenyl, aralkyl, aryl and with substituent group aryl (with Under, referred to as substituted aryl) in group.Substituted aryl can enumerate the hydrogen atom of aromatic rings 1,2 or 3 is substituted Aryl.From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, R³¹Alkyl be preferably selected from alkyl and alkenyl In group.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, R³¹Alkyl be preferably aliphatic alkyl, More preferably straight-chain aliphatic alkyl-alkyl.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, R³¹Alkenyl be preferably aliphatic alkenyl, More preferably straight-chain aliphatic alkenyl.

From the viewpoint of the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and economy, R³¹Preferably alkyl.

Dissolution from the viewpoint of the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and in water is easy, R³¹Preferably alkenyl.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, R³¹Carbon number be preferably selected from 8 or more, Be more preferably selected from 12 or more, further preferably selected from 16 or more, also, be preferably selected from 22 or less, be more preferably selected from 20 or less, into One step is preferably selected from 18 or less.

If enumerating R³¹Concrete example, then from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, preferably It enumerates and is selected from 10 or more carbon number, is more preferably 12 or more, also, preferably 27 or less, is more preferably 26 or less, is further preferred The group in alkyl being substituted with a substituent for the hydrogen atom of 24 alkyl and the alkyl below.

If enumerating R³¹Other concrete examples can then from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body It is preferred that enumerate selected from 10 or more carbon number, more preferably 12 or more, also, preferably 27 or less, more preferably 26 or less, further The group in group that the hydrogen atom of preferably 24 alkyl or alkenyls below and the alkyl or the alkenyl is substituted with a substituent.

If enumerating R³¹Other concrete examples can then from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body It is preferred that enumerate selected from 10 or more carbon number, more preferably 12 or more, also, preferably 27 or less, more preferably 26 or less, further Preferably 24 alkyl below, preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl, and preferably carbon number 10 with It is upper, more preferably 12 or more, also, preferably 27 or less, more preferably 26 or less, further preferably 24 alkenyls below, Preferably aliphatic alkenyl, the group being more preferably in straight-chain aliphatic alkenyl.

More specifically, as R³¹, can enumerate for example selected from decyl, lauryl, myristyl, palmityl, hard Group in aliphatic radical, behenyl base, iso stearyl and oil base, from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and From the perspective of mobility improves, preferably enumerate selected from lauryl, myristyl, palmityl, stearyl, behenyl base, different hard Group in aliphatic radical and oil base, it may be more preferable to enumerate the base in lauryl, myristyl, palmityl, stearyl and oil base Group.

In general formula (B3), AO is the alkylene oxide group below of carbon number 2 or more and 4, from centrifugal forming and/or case-hardening(drying) body Intensity from the perspective of, be preferably selected from the group of one or more of the alkylene oxide group of carbon number 2 and the alkylene oxide group of carbon number 3. From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, AO preferably comprises the alkylene oxide group of carbon number 2.

In general formula (B3), n₃And n₄It is 0 or more number for the average addition molal quantity of AO identical or different respectively.From from From the perspective of the viewpoint and cement of heart mouldability and/or the intensity of case-hardening(drying) body dispersibility, n₃And n₄Add up to 1 or more, Preferably 10 or more, 20 or more are more preferably, also, from the viewpoint of economy, be 200 hereinafter, preferably 60 or less, it is more excellent It is selected as 40 numbers below.

In general formula (B3), R³²And R³³It is the identical or different, hydrogen atom of difference or the alkyl below of carbon number 1 or more and 3. From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, R³²And R³³It is respectively preferably hydrogen atom.

As compound (B3), the polyalkylene oxides alkylamine such as polyoxyethylene amine can be enumerated.

< compound (B4) >

Compound (B4) is compound represented by the general formula (B4).

R in general formula (B4)⁴¹For the alkyl below of carbon number 4 or more and 27.The alkyl includes the alkyl comprising substituent group.It takes Described in Dai Jiru compound (B1).

As R⁴¹Alkyl, can enumerate selected from alkyl, alkenyl, aralkyl, aryl and with substituent group aryl (with Under, referred to as substituted aryl) in group.Substituted aryl can enumerate the hydrogen atom of aromatic rings 1,2 or 3 is substituted Aryl.From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, R⁴¹Alkyl be preferably selected from alkyl and alkenyl In group.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, R⁴¹Alkyl be preferably aliphatic alkyl, More preferably straight-chain aliphatic alkyl.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, R⁴¹Alkenyl be preferably aliphatic alkenyl, More preferably straight-chain aliphatic alkenyl.

From the viewpoint of the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and economy, R⁴¹Preferably alkyl.

Dissolution from the viewpoint of the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and in water is easy, R⁴¹Preferably alkenyl.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, R⁴¹Carbon number be preferably selected from 8 or more, Be more preferably selected from 12 or more, further preferably selected from 16 or more, also, be preferably selected from 22 or less, be more preferably selected from 20 or less, into One step is preferably selected from 18 or less.

If enumerating R⁴¹Concrete example, then from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, preferably It enumerates and is selected from 10 or more carbon number, is more preferably 12 or more, also, preferably 27 or less, is more preferably 26 or less, is further preferred The group in alkyl being substituted with a substituent for the hydrogen atom of 24 alkyl below and the alkyl.

If enumerating R⁴¹Other concrete examples can then from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body It is preferred that enumerate selected from 10 or more carbon number, more preferably 12 or more, also, preferably 27 or less, more preferably 26 or less, further The group in group that the hydrogen atom of preferably 24 alkyl or alkenyls below and the alkyl or the alkenyl is substituted with a substituent.

If enumerating R⁴¹Other concrete examples can then from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body It is preferred that enumerate selected from 10 or more carbon number, more preferably 12 or more, also, preferably 27 or less, more preferably 26 or less, further Preferably 24 alkyl below, preferably aliphatic alkyl, more preferably straight-chain aliphatic alkyl, and preferably carbon number 10 with It is upper, more preferably 12 or more, also, preferably 27 or less, more preferably 26 or less, further preferably 24 alkenyls below, Preferably aliphatic alkenyl, the group being more preferably in straight-chain aliphatic alkenyl.

More specifically, as R⁴¹, can enumerate for example selected from decyl, lauryl, myristyl, palmityl, hard Group in aliphatic radical, behenyl base, iso stearyl and oil base, from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and From the perspective of mobility improves, preferably enumerate selected from lauryl, myristyl, palmityl, stearyl, behenyl base, different hard Group in aliphatic radical and oil base, it may be more preferable to enumerate the base in lauryl, myristyl, palmityl, stearyl and oil base Group.

In general formula (B4), AO is the alkylene oxide group below of carbon number 2 or more and 4, from centrifugal forming and/or case-hardening(drying) body Intensity from the perspective of, be preferably selected from the group of one or more of the alkylene oxide group of carbon number 2 and the alkylene oxide group of carbon number 3. From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, AO preferably comprises the alkylene oxide group of carbon number 2.

In general formula (B4), Y¹、Y²For identical or different respectively hydrogen atom or SO₃M, Y¹、Y²At least one be SO₃M。M For counter ion counterionsl gegenions, hydrogen ion, alkali metal ion, alkaline-earth metal ion (1/2 ion), ammonium ion etc. can be enumerated.From centrifugation From the perspective of the manufacture of the viewpoint and compound of mouldability and/or the intensity of case-hardening(drying) body is easy, M is preferably ammonium ion. From the viewpoint of the peculiar smell of the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and compound, M is preferably alkali metal Ion, the alkali metal ion more preferably in sodium ion and potassium ion.

In general formula (B4), n₅And n₆It is 0 or more number for the average addition molal quantity of AO identical or different respectively.n₅For In the case where 0, Y¹It is hydrogen atom, n₆In the case where 0, Y²For hydrogen atom.From the strong of centrifugal forming and/or case-hardening(drying) body From the perspective of viewpoint and the cement dispersibility of degree, n₅And n₆Add up to 1 or more, preferably 20 or more, more preferably 50 with On, also, from the viewpoint of the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and economy, it is 200 hereinafter, excellent 150 are selected as hereinafter, more preferably 100 numbers below.n₅And n₆It is not simultaneously 0.Therefore compound (B4) has (AO)_n5-SO₃M and (AO)_n6-SO₃At least the 1 of M.

As compound (B4), the aliphatic amine alkylene of tallow amine ethylene oxide adduct sulfuric ester compound etc. can be enumerated The sulfuric ester compound of base addition product.

(B) ingredient is also possible to belong to the change of compound (B1), compound (B2), compound (B3) and compound (B4) 1 kind or more for closing object.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, (B) ingredient is preferably selected from compound (B1), the compound of one or more of compound (B2) and compound (B3).

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, (B) ingredient is preferably selected from compound (B1) With the compound of one or more of compound (B2).

The viewpoint of the intensity of centrifugal forming hydraulic-composition of the invention from centrifugal forming and/or case-hardening(drying) body It sets out, as (B) ingredient, preferably comprises the change selected from one or more of compound (B1), compound (B2) and compound (B3) Close object, the further preferably compound selected from one or more of compound (B1) and compound (B2).

