JP2003002719A - Admixture for extruded formed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an admixture for extruded formed body by which the extruding speed is not varied independent of temperature of cement composition and the stable quality can be obtained through a year. SOLUTION: This admixture consists of a copolymer mixture (a) which is obtained by copolymerizing a specified monomer A1 such as ethylene type unsaturated carboxylic acid derivative having polyoxyalkylene groups and a specified monomer A2 such as (meth)acrylic acid and has the molar ratio A1/A2 which is changed at least one time in the process of reaction, and a specified water soluble polymer (b) such as a nonionic cellulose ether.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cement-based admixture for extrusion-molded articles, and more specifically, it suppresses fluctuations in extrusion rate of a water-kneaded product containing a cementitious material as a main raw material due to temperature change, and The present invention relates to an admixture for a cement-based extruded product, which reduces the resistance of the composition.

[0002]

2. Description of the Related Art Cement-based extrusion moldings are obtained by molding a clay-like ultra-high viscosity substance containing cementitious material as a main component by an extrusion molding machine. Conventionally, asbestos, carbon fiber, vinylon fiber Bending strength is increased by mixing organic and inorganic fibers such as nylon fiber. A water-kneaded product of a cementitious material has low shape retention and water retention even if it is extrusion-molded as it is, slippage in the cylinder and die of the extruder is poor, and mold release at the die exit is poor. Therefore, a product having a smooth surface cannot be obtained, resulting in a molded product that does not conform to a predetermined shape.

The idea of adding plasticity to a cement-based extruded product by adding a water-soluble polymer such as methylcellulose or hydroxymethylcellulose has also been proposed (for example, JP-A-61-256957). However, in the case of these admixtures, the tackiness is too large, and the slipperiness and releasability are poor,
The extrusion speed is low, and the surface smoothness of the molded product is poor, so that a satisfactory product has not been obtained.

In order to solve these problems, a polycarboxylic acid type admixture having a specific structure (JP-A-6-100347).
No.) was developed, but when this polycarboxylic acid-based admixture is used, the extrusion speed varies depending on the temperature of the cement composition for extrusion molding, and stable quality may not be obtained throughout the year. Had.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an admixture for an extruded product, the extrusion rate of which does not vary depending on the temperature of the cement composition, and which allows stable quality throughout the year.

[0006]

The present invention has the following general formula:
(a1) is obtained by copolymerizing at least one monomer (A1) represented by the following general formula (a2) and at least one monomer (A2) represented by the following general formula (a2), and Monomer (A1) and (A2) molar ratio
A copolymer mixture (A) in which (A1) / (A2) is changed at least once during the reaction, and at least one water-soluble polymer (B) selected from the following (B1) to (B8) It relates to an admixture for an extruded body containing

[0007]

[Chemical 3]

(In the formula, R ¹ and R ² : hydrogen atom or methyl group R ³ : hydrogen atom or --COO (AO) _{m 1} X m: number of 0-2 p: 0 or number of 1 n: 2-300 AO: an oxyalkylene group having 2 to 4 carbon atoms or an oxystyrene group X: represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)

[0009]

[Chemical 4]

(In the formula, R ^{4 to} R ^{6 are a} hydrogen atom, a methyl group or (CH ₂ ) _{m 1} COOM ² ,
(CH _{²⁾ m1} COOM ₂ may form a COOM ¹ or another (CH _{²⁾ m1} COOM ₂ and anhydride, in which case, M ^1, M ² in these groups are not present. M ¹ , M ² : hydrogen atom, alkali metal, alkaline earth metal,
An ammonium group, an alkylammonium group, or a substituted alkylammonium group m1: represents the number of 0 to 2. ) (B1) Nonionic cellulose ether (B2) Acrylic acid copolymer (B3) Polyalkylene glycol (B4) Polysaccharide obtained by fermentation (B5) Xanthan gum (B6) Monohydric alcohol or carbon having 6 to 30 carbon atoms Average of alkylene oxide to C6 to C30 monovalent mercaptan, C6 to C30 alkyl-containing alkylphenol, C6 to C30 amine or C6 to C30 carboxylic acid
Alkylene oxide derivative (B7) having 10 to 1000 moles added thereto has an average of 10 alkylene oxides in a monohydric alcohol having 6 to 30 carbon atoms, a monohydric mercaptan having 6 to 30 carbon atoms or an alkylphenol having an alkyl having 6 to 30 carbon atoms.
The reaction product of the alkylene oxide derivative added with ˜1000 mol and the compound having one or more epoxy groups (B8) The hydrogen atom of all or part of the hydroxyl groups of the polysaccharide or its alkylated or hydroxyalkylated derivative is carbon. A hydrophobic substituent (P) having a hydrocarbon chain of the number 8 to 40 as a partial structure, and one or more groups selected from the group consisting of sulfonic acid groups, carboxyl groups, phosphoric acid groups, sulfuric acid ester groups and salts thereof. A polysaccharide derivative which is substituted with an ionic hydrophilic group (Q) having a partial structure of.