Hydraulic powder used in centrifugal forming hydraulic-composition of the invention is with passing through hydration reaction The powder of the physical property of hardening can enumerate cement, gypsum etc..Preferably cement, more preferably ordinary portland cement, belite The cement such as cement, moderate heat cement, high-early (strength) cement, super-early strength cement, sulfate-resistant cement.Alternatively, it is also possible to being into cement etc. Add powder, the mountain flour (calcium carbonate powder) with pozzolanic action and/or latent hydraulicity such as blast-furnace slag, flyash, silicon ash Blast furnace slag cement, pulverized fuel ash cement Deng obtained by, Silica fume cement etc..

Centrifugal forming hydraulic-composition of the invention contains aggregate.As aggregate, can enumerate selected from fine aggregate and Aggregate in coarse aggregate.As fine aggregate, the aggregate of 2311 defined of number in JIS A0203-2014 can be enumerated.As Fine aggregate can enumerate river sand, land sand, mountain sand, sea sand, lime sand, silica sand and their broken sand, blast-furnace slag fine aggregate, nickel Scum fine aggregate, lightweight fine aggregate (artificial and natural) and recycled fine aggregate etc..In addition, JIS can be enumerated as coarse aggregate The aggregate of 2312 defined of number in A0203-2014.For example, river sand gravel, land gravel, mountain sand can be enumerated as coarse aggregate Gravel, sea sand gravel, lime gravel, their rubble, blast-furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and day So) and regenerated coarse aggregate etc..Diverse aggregate can be used in mixed way by fine aggregate, coarse aggregate, also can be used single kind The aggregate of class.

From the viewpoint and performance steam curing of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming From the perspective of the intensity of hardenite afterwards, in centrifugal forming hydraulic-composition of the invention, the content of (B) ingredient is opposite In total ratio of the content of the content and (B) ingredient of (A) ingredient be preferably 3 mass % or more and 60 mass % or less.It should Ratio is found out by [content of (B) ingredient/(content of (A) ingredient+(B) ingredient content)] × 100 (quality %).With Under, which is shown as (B)/((A)+(B)).From centrifugal forming and/or performance centrifugal forming after hardenite intensity, with And performance steam curing after hardenite intensity from the perspective of, (B)/((A)+(B)) be more preferably 3 mass % or more, into One step be preferably 5 mass % or more, still more preferably for 10 mass % or more, be still more preferably 20 mass % or more, Also, more preferably 50 mass % or less, further preferably 40 mass % or less, still more preferably for 30 mass % with Under.(B)/((A)+(B)) can combined amount based on (A) ingredient when manufacturing centrifugal forming hydraulic-composition of the invention and (B) combined amount of ingredient calculates.

From the viewpoint of the intensity for showing the hardenite after steam curing, in R¹¹For the hydrocarbon below of carbon number 16 or more and 20 In the case where base, (B)/((A)+(B)) is preferably 7 mass % or more, is more preferably 15 mass % or more, also, preferably 55 Quality % or less, more preferably 45 mass % or less, further preferably 35 mass % are hereinafter, be still more preferably 25 matter Measure % or less.

In addition, from the viewpoint of the intensity for showing the hardenite after steam curing, in R¹¹For carbon number 6 or more and 10 or less Alkyl in the case where, (B)/((A)+(B)) is preferably 7 mass % or more and 15 mass % or less.

In the case where (A) ingredient is the high-molecular compound with the monomeric unit containing naphthalene nucleus, centrifugation of the invention Molding in hydraulic-composition, from the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming and From the perspective of intensity after showing steam curing, the total amount of (B) ingredient is relative to the monomeric unit containing naphthalene nucleus in (A) ingredient Molar ratio be preferably 0.2% or more and 50% or less.According to identical viewpoint, the molar ratio be preferably 0.5% with It is upper, more preferably 0.8% or more, further preferably 1.5% or more, be still more preferably 5% or more, also, preferably 45% or less, 30% or less, further preferably 20% is more preferably hereinafter, still more preferably for 15% hereinafter, more into one Step preferably 10% is hereinafter, be still more preferably 8% or less.

In R¹¹In the case where for aralkyl, the molar ratio is preferably 1.5% or more, more preferably 2% or more, and And preferably 7% or less, more preferably 6% or less, further preferably 5% hereinafter, still more preferably be 4.5% hereinafter, It is still more preferably 3% or less.

In R¹¹In the case where for alkenyl, the molar ratio is preferably 1.5% or more, is more preferably 3% or more, is further It preferably 4% or more, is still more preferably 6.5% or more, also, preferably 9% or less, more preferably 8% or less.

In R¹¹In the case where the alkyl below of carbon number 16 or more and 18, the molar ratio is preferably 0.5% or more, more Preferably 1% or more, be more preferably 2% or more, still more preferably for 3.5% or more, be still more preferably 5% with On, also, preferably 45% or less, more preferably 40% or less, further preferably 25% hereinafter, being still more preferably It 15% or less, is still more preferably 10% or less.

In R¹¹In the case where the alkyl below of carbon number 6 or more and 10, the molar ratio is preferably 0.3% or more, more Preferably 0.5% or more, be more preferably 1.5% or more, also, preferably 7% or less, more preferably 6% or less, into one Step preferably 3% or less.

In addition, in centrifugal forming hydraulic-composition of the invention, from the viewpoint of the raising of concrete Combination, (B) total amount of ingredient relative to the molar ratio of the monomeric unit containing naphthalene nucleus in (A) ingredient be preferably 16.1% or more and 50% hereinafter, more preferably 30.1% or more.

It should be noted that the total amount of (B) ingredient is relative to wrapping rubbing for naphthalene-ring containing monomeric unit in described (A) ingredient You are calculated ratio based on the total amount of the total amount and (B) ingredient of wrapping naphthalene-ring containing monomeric unit in (A) ingredient.Specifically, logical Following formula is crossed to calculate.

Molar ratio (%)=[(total amount (mole) of (B) ingredient)/(the total of naphthalene-ring containing monomeric unit is wrapped in (A) ingredient Measure (mole))] × 100

(A) in the case that ingredient is naphthalene sulfonic acid-formaldehyde condensation product or its salt, wrap naphthalene-ring containing monomeric unit be naphthalene sulfonic acids or The monomeric unit that its salt is formed with formaldehyde generation dehydration condensation.(A) ingredient is the sodium salt of naphthalene sulfonic acid-formaldehyde condensation product In the case of, the total amount (mole) that naphthalene-ring containing monomeric unit is wrapped in the compound is calculated by following formula.In formula, by naphthalene sulfonic acids The sodium salt of formaldehyde condensation products is indicated with NSF.

The total amount (mole) of naphthalene-ring containing monomeric unit=(quality of naphthalene-ring containing monomeric unit is wrapped in NSF is wrapped in NSF Total amount)/(molecular weight of naphthalene-ring containing monomeric unit is wrapped in NSF)

In the case where (A) ingredient is the condensation product of naphthalene sulfonic acids or its salt and formaldehyde, naphthalene-ring containing monomer is wrapped in (A) ingredient The total amount of the quality of unit is the gross mass of the compound.

In addition, in the feelings for the condensation product that (A) ingredient is naphthalene sulfonic acids or its salt, formaldehyde and not naphthalene-ring containing other monomers Under condition, the total amount of the quality of naphthalene-ring containing monomeric unit is wrapped in (A) ingredient to be subtracted from the gross mass of the compound derived from institute State the quality of the quality of the monomeric unit of not naphthalene-ring containing other monomers and formaldehyde.

Quality derived from the monomeric unit of the not naphthalene-ring containing other monomers can be calculated from inventory when synthesizing, Also nuclear magnetic resonance spectral apparatus etc., which can be used, can find out the general resolver of copolymerization mass ratio to calculate.

In addition, wrapping naphthalene-ring containing list in (A) ingredient in the case where (A) ingredient is the sodium salt of naphthalene sulfonic acid-formaldehyde condensation product The molecular weight of body unit can be to subtract work from the sum of molecular weight (30.0) of the molecular weight of sodium naphthalene sulfonate (230.2) and formaldehyde It is determined for the mode of the numerical value (i.e. 242.2) of the molecular weight (18.0) of the water of the secondary product of condensation reaction.

In centrifugal forming hydraulic-composition of the invention, such as in the sodium that (A) ingredient is naphthalene sulfonic acid-formaldehyde condensation product In the case that salt, (B) ingredient are polyoxyethylene ether sulfuric ester ammonium salt, the total amount of (B) ingredient in (A) ingredient relative to containing Having the molar ratio of the monomeric unit of naphthalene nucleus can use the general methods such as reprecipitation method, liquid separation method by (A) ingredient and (B) ingredient Separation, and the mass ratio is measured to be calculated to acquire.

In addition, the construction of (A) ingredient in centrifugal forming hydraulic-composition and (B) ingredient can with reprecipitation method, The general method such as liquid separation method separates (A) ingredient with (B) ingredient, and uses nuclear magnetic resonance spectroscopy device, liquid chromatogram etc. General resolver is parsed.

In the case where centrifugal forming is concrete with hydraulic-composition, about the dosage of coarse aggregate, from performance hydraulic Property composition intensity and reduce the dosage of hydraulic powders such as cement, improve to go out to the viewpoint of the fillibility of the fillings such as molding box Hair, loose dressing product preferably 50% or more, more preferably 55% or more, further preferably 60% or more, also, preferably 100% or less, it is more preferably 90% or less, further preferably 80% or less.Loose dressing product is 1m³Coarse aggregate in concrete Volume (include gap) ratio.

In addition, in the case where centrifugal forming is concrete with hydraulic-composition, about the dosage of fine aggregate, from raising To from the perspective of the fillibility of the fillings such as molding box, preferably 500kg/m³Above, it is more preferably 600kg/m³Above, further Preferably 700kg/m³More than, also, preferably 1,000kg/m³Below, it is more preferably 900kg/m³Below.

In the case where centrifugal forming is mortar with hydraulic-composition, the dosage of fine aggregate is preferably 800kg/m³With Upper, more preferably 900kg/m³It above, is more preferably 1,000kg/m³More than, also, preferably 2,000kg/m³Below, More preferably 1,800kg/m³It below, is more preferably 1,700kg/m³Below.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body and further increase water reducing ability and flowing is protected From the perspective of the viewpoint of holding property and the intensity of the hardenite after performance steam curing, centrifugal forming hydraulic of the invention Property composition can contain (C) polycarboxylic-acid copolymer (hereinafter referred to as (C) ingredient).

As (C) ingredient, can enumerate comprising shown in monomer (C1) shown in the following general formula (C1) and the following general formula (C2) Monomer (C2) as constitute monomer copolymer (hereinafter referred to as copolymer (C)).

[chemical formula 2]

(in formula,

R^11c、R^12c: it is optionally identical or different, indicate hydrogen atom or methyl；

R^13c: indicate hydrogen atom or-COO (AO)_n’X¹；

X¹: indicate the alkyl below of carbon number 1 or more and 4；

AO: the group in ethyleneoxy group and propylidene oxygroup is indicated；

N ': for the average addition molal quantity of AO, 1 or more and 300 numbers below are indicated；

P: 0 or more and 2 numbers below are indicated.〕

[chemical formula 3]

(in formula,

R^21c、R^22c、R^23c: it is optionally identical or different, it is hydrogen atom, methyl or (CH₂)_rCOOM², (CH₂)_rCOOM²Optionally with COOM¹Or other (CH₂)_rCOOM²Acid anhydrides is formed, at this point, M is not present in these groups¹、M²。

M¹、M²: it is optionally identical or different, indicate hydrogen atom, alkali metal, alkaline-earth metal (1/2 atom), ammonium, alkyl ammonium group Or replace alkyl ammonium group；

R: 0 or more and 2 numbers below are indicated.〕

In general formula (C1), R^11cPreferably hydrogen atom.

In general formula (C1), R^12cPreferably methyl.

In general formula (C1), R^13cPreferably hydrogen atom.

In general formula (C1), X¹Preferably methyl.

In general formula (C1), AO is preferably ethyleneoxy group.AO preferably comprises ethyleneoxy group.

In general formula (C1), it is 1 or more and 300 numbers below that n ', which is the average addition molal quantity of AO,.From centrifugal forming And/or from the perspective of the intensity of the hardenite after performance centrifugal forming, n ' is preferably 100 or more, more preferably 110 or more, Also, preferably 200 or less, it is more preferably 150 numbers below.

In addition, n ' is preferably 5 or more, is more preferably from the viewpoint of the intensity for showing the hardenite after steam curing It 20 or more, is more preferably 40 or more, also, preferably 200 or less, more preferably 150 or less, further preferably 100 Below, it is still more preferably 80 or less, is still more preferably 50 numbers below.

In general formula (C1), p is preferably 0.

In general formula (C2), R^21cPreferably hydrogen atom.

In general formula (C2), R^22cPreferably methyl.

In general formula (C2), R^23cPreferably hydrogen atom.

About (CH₂)_rCOOM², can be with COOM¹Or others (CH₂)_rCOOM²Acid anhydrides is formed, in this case, these The M of group¹、M²It is not present.

About copolymer (I), in general formula (C2), M¹、M²Can be identical or different, it is respectively preferably hydrogen atom.

(CH in general formula (C2)₂)_rCOOM²R be preferably 1.

The list in monomer is constituted from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, in copolymer (C) The total amount of body (C1) and monomer (C2) be 90 mass % or more, preferably 92 mass % or more, more preferably 95 mass % with On, also, be 100 mass % or less.The total amount can be 100 mass %.

From the viewpoint of the hardenite intensity after centrifugal forming and/or centrifugal forming, monomer (C2) in copolymer (C) Total ratio relative to monomer (C1) and monomer (C2) is preferably 80 moles of % or more, is more preferably 90 moles of % or more, Also, preferably 98 moles of % or less, more preferably 97 moles of % or less.

From the viewpoint of the intensity for showing the hardenite after steam curing, monomer (C2) is relative to list in copolymer (C) Total ratio of body (C1) and monomer (C2) is preferably 60 moles of % or more, more preferably 75 moles of % or more, also, preferred For 90 moles of % or less, more preferably 80 moles of % or less, further preferably 77 moles of % or less.

The weight average molecular weight of copolymer (C) is preferably 10,000 or more, more preferably 15,000 or more, also, preferably 100,000 or less, 70,000 or less, further preferably 45,000 or less are more preferably.The weight average molecular weight passes through following The gel permeation chromatography (GPC) of part measures.

* GPC condition

Device: GPC (HLC-8320GPC) TOSOH Co., Ltd system

Column: G4000PWXL+G2500PWXL (TOSOH Co., Ltd's system)

Eluent: 0.2M phosphate buffer/CH₃CN=9/1

Flow: 1.0mL/min

Column temperature: 40 DEG C

Detection: RI

Sample size: 0.2mg/mL

Standard substance: polyethylene glycol conversion (monodispersed polyethylene glycol: molecular weight 87,500,250,000,145,000, 46,000、24,000)

In the past, sufficient effect was not shown being used in mixed way (A) ingredient and (C) ingredient yet.By inference this be because For with poly- alkylene oxide group interaction occurs for aromatic rings, the dispersion force of the two offsets, and two-component is macromolecule chemical combination Object, therefore doubtful molecular weight increases and thickening occurs, motility is greatly reduced, so that dispersibility reduces.But in the present invention, If by inference and with (B) ingredient, the alkyl of the aromatic rings and (B) ingredient of (A) ingredient interacts, it is suppressed that (A) at Divide the interaction with (C) ingredient, thus it is speculated that thus and with (A) ingredient and (C) ingredient be possibly realized for the first time.

1 mode of the invention is a kind of centrifugal forming hydraulic-composition, for containing (A) ingredient, (B) ingredient, The centrifugal forming hydraulic-composition of hydraulic powder, aggregate and water, the ratio between water/hydraulic powder is more than 25 mass % and is 35 mass % or less.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, the centrifugal forming hydraulicity of the invention The ratio between water/hydraulic powder of composition more than 25 mass %, preferably 25.5 mass % or more, more preferably 26 mass % with On, also, be 35 mass % or less, preferably 30 mass % or less, more preferably 27 mass % or less.

Herein, the ratio between water/hydraulic powder is the quality percentage (matter of water and hydraulic powder in hydraulic-composition Measure %), it is calculated by quality/hydraulic powder quality × 100 of water.Amount of the ratio between the water/hydraulic powder based on water and The amount of powder with the physical property being cured by hydration reaction is calculated.With the object being cured by hydration reaction Property powder include in the powder with pozzolanic action, the powder with latent hydraulicity and the mountain flour (calcium carbonate powder) Powder in the case where, in the present invention, their amount is also included in the amount of hydraulic powder.In addition, having anti-by hydration In the case that the powder for the physical property that should be cured contains high-intensitive mixed material, the amount of high-intensitive mixed material is also included in water The amount of rigid powder.This respect, mass parts below relevant to the quality of hydraulic powder are also identical.

Another 1 mode of the invention is a kind of centrifugal forming hydraulic-composition, for containing (A) ingredient, (B) at Divide, the centrifugal forming hydraulic-composition of hydraulic powder, aggregate and water, without high-intensitive admixture.

Another 1 mode of the invention is a kind of centrifugal forming hydraulic-composition, for containing (A) ingredient, (B) at Divide, the centrifugal forming hydraulic-composition of hydraulic powder, aggregate and water, is free of high-intensitive admixture, and water/hydraulicity powder The ratio between body is more than 25 mass % and is 35 mass % or less.The ratio between water/hydraulic powder in which can use above-mentioned Preferred scope.

As high-intensitive admixture, can enumerate Bo Shi value is 2,500cm²/ g or more or BET specific surface area are 10m²/ g with On powder, and then inorganic particle (not including cement) can be enumerated.As the constituent of high-intensitive admixture, can enumerate Powder in anhydrous gypsum, silicon ash and flyash.High-intensitive admixture can enumerate the DENKA Σ as commercially available product (Pacific Ocean material is public by 1000 (DENKA companies), DENKA Σ 2000 (DENKA company), Pacific Ocean ULTRA SUIPER MIX Department) etc..

In centrifugal forming hydraulic-composition of the invention, relative to hydraulic powder, and then 100 mass parts of cement, The content of high-intensitive admixture be preferably 5 below the mass, further preferably 2 below the mass, further preferably 1 mass Part or less, further preferably 0.5 below the mass, further preferably 0.2 below the mass, further preferably 0.1 matter Measure part or less, further preferably 0.05 below the mass, further preferably 0.02 below the mass, further preferably 0.01 below the mass, further preferably 0.005 below the mass, further preferably 0.002 below the mass, further Preferably 0.001 below the mass.Centrifugal forming of the invention is preferably substantially free of high-intensitive blending with hydraulic-composition Material.Herein, it is substantially free of and refers to show the amount of its target effect and without high-intensitive admixture.For example, that can not keep away It has been mixed into that case of high-intensitive admixture on a small quantity with exempting from, can be described as being substantially free of sometimes.As described above, of the invention 1 mode be free from the centrifugal forming hydraulic-composition of high-intensitive admixture.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, the centrifugal forming hydraulicity of the invention In composition, relative to 100 mass parts of hydraulic powder, 0.001 mass parts of (A) ingredient or more, more preferable 0.01 are preferably comprised More than mass parts, more than further preferred 0.1 mass parts, also, preferably 10 below the mass, more preferably 5 below the mass, into One step preferably 3 is below the mass, further preferably 2 below the mass, still more preferably 1 below the mass.

From the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, the centrifugal forming hydraulicity of the invention In composition, relative to 100 mass parts of hydraulic powder, 0.0001 mass parts of (B) ingredient or more, more preferably are preferably comprised It is more than 0.001 mass parts, it is more than further preferred 0.01 mass parts, it is more than still more preferably 0.03 mass parts, further It is preferred that more than 0.05 mass parts, also, preferably 10 below the mass, more preferably 5 below the mass, further preferably 1 mass parts Below, further preferably 0.5 below the mass, still more preferably 0.35 below the mass.

From the viewpoint of the intensity of the hardenite after centrifugal forming and/or performance centrifugal forming, centrifugation of the invention In molding hydraulic-composition, relative to 100 mass parts of hydraulic powder, (A) ingredient and (B) are preferably comprised into subtotaling It is more than 0.1 mass parts, it is more than more preferable 0.25 mass parts, also, preferably 10 below the mass, more preferably 5 below the mass, into One step preferably 2 is below the mass.

In the case where centrifugal forming hydraulic-composition of the invention contains (C) ingredient, from centrifugal forming and/or From the perspective of the intensity of case-hardening(drying) body, relative to 100 mass parts of hydraulic powder, 0.01 mass of (C) ingredient is preferably comprised Part or more, it is more than more preferable 0.05 mass parts, also, preferably 2 below the mass, more preferably 1 below the mass, further preferably 0.5 below the mass, further preferably 0.3 below the mass.

In addition, in the case where centrifugal forming hydraulic-composition of the invention contains (C) ingredient, from the de- of hardenite From the perspective of type and intensity expression power, relative to 100 mass parts of hydraulic powder, 0.001 mass of (C) ingredient is preferably comprised Part or more, it is more than more preferable 0.01 mass parts, also, preferably 0.5 below the mass, more preferably 0.2 below the mass.

In centrifugal forming hydraulic-composition of the invention, from the intensity of centrifugal forming and/or case-hardening(drying) body From the perspective of viewpoint and the mobility of raising hydraulic-composition, (C) ingredient and mass ratio (C)/(A) of (A) ingredient are excellent Be selected as 0.1 or more, more preferably 0.2 or more, further preferably 0.5 or more, be still more preferably 1 or more, further Preferably 1.3 or more, also, preferably 10 or less, more preferably 7 or less, further preferably 4 or less.

As hydraulic-composition, concrete etc. can be enumerated.Wherein it is preferable to use the concrete of cement.Of the invention Hydraulic-composition is in Self-leveling use, used for refractory material, gypsum use, lightweight or heavy concrete is used, AE is used, repairing use, is pre-installed With, perfusion is used, foundation improvement is used, grouting is used, cold snap with etc. be useful in any field.

Centrifugal forming hydraulic-composition of the invention can also containing the early strength agent such as glycerol and N methyldiethanol amine, The chelating agents such as disodium edta.From the viewpoint of showing the intensity after steam curing, the content of chelating agent relative to 100 mass parts of hydraulic powder are preferably 0.1 mass parts.

Centrifugal forming hydraulic-composition of the invention can contain previous cement dispersants, water soluble polymer Close object, air entraining agent, cement wetting agents, swelling agent, waterproofing agent, delay agent, accelerator, foaming agent, foaming agent, waterproofing agent, flowing The ingredients such as agent, thickener, agglutinant, dry shrinking agent, intensity enhancer, hardening accelerator, preservative, defoaming agent (do not include It is equivalent to the ingredient of (A) ingredient, (B) ingredient or (C) ingredient).

The HLB (Davis's method) of defoaming agent and then aliphatic ester system defoaming agent and ether system defoaming agent is preferably smaller than 0.In addition, The HLB (Griffin method) of defoaming agent and then aliphatic ester system defoaming agent and ether system defoaming agent is preferably 8 or less.In addition, defoaming agent 1 mass % water slurry preferably separated or gonorrhoea under visually.In addition, 1 mass % water slurry of defoaming agent Turbidity is preferably 100NTU or more.In addition, defoaming agent does not preferably have foaming characteristic.It should be noted that above-mentioned 1 mass % water is outstanding The turbidity of supernatant liquid can be used portable nephelometer TN100IR (NIKKO HANSEN corporation) and be measured.

(manufacturing method of centrifugal forming hydraulic-composition)

The present invention provides a kind of manufacturing method of centrifugal forming hydraulic-composition, for by (A) ingredient, (B) ingredient, The manufacturing method for the centrifugal forming hydraulic-composition that hydraulic powder, aggregate and water are mixed, by water and hydraulicity powder Body more than 25 mass % and is to be mixed in a manner of 35 mass % are below by the ratio between water/hydraulic powder.Pass through the manufacturer Method, manufacture contains (A) ingredient, (B) ingredient, hydraulic powder, aggregate and water, and the ratio between water/hydraulic powder is more than 25 matter It measures % and is 35 mass % centrifugal forming hydraulic-composition below.

In addition, the present invention provides a kind of manufacturing method of centrifugal forming hydraulic-composition, it is by (A) ingredient, (B) The manufacturing method for the centrifugal forming hydraulic-composition that ingredient, hydraulic powder, aggregate and water are mixed, does not mix high-strength Spend admixture.By the manufacturing method, manufacture contains (A) ingredient, (B) ingredient, hydraulic powder, aggregate and water, but without height The centrifugal forming hydraulic-composition of intensity admixture.

In addition, the present invention provides a kind of manufacturing method of centrifugal forming hydraulic-composition, it is by (A) ingredient, (B) The manufacturing method for the centrifugal forming hydraulic-composition that ingredient, hydraulic powder, aggregate and water are mixed, does not mix high-strength Admixture is spent, by water and hydraulic powder with the ratio between water/hydraulic powder more than 25 mass % and for 35 mass % sides below Formula is mixed.By the manufacturing method, manufacture contains (A) ingredient, (B) ingredient, hydraulic powder, aggregate and water, but is free of The ratio between high-intensitive admixture, water/hydraulic powder are more than 25 mass % and are the 35 mass % centrifugal forming hydraulicity below Composition.

By these manufacturing methods, centrifugal forming hydraulic-composition of the invention can be manufactured.

(A) ingredient used in the manufacturing method of these centrifugal forming hydraulic-compositions of the invention and (B) ingredient Concrete example and preferred embodiment it is identical as the content illustrated in centrifugal forming hydraulic-composition of the invention respectively.About this The manufacturing method of the hydraulic-composition of invention, can also apply (B)/((A)+(B)), which can also be used based on mixing The amount of (A) ingredient and the amount of (B) ingredient calculate.(B)/((A)+(B)) in manufacturing method can be by the content of each ingredient Combined amount is interpreted as to calculate.When manufacturing centrifugal forming hydraulic-composition of the invention, the preferred model of (B)/((A)+(B)) It encloses identical with the range recorded in hydraulic-composition as centrifugal forming of the invention.

In addition, hydraulic powder used in the manufacturing method of these centrifugal forming hydraulic-compositions of the invention The content recorded in concrete example and preferred embodiment and hydraulic-composition of the invention is identical.Hydraulic powder is preferably with water/water The mode that the ratio between rigid powder reaches the range recorded in hydraulic-composition of the invention come using.

In addition, the concrete example of aggregate used in the manufacturing method of these centrifugal forming hydraulic-compositions of the invention It is identical with the content illustrated in preferred embodiment and hydraulic-composition of the invention.In addition, the dosage of aggregate also with it is of the invention The content recorded in hydraulic-composition is identical.

In addition, the tool of (C) ingredient illustrated in the manufacturing method of these centrifugal forming hydraulic-compositions of the invention Body example and preferred embodiment are identical with the content recorded in hydraulic-composition as centrifugal forming of the invention.

Centrifugal forming of the invention can be suitably applied to hydraulic of the invention with the item recorded in hydraulic-composition The manufacturing method of property composition.

In the manufacturing method of centrifugal forming hydraulic-composition of the invention, from centrifugal forming and/or case-hardening(drying) From the perspective of the intensity of body, relative to 100 mass parts of hydraulic powder, preferably more than mixing 0.001 mass parts of (A) ingredient, More than more preferable 0.01 mass parts, more than further preferred 0.1 mass parts, also, preferably 10 below the mass, more preferably 5 matter Measure part or less, further preferred 3 below the mass, further preferably 2 below the mass, still more preferably 1 below the mass. It is preferred that mixing (A) ingredient in a manner of the content of (A) ingredient in hydraulic-composition to reach centrifugal forming of the invention.

In addition, in the manufacturing method of centrifugal forming hydraulic-composition of the invention, from centrifugal forming and/or performance From the perspective of the intensity of hardenite, relative to 100 mass parts of hydraulic powder, preferably mixing 0.0001 mass parts of (B) ingredient Above, more than more preferable 0.001 mass parts, more than further preferred 0.01 mass parts, still more preferably 0.03 mass parts with More than upper, still more preferably 0.05 mass parts, also, preferably 10 below the mass, more preferably 5 below the mass, further It is preferred that 1 below the mass, further preferably 0.5 below the mass, still more preferably 0.35 below the mass.It is preferred that reach Centrifugal forming of the invention mixes (B) ingredient with the mode of the content of (B) ingredient in hydraulic-composition.

In addition, in the manufacturing method of centrifugal forming hydraulic-composition of the invention, from centrifugal forming and/or performance From the perspective of the intensity of hardenite after centrifugal forming, relative to 100 mass parts of hydraulic powder, preferably mixing (A) ingredient (B) at 0.1 mass parts of subtotaling more than, it is more than more preferable 0.25 mass parts, also, preferably 10 below the mass, more preferably 5 Below the mass, further preferably 2 below the mass, further preferably 1 below the mass.

In the case where use (C) ingredient, in the manufacturing method of centrifugal forming hydraulic-composition of the invention, from from From the perspective of heart mouldability and/or the intensity of case-hardening(drying) body, relative to 100 mass parts of hydraulic powder, preferably mixing (C) More than 0.001 mass parts of ingredient, more than more preferable 0.01 mass parts, more than further preferred 0.05 mass parts, also, preferably 2 Below the mass, more preferably 1 below the mass, further preferably 0.5 below the mass, further preferably 0.3 below the mass.

In the manufacturing method of centrifugal forming hydraulic-composition of the invention, from centrifugal forming and/or case-hardening(drying) From the perspective of the viewpoint of the intensity of body and the mobility of raising hydraulic-composition, with the matter of (C) ingredient and (A) ingredient Amount than (C)/(A) is preferably 0.1 or more, more preferably 0.2 or more, further preferably 0.5 or more, be still more preferably 1 It above, is still more preferably 1.3 or more and preferably 10 or less, more preferably 7 or less, further preferably 4 sides below Formula uses (A) ingredient and (C) ingredient.

In the manufacturing method of centrifugal forming hydraulic-composition of the invention, from making (A) ingredient and (B) ingredient and cement From the perspective of equal hydraulic powders successfully mix, preferably (A) ingredient and (B) ingredient are pre-mixed with water, and and hydraulic Property powder is mixed.

It is mixed that mortar can be used in the mixing of hydraulic powder, water, (A) ingredient, (B) ingredient and ingredient used as needed Clutch forces the mixers such as double-screw mixer to carry out.

Additionally, it is preferred that mixing 1 minute it is above, more preferably mixing 2 minutes or more, also, preferably mix 5 minutes or less, more It is preferred that mixing 3 minutes or less.When preparing hydraulic-composition, the material illustrated in hydraulic-composition, medicine can be used The amount of agent and they.

Hydraulic-composition is further filled into molding box and conserved, solidify resulting hydraulic-composition.Make For molding box, the molding box of building, molding box of concrete product etc. can be enumerated.As filling to molding box method, can enumerate from Method, method that hydraulic-composition force feed is imported into molding box with pump that blender is directly put into etc..

When the maintenance of hydraulic-composition, its solidification can be promoted in order to promote solidification to carry out heating curing.Here, add Thermal curing can keep hydraulic-composition under 40 DEG C or more and 90 DEG C of temperature below to promote to solidify.

(manufacturing method of the hardenite of hydraulic-composition)

The present invention provides a kind of manufacturing method of the hardenite of hydraulic-composition, wherein will comprising (A) ingredient, (B) at Point, the hydraulic-composition of hydraulic powder, aggregate and water mixed with material, the centrifugal forming for preparing aforementioned present invention is used Hydraulic-composition after filling the hydraulic-composition to molding box, applies centrifugal force and is molded.The manufacturing method In, (C) ingredient is also used with material as hydraulic-composition.

(A) ingredient used in the manufacturing method of the hardenite of hydraulic-composition of the invention is specific with (B) ingredient Example and preferred embodiment are identical as the content recorded in hydraulic-composition of the invention respectively.For the hardening of hydraulic-composition The manufacturing method of body can apply (B)/((A)+(B)), but the ratio can also be based on the amount of (A) ingredient used in mixing The amount of (B) ingredient is calculated.That is, (B)/((A)+(B)) in the manufacturing method of the hardenite of hydraulic-composition can be with The content of each ingredient is interpreted as combined amount to calculate.

In addition, the concrete example of hydraulic powder used in the manufacturing method of the hardenite of hydraulic-composition of the invention It is identical with the content recorded in hydraulic-composition with preferred embodiment as centrifugal forming of the invention.

In addition, the concrete example of aggregate used in the manufacturing method of the hardenite of hydraulic-composition of the invention and preferably The content illustrated in mode and hydraulic-composition of the invention is identical.In addition, the dosage of aggregate also with the hydraulicity of the invention The content recorded in composition is identical.

In addition, (C) ingredient used in the manufacturing method of the hardenite of these hydraulic-compositions of the invention is specific The content illustrated in example and preferred embodiment and hydraulic-composition of the invention is identical.

The item illustrated in the manufacturing method of hydraulic-composition and hydraulic-composition of the invention can be applied suitably In the manufacturing method of the hardenite of hydraulic-composition of the invention.

In the present invention, it is more than 25 mass % and below of the invention for 35 mass % to prepare the ratio between water/hydraulic powder Centrifugal forming hydraulic-composition, is filled with to molding box, carries out centrifugal forming.

In addition, of the invention centrifugal forming hydraulic-composition of the preparation without high-intensitive admixture will in the present invention It is filled to molding box, and centrifugal forming is carried out.

In addition, in the present invention, preparation without high-intensitive the ratio between admixture and water/hydraulic powder more than 25 mass % and It for 35 mass % centrifugal forming hydraulic-composition of the invention below, is filled with to molding box, carries out centrifugal forming.

In the present invention, from when manufacture hydraulic-composition can also easily mixed uniformly viewpoint, preferably will packet The mixture of aqueous, (A) ingredient and (B) ingredient is added to aggregate and hydraulic powder and mixed method.Said mixture can To further include (C) ingredient.

Centrifugal forming hydraulic-composition can be by mixing hydraulic powder with aggregate, and to reach as described above The mode of combined amount adds the mixture comprising water, (A) ingredient and (B) ingredient, is kneaded to prepare.Said mixture can be with Further include (C) ingredient.

(A) ingredient, (B) ingredient, (C) ingredient can be added separately to water, hydraulic powder, aggregate in turn, and mixed It closes.

Water, (A) ingredient, (B) ingredient, in turn preferred scope and sheet of (C) ingredient relative to the mixing amount of hydraulic powder The preferred scope of the content of each ingredient in the centrifugal forming hydraulic-composition of invention is identical.

In the present invention, from the viewpoint of the intensity of centrifugal forming and/or case-hardening(drying) body, water/hydraulicity powder is prepared The ratio between body more than 25 mass %, preferably 25.5 mass % or more, more preferably 26 mass % or more and for 35 mass % with Under, preferably 30 mass % or less, more preferably 27 mass % centrifugal forming hydraulic-composition below.It is preferred that with water/ The mode that the ratio between hydraulic powder reaches the range mixes hydraulic powder.

Molding box is contemplated that the purposes of the hardenite of centrifugal forming hydraulic-composition suitably to select.Above-mentioned hydraulicity group Closing filling of the object into molding box can be carried out by known method.

Gained centrifugal forming can be enumerated for example with the method that hydraulic-composition is filled to molding box by the water after mixing Hydraulic composition is discharged from mixing unit, and puts into molding box by manual working and carry out smooth method.

In the present invention, centrifugal force is applied with hydraulic-composition to centrifugal forming of the filling into molding box and is molded. At this point, preferably at least changing 1 centrifugal force.In the present invention, interim become can be applied to centrifugal forming hydraulic-composition The centrifugal force of change is simultaneously molded.That is, can at least change 1 centrifugation to centrifugal forming hydraulic-composition in the present invention Power is simultaneously molded, and then is applied interim change, the interim centrifugal force to become larger and molded.

In the present invention, the centrifugal forming hydraulic-composition preferably by filling into molding box is with the centrifugal force of 0.5G or more It is molded.The centrifugal force of centrifugal forming is preferably 0.5G or more, also, is 30G or less, more preferably 25G or less.From energy Set out in terms of aspect and mouldability that cost reduces, preferably by centrifugal force in 15G or more and 30G or less so 25G it is below It is kept for 1 minute or more at range (also referred to as high centrifugal force).

Compacting based on centrifugal force, for example, with 0.5G or more and 30G centrifugal force below carry out preferably 5 minutes or more, more It is preferred that 7 minutes or more, further preferred 9 minutes or more, and preferably 40 minutes or less.From the viewpoint for being smoothly compacted formed body Set out, by keep the compacting realized of centrifugal force of high centrifugal force, such as 20G or more carry out preferably 1 minute or more, it is more preferable 3 minutes or more, further preferred 5 minutes or more, and preferably 15 minutes or less.That is, in the present invention, can by 0.5G or more and 30G centrifugal force application preferably 5 minutes or more, more preferable 7 minutes below or more, further preferred 9 minutes or more and preferably 40 Minute is hereinafter, to mold centrifugal forming with hydraulic-composition.In addition, holding 20G can will be passed through in the present invention Above centrifugal force and the compacting realized carry out preferably 1 minute or more, more preferable 3 minutes or more, further preferred 5 minutes with On, and preferably 15 minutes or less.

Compacting based on centrifugal force can carry out stage by stage, from the viewpoint of mouldability, make to be centrifuged preferably in stages The method that power G becomes larger.It can be compacted with stage conditions as follows, until becoming required centrifugal force.For example, In the case where five stages, in the present invention, the molding of centrifugal forming hydraulic-composition is preferably carried out by the following conditions: (1) first stage with initial velocity be centrifugal force of the 0.5G more than and less than 2G, be greater than 0 minute and 15 minutes hereinafter, (2) second-order Section with two speed be centrifugal force of the 2G more than and less than 5G, be greater than 0 minute and 15 minutes hereinafter, (3) phase III with three speed Centrifugal force for 5G more than and less than 10G, be greater than 0 minute and 15 minutes hereinafter, (4) fourth stage with four-speed for 10G or more And less than 20G centrifugal force, be greater than 0 minute and 15 minutes hereinafter, (5) the 5th stages with five speed be 20G or more and 30G or less Centrifugal force, be greater than 0 minute and 15 minutes or less.

In the present invention, after preferably centrifugal forming is applied centrifugal force and molded with hydraulic-composition, then added Thermal curing.

In turn, the present invention in, preferably carry out include following processes heating curing, the process are as follows: preparative centrifugation at After type hydraulic-composition, after during temperature and time is specific curing degree, kept for 1 hour or more with 75 DEG C or more Process.

That is, will be used comprising the hydraulic-composition of (A) ingredient, (B) ingredient, hydraulic powder, aggregate and water in the present invention Material is mixed and prepares centrifugal forming hydraulic-composition of the invention, but preferably carry out include following processes heating Maintenance, the process are as follows: in above-mentioned mixing, through overdone within 6 hours from the time of water is initially contacted with hydraulic powder It is small with 75 DEG C or more holdings 1 after change degree is 60 DEG C of h or more and 150 DEG C of h period below (hereinafter referred to as during curing degree) When more than process.

In other words, present invention it is preferred that: by the hydraulic-composition material comprising water, hydraulic powder and aggregate Material is mixed and prepares centrifugal forming hydraulic-composition of the invention, which is filled with hydraulic-composition After in molding box, carry out heating curing, in above-mentioned mixing, from the time of water and hydraulic powder initially contact 6 hours with It is interior, during being 60 DEG C of h or more and 150 DEG C of h curing degrees below there are curing degree, during the curing degree after exist with 75 DEG C or more keep 1 hour it is above during (during following otherwise referred to as holding), heating curing at least during holding into Row.

Heating curing is carried out at preferably 75 DEG C or more and preferably 100 DEG C or less, more preferable 90 DEG C or less.Heating curing can be with Process including being kept for 1 hour or more with 75 DEG C or more.It should be noted that heat-cured temperature is filled with hydraulicity group Close the temperature of the surrounding atmosphere of the molding box of object.

Above-mentioned curing degree is calculated by formula (C-30) × T integrating, and herein, T is initially reached with the ambient temperature of molding box As starting point and the ambient temperature of molding box is in 30 DEG C or more and 65 DEG C times (time) below, C at the time of to 30 DEG C or more The ambient temperature (DEG C) of molding box when for time T.In other words, in the calculating of curing degree, the time is at the time of 30 DEG C to reach Starting point, i.e. zero point.For example, the situation that the molding box that centrifugal forming hydraulic-composition is arranged in the atmosphere for being set as 40 DEG C is such Under, temperature C at the time of initially reaching 30 DEG C or more is 40 DEG C, and using 30 DEG C of zero point as benchmark, 40 DEG C are used as (40 DEG C -30 DEG C)=10 DEG C calculate curing degree.

It further include the temperature and time of this period to calculate curing when with 30 DEG C or more progress centrifugal formings, low temperature reservation Degree.

In the case where applying centrifugal force and being molded, from the viewpoint of the loss that collapses, the ambient temperature (week of molding box Enclose temperature) be preferably 35 DEG C or less, further preferably 30 DEG C or less, be more preferably 25 DEG C hereinafter, from the sight of intensity expression power Point sets out, and preferably 10 DEG C or more, further preferably 15 DEG C or more, more preferably 20 DEG C or more.

During curing degree, the ambient temperature of molding box is in 30 DEG C or more and 65 DEG C or less.In addition, during curing degree Within 6 hours from the time of above-mentioned mixing Shi Shuiyu hydraulic powder initially contacts.Therefore, even if in above-mentioned mixing Within 6 hours from the time of water and hydraulic powder initially contact, in time of the ambient temperature of molding box less than 30 DEG C or In the case where 65 DEG C, the temperature and time in the region is not used in the calculating of curing degree.Similarly, even if it is warm around molding box Degree for 30 DEG C or more and 65 DEG C hereinafter, in above-mentioned mixing, more than 6 hours from the time of water is initially contacted with hydraulic powder In the case where, the temperature and time in the region is without in the calculating of curing degree.

Curing degree can calculate as follows: the relationship of the temperature and time of curing condition is tabulated, as in above-mentioned mixing from From at the time of water and hydraulic powder initially contact within 6 hours, temperature is in the face in 30 DEG C or more and 65 DEG C regions below Product is to calculate.

Curing degree as integrating temperature be it is known, calculating formula is also known those skilled in the art.As The standard of curing degree is stated, such as it has been known that there is ASTM C1074 etc..In addition, the simple device that can measure curing degree is also known 's.Consider condition of the invention, also can use these documents, device etc..That is, curing degree of the invention can also refer to it is well known Calculating formula is calculated, if indicating the calculating formula of curing degree based on condition of the invention, such as follows.

M=Σ (C-30) Δ T

M: curing degree

T: as starting point at the time of initially reaching 30 DEG C or more using the ambient temperature of molding box, the ambient temperature of molding box is in 30 DEG C or more and 65 DEG C of times (hour) below

C: the average ambient temperature (DEG C) of molding box when Δ T

Herein, in the present invention, when " T " in formula is the mixing for being used to prepare hydraulic-composition, from water and hydraulicity powder Time present in region from the time of body initially contacts within 6 hours.In addition, " C " in formula indicates (example per unit time Such as every 1 minute) measurement ambient temperature the unit time mean temperature.

The lower limit of curing degree can be selected from 60 DEG C of h or more, 65 DEG C of h or more or 70 DEG C of h or more.In addition, The upper limit of curing degree can be selected from 150 DEG C of h or less, 140 DEG C of h or less or 130 DEG C of h or less.

In general, in the manufacture of the hardenite of hydraulic-composition, low temperature reservation is carried out to hydraulic-composition, is connect , carry out heating curing.It can be set during curing degree of the invention between low temperature reservation and heating curing.In addition, low temperature During part or all of maintenance may be embodied in curing degree.In addition, heat-cured a part may be embodied in curing During degree.

Present invention it is preferred that before beginning to warm up maintenance, in above-mentioned mixing, most with water and hydraulic powder As starting point, progress 1 hour or more low temperature reservation at the time of just contact.

Low temperature reservation preferably 0 DEG C or more, more preferable 10 DEG C or more and preferably 40 DEG C or less, more preferable 30 DEG C or less into Row.

Low temperature reservation preferably carries out 1 hour or more, more preferably progress 2 hours or more, also, preferred progress 5 hours or less, More preferably carry out 4 hours or less.

Low temperature reservation preferably during curing degree before carry out.For example, curing temperature is less than 30 before during curing degree Preferably exist 1 hour or more during DEG C.

When changing heat-cured temperature stage, it is easy to make to be contained in heat-cured a part during curing degree.

Hereinafter, being illustrated for the situation of a part during being present in heating curing during curing degree.

It, can be with for the heating curing (heating curing hereinafter also referred to during curing degree) during curing degree in the present invention Atmosphere temperature heating around molding box is carried out, also can be set in the atmosphere of specific temperature filled with centrifugal forming hydraulic The molding box of property composition carries out.

At least part in heating curing during curing degree is carried out at 30 DEG C or more and 65 DEG C or less.It needs to illustrate It is that the heating curing temperature during curing degree is filled with the temperature of the surrounding atmosphere of the molding box of centrifugal forming hydraulic-composition Degree.

In the present invention, by the heating curing during curing degree, to ripe for carrying out from the time of initially reaching 30 DEG C Heat-cured heating after during change degree start until during curing degree be preferably above range.

The temperature in heating curing during curing degree can fix, and can also change.Temperature change can be continuity, Any one of interim, deficient property.Temperature change is preferably the variation that temperature rises.In the present invention, adding during curing degree Temperature in thermal curing rises preferably in stages.

In heating curing during curing degree, the phase of temperature risen with holding during increase temperature is preferably included Between.It can be respectively present during these multiple.Keep temperature to refer to: the amplitude of variation of temperature can be 5 DEG C/h or less.Make During temperature rising, the rate of climb of temperature is preferably 5 DEG C/h or more and 20 DEG C/h or less.

As the heat-cured more specific example during curing degree, example below can be enumerated.

Following heating curing can be enumerated:

(1) ambient temperature that will be filled with the molding box of centrifugal forming hydraulic-composition is set as 30 DEG C more than and less than 55 DEG C, and kept for 0.5 hour or more；Then,

(2) it will be filled with the ambient temperature of the molding box of centrifugal forming hydraulic-composition to protect with 55 DEG C or more and 65 DEG C or less It holds 0.5 hour or more, in the heating curing, total curing degree that the retention time of (1) and (2) is in (1) and (2) reaches 60 DEG C h or more and 150 DEG C of h range below.

In the present invention, heating curing is preferably carried out by steam curing.Steam curing is for example by filled with centrifugation Vapor is applied around the molding box of formed hydraulic composition, keeps certain time to carry out with specific temperature.Herein plus Thermal curing include curing degree during heating curing.

It is included in the heating for keeping the process on 1 hour after during curing degree, with 75 DEG C or more in the present invention It conserves (heating curing after hereinafter also referred to during curing degree).

Preferred progress 1 hour or more is played after during the auto-cure degree of heating curing after during curing degree and preferably 6 is small When below, more preferable 5 hours or less.

Heating curing after during curing degree is preferably carried out by steam curing.Steam curing is for example by being filled with Vapor is applied around the molding box of centrifugal forming hydraulic-composition, keeps certain time to carry out with specific temperature.

It is after heating curing after during curing degree, hydraulic-composition is cooling, it can be demoulded from molding box.Separately Outside, the hardenite of the hydraulic-composition demoulded can be conserved at normal temperatures and pressures.

For example, after heating curing after during curing degree, for example, can immediately be cooled to room temperature ambient temperature, Such as until 20 DEG C, for example, ambient temperature can be cooled to room with every 1 hour 5 DEG C or more and 20 DEG C of cooling rates below Temperature, until such as 20 DEG C.After the cooling period, formed body is demoulded.From inhibition strength reduction as caused by the crackle of hardenite From the perspective of, cooling rate be preferably every 1 hour 20 DEG C or less.Furthermore it is possible at normal temperatures and pressures to gained hydraulicity group The hardenite for closing object is conserved.Specifically, can be saved under 20 DEG C, atmospheric pressure.

In the manufacturing method of hardenite of the invention, mass ratio (C)/(A) of (C) ingredient and (A) ingredient be preferably 0.1 with It goes up, be more preferably 0.2 or more, be more preferably 0.5 or more, be still more preferably 1 or more, be still more preferably 1.3 More than, also, preferably 10 or less, more preferably 7 or less, further preferably 4 or less.

The hardenite for the hydraulic-composition that the manufacturing method of hardenite through the invention obtains can be used as centrifugal forming Concrete product uses, specifically, stake, bar, smoke pipe etc. can be enumerated.The manufacturer of first group of hardenite through the invention The initial strength of the hardenite for the hydraulic-composition that method obtains is excellent, while the occurrence quantity of slag when manufacturing is few, can subtract The waste at the manufacture scene of few product.In addition, excellent due to being compacted, the inner face of the product and the bumps of end face are few, Surface aesthetic is excellent, and is smooth shape further as product inner face, therefore when piling, middle hole engineering method (boring method in stake) The failure of cutter is improved.

In addition to that mentioned above, the invention discloses contain (A) ingredient, (B) ingredient, hydraulic powder, aggregate and water, and The ratio between water/hydraulic powder is used as centrifugal forming hydraulicity group more than 25 mass % and for 35 mass % compositions below Close the purposes of object.

In addition, the invention discloses (A) ingredient, (B) ingredient, hydraulic powder, aggregate and water is contained, but without high intensity The purposes as centrifugal forming hydraulic-composition of the composition of admixture.

In addition, the invention discloses (A) ingredient, (B) ingredient, hydraulic powder, aggregate and water is contained, but without high intensity The ratio between admixture, water/hydraulic powder as centrifugal forming more than 25 mass % and using for 35 mass % compositions below The purposes of hydraulic-composition.

These with can suitably apply on the way hydraulic-composition of the invention, hydraulic-composition manufacturing method, with And the item described in the manufacturing method of the hardenite of hydraulic-composition.

In addition, the invention discloses the composition for centrifugal forming hydraulic-composition, the composition contain (A) at Point, (B) ingredient, hydraulic powder, aggregate and water, and the ratio between water/hydraulic powder be more than 25 mass % and be 35 mass % with Under.

In addition, the invention discloses the composition for centrifugal forming hydraulic-composition, the composition contain (A) at Point, (B) ingredient, hydraulic powder, aggregate and water, but without high-intensitive admixture.

In addition, the invention discloses the composition for centrifugal forming hydraulic-composition, the composition contain (A) at Point, (B) ingredient, hydraulic powder, aggregate and water, but without high-intensitive admixture, the ratio between water/hydraulic powder is more than 25 matter It measures % and is 35 mass % or less.

Can suitably be applied in these compositions hydraulic-composition of the invention, hydraulic-composition manufacturing method, And the item described in the manufacturing method of the hardenite of hydraulic-composition.

Embodiment

The hardenite of concrete is manufactured, intensity is evaluated.It is as described below respectively for the cooperation, preparation, evaluation of concrete.

(1) proportion of concrete

The gradation composition and concrete mixer of concrete are as follows.

(A) ingredient: the sodium salt of naphthalene sulfonic acid-formaldehyde condensation product, weight average molecular weight 15,000

(B) ingredient: polyoxyethylene (average addition molal quantity is 50) stearyl ether (HLB (Davis's method) is 0 or more)

(C) ingredient: polycarboxylic acid system dispersant, weight average molecular weight 30,000, AK ChemTech Co., LTD., VAM 533

It is kneaded water (W): tap water

Cement (C): cement 52.5R (foreign-style house cement company system), density 3.16g/cm³

Fine aggregate (S): Chengyang Shan Shan sand (the Japan Ishikawa County Ha Noi village broken sand in the mountain Chan An), density 2.50g/cm³

Coarse aggregate (G1): rubble (Japan Hyogo Prefecture Xi Dao produces rubble 2010), density 2.63g/cm³

Coarse aggregate (G2): rubble (Japan Hyogo Prefecture Xi Dao produces rubble 1005), density 2.63g/cm³

Concrete mixer: IHI corporation forces double-screw mixer, 20 liters of mixings

(2) preparation of concrete hardening body

Cement, fine aggregate, coarse aggregate are put into using concrete mixer according to matching requirements shown in table 1, carries out 30 Second it is empty be kneaded, the water of the half of water (W) is added, 60 seconds (revolving speed 45rpm) is kneaded, thereafter, by (A) ingredient, (B) Ingredient, (C) ingredient, defoaming agent and hydration simultaneously, are added surplus water (W), after being kneaded 60 seconds, obtain concrete.With (A) at Divide, the additive amount mode as shown in Table 2 of (B) ingredient, (C) ingredient relative to 100 mass parts of cement, is added in water, obtains Centrifugal forming concrete.

Defoaming agent is FOAMLEX 797 (Nicca Chemical Co., Ltd).There is only do not add to disappear when (A) ingredient in comparative example Infusion.There is only when (C) ingredient, add the defoaming agent for being 0.5 mass % relative to (C) ingredient in comparative example.Add in embodiment Add the defoaming agent for being 3 mass % relative to (B) ingredient.

Centrifugal forming condition:

Centrifugal forming is put into concrete 15kg into centrifugal forming molding box (internal diameter 20cm × height 30cm), centrifugation pressure It is real to be carried out 5 minutes with initial velocity 1G progress 3 minutes, with two speed 5G progress 1 minute, with three speed 10G progress 1 minute, with four-speed 25G. Room temperature in centrifugal forming is 22 DEG C.

Curing condition:

For the concrete after centrifugal forming, 2 hours low temperature reservations are carried out with 22 DEG C, then, are carried out 1 hour with 40 DEG C Heating curing be then warming up to 60 DEG C with 1 hour, then, be warming up to 65 DEG C with 1.5 hours, then, with 1.5 hours heat up To 85 DEG C, then, 1.5 hours heating curings are carried out with 85 DEG C.Natural cooling is carried out later.

Under this condition, from after during curing degree is 78.75 DEG C of h, heating curing is carried out.

It should be noted that in centrifugal forming in low temperature reservation be 22 DEG C, due to not counting curing less than 30 DEG C In degree.

(3) evaluation of the workability of concrete

After mixer mixing, the workability of concrete when discharge is evaluated according to following benchmark.Show the result in table 2。

Zero: workability is good.The concrete of the level is easily processed, and also fits easily in molding box.

△: workability is general.Although the concrete viscosity of the level is up to a certain degree, it is packed into without hindrance.

×: workability is poor.The viscosity of the concrete of the level is high, it is difficult to handle.

(4) evaluation of concrete hardening body

After demoulding, hardenite is placed under room temperature (20 DEG C), prepares hydraulic-composition Shi Shuiyu hydraulicity powder certainly From at the time of body initially contacts after 3 days, the compressive strength of hardenite is measured based on JIS A 1108.It is strong using result as 3 days It spends and is shown in table 2.

In addition, observing the appearance of hardenite by visual observation, and mouldability is evaluated according to following benchmark.It shows the result in Table 2.

Zero: good forming ability.There is no gap, defect, floating sand, collapse, the hardenite of beautiful appearance can be obtained.

△: mouldability is common.Although there are small gap, it is several collapse, can obtain permitting as product Perhaps the hardenite of level.

×: insufficient formability.Hardenite can not be obtained by centrifugal forming.

[table 1]

[table 2]

In table 2, additive amount is mass parts of the solid component relative to 100 mass parts of cement.

Comparative example 1 and 2 is that there is only the evaluation results of (A) ingredient.As the comparative example 1, in proportion 1, in order to obtain Good workability, mouldability can reduce the additive amount of (A) ingredient, but can not obtain intensity.In addition, as comparative example 2 that Sample, in proportion 2, only the intensity as obtained from (A) ingredient is 89.50N/mm², in order to improve intensity, additive amount needs are More.

If mixing agent and known (C) ingredient used as concrete for proportion 2, as comparative example 3 and 4, though Right intensity improves, but workability and mouldability deteriorate.

In contrast, in the embodiment that combination has (A) ingredient and (B) ingredient, can take into account high-intensitive and workability, at Type.

Claims

1. a kind of centrifugal forming hydraulic-composition, contains:

(A) comprising the hydraulic powder dispersing agent of the high-molecular compound containing aromatic rings；

(B) selected from shown in the following general formula (B1) compound represented, the following general formula (B2) compound represented, the following general formula (B3) Compound and one or more of the following general formula (B4) compound represented compound；

Hydraulic powder；

Aggregate；And

Water,

The ratio between water/hydraulic powder of the centrifugal forming hydraulic-composition more than 25 mass % and for 35 mass % with Under,

In formula,

X indicates O or COO；

AO indicates the alkylene oxide group below of carbon number 2 or more and 4；

n₃、n₄Identical or different, the average addition molal quantity of respectively AO, is 0 or more number, n₃With n₄1 or more total expression And 200 number below；

n₅、n₆Identical or different, the average addition molal quantity of respectively AO, is 0 or more number, n₅With n₆Add up to 1 or more and 200 numbers below, n₅When being 0, Y¹For hydrogen atom, n₆When being 0, Y²For hydrogen atom；

M indicates counter ion counterionsl gegenions.

2. a kind of centrifugal forming hydraulic-composition, contains:

Hydraulic powder；

Aggregate；And

Water,

Centrifugal forming hydraulic-composition is free of high-intensitive admixture,

In formula,

X indicates O or COO；

AO indicates the alkylene oxide group below of carbon number 2 or more and 4；

M indicates counter ion counterionsl gegenions.

3. a kind of centrifugal forming hydraulic-composition, contains:

Hydraulic powder；

Aggregate；And

Water,

Centrifugal forming hydraulic-composition is free of high-intensitive admixture, and the ratio between water/hydraulic powder is more than 25 mass % And be 35 mass % hereinafter,

In formula,

X indicates O or COO；

AO indicates the alkylene oxide group below of carbon number 2 or more and 4；

M indicates counter ion counterionsl gegenions.

4. centrifugal forming hydraulic-composition described in any one of claim 1 to 3, wherein relative to the hydraulicity 100 mass parts of powder, the total content of (A) and (B) be 0.25 mass parts or more and 10 below the mass.

5. centrifugal forming hydraulic-composition according to any one of claims 1 to 4, wherein relative to the hydraulicity 100 mass parts of powder, containing more than 0.001 mass parts and 10 (A) below the mass.

6. centrifugal forming hydraulic-composition according to any one of claims 1 to 5, wherein relative to the hydraulicity 100 mass parts of powder, containing more than 0.0001 mass parts and 10 (B) below the mass.

7. centrifugal forming hydraulic-composition described according to claim 1~any one of 6, wherein (A) is to include high score The hydraulic powder dispersing agent of sub- compound, the high-molecular compound have the monomeric unit containing aromatic rings.

8. centrifugal forming hydraulic-composition according to any one of claims 1 to 7 also contains (C) polycarboxylic acids Based copolymer.

9. a kind of manufacturing method of the hardenite of hydraulic-composition, hydraulic-composition is mixed with material, preparation Centrifugal forming hydraulic-composition according to any one of claims 1 to 8, which is filled to molding box Afterwards, apply centrifugal force and molded,

The hydraulic-composition includes with material:

Hydraulic powder；

Aggregate；And

Water,

In formula,

X indicates O or COO；

AO indicates the alkylene oxide group below of carbon number 2 or more and 4；

M indicates counter ion counterionsl gegenions.

10. the manufacturing method of the hardenite of hydraulic-composition according to claim 9, wherein to the hydraulicity group After closing object application centrifugal force and being molded, heating curing is carried out.

11. the manufacturing method of the hardenite of hydraulic-composition according to claim 10, wherein in the mixing, From at the time of water and hydraulic powder initially contact within 6 hours by curing degree be 60 DEG C of h or more and 150 DEG C of h with After during lower, the heating curing is carried out,

The curing degree is calculated by formula (C-30) × T integrating,

Herein, T is at the time of initially reaching 30 DEG C or more using the ambient temperature of molding box as at starting point and the ambient temperature of molding box In 30 DEG C or more and 65 DEG C of times below, the unit of the time is hour, the ambient temperature of molding box when C is time T, this week Enclose temperature unit be DEG C,

The heating curing includes the process for being kept for 1 hour or more at 75 DEG C or more.

12. the manufacturing method of the hardenite of hydraulic-composition described in 0 or 11 according to claim 1, wherein beginning to warm up It is small carrying out 1 lower than 40 DEG C as starting point at the time of initially contact using the water when mixing with hydraulic powder before maintenance When more than low temperature reservation.

13. a kind of purposes as centrifugal forming hydraulic-composition of composition, the composition contain:

Hydraulic powder；

Aggregate；And

Water,

The ratio between water/hydraulic powder of the composition more than 25 mass % and be 35 mass % hereinafter,

In formula,

X indicates O or COO；

AO indicates the alkylene oxide group below of carbon number 2 or more and 4；

M indicates counter ion counterionsl gegenions.

14. a kind of purposes as centrifugal forming hydraulic-composition of composition, the composition contain:

Hydraulic powder；

Aggregate；And

Water,

The composition is free of high-intensitive admixture,

In formula,

X indicates O or COO；

AO indicates the alkylene oxide group below of carbon number 2 or more and 4；

M indicates counter ion counterionsl gegenions.

15. a kind of purposes as centrifugal forming hydraulic-composition of composition, the composition contain:

Hydraulic powder；

Aggregate；And

Water,

The composition is free of high-intensitive admixture, the ratio between water/hydraulic powder be more than 25 mass % and for 35 mass % hereinafter,

In formula,

X indicates O or COO；

AO indicates the alkylene oxide group below of carbon number 2 or more and 4；

M indicates counter ion counterionsl gegenions.