The present invention also relates to an extruded product produced by using the admixture for an extruded product of the present invention.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In order for the polycarboxylic acid-based copolymer to which alkylene oxide is added to exhibit stable properties with respect to temperature changes of the extrusion molding cement composition,
It is necessary that a large number of copolymers having different weight ratios of the monomer (A2) be mixed.

However, when copolymers having different weight ratios of the monomer (A2) are produced and mixed, the production efficiency is low for mass production and the production cost increases, so that the types that can be mixed are different. Limited

On the other hand, the copolymer mixture (a) used in the present invention has a molar ratio (A1) / (A2) of the monomers (A1) and (A2).
Is considered to be a copolymer mixture in which the weight ratio of the monomer (A2) is continuously distributed by changing at least once during the reaction, and an admixture capable of imparting stable properties to the use temperature. Can be obtained in large quantities and at low cost.

[Monomer (A1)] In order to impart a good extrusion speed to the cement composition for extrusion molding, the addition mole number n of alkylene oxide in the monomer (A1) is 50 <n.
Is preferable, 70 ≦ n is more preferable, and 80 ≦ n
Is more preferable, 90 ≦ n is more preferable, 100 ≦ n is further preferable, and 110 ≦ n is most preferable.

When n is too large, the viscosity of the cement composition for extrusion molding becomes excessive and the extrusion rate is rather lowered. Therefore, it is necessary that n≤300, preferably n≤200, and n≤150. Most preferred.

In order to further suppress the variation of the cement composition for extrusion molding with respect to temperature change, the number of moles n of alkylene oxide added in the monomer (A1) is 2 ≦ n ≦ 5.
0 is preferable, 5 ≦ n ≦ 40 is more preferable, and 5 ≦ n ≦ 40 is preferable.
≦ n ≦ 30 is more preferable, and 5 ≦ n ≦ 20 is most preferable.

Further, in order to impart a high level of extrusion rate and temperature stability to the cement composition for extrusion molding, it is preferable that the monomer (A1) contains different n monomers. In this case, it is preferable to contain at least n1 and n2 monomers satisfying 2 ≦ n1 ≦ 50 <n2 ≦ 300. When emphasizing the extrusion speed more, 70 ≦ n2 is more preferable, 80 ≦ n2
n2 is more preferable, 90 ≦ n2 is further preferable, 100 ≦ n2 is further preferable, and 110 ≦ n2 is most preferable. Further, when more importance is attached to stability against temperature change, 5 ≦ n1 ≦ 40 is preferable, 5 ≦ n1 ≦ 30 is more preferable, and 5 ≦ n1 ≦ 20 is most preferable.

[Monomer (A2)] Examples of the monomer (A2) represented by the general formula (a2) used for producing the copolymer mixture (a) include (meth) acrylic acid and crotonic acid. Monocarboxylic acid type monomers, maleic acid, itaconic acid, dicarboxylic acid type monomers such as fumaric acid, or their anhydrides or salts,
For example, an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and a mono-, di-, or trialkyl (having 2 to 8 carbon atoms) ammonium salt in which a hydroxyl group may be substituted are preferable,
(Meth) acrylic acid, maleic acid, maleic anhydride are more preferable, and (meth) acrylic acid or an alkali metal salt thereof is more preferable.

[Copolymer Mixture (a)] The copolymer mixture (a) comprises the monomers (A1) and (A2), preferably (A1) / (A
2) contains a copolymer mixture (A) obtained by reacting at a molar ratio in the range of 0.02 to 4, and these molar ratios (A1) / (A
2) is changed at least once during the reaction.
And, in the present invention, the average weight ratio (X _I ) of the monomer (A2) to all the monomers for producing the copolymer mixture (a) and the average weight ratio (X _II ) different from that were obtained. It is preferable to use the copolymer mixture (a ′) together. That is, the copolymer mixture (a ′) is obtained by reacting the above monomers (A1) and (A2) with each other, preferably in a molar ratio of (A1) / (A2) = 0.02 to 4. A copolymer mixture having a molar ratio (A
1) / (A2) is changed at least once during the reaction, and the average weight ratio (X _II of the monomers (A2) to all the monomers for producing the copolymer mixture (a ′) is ) Is different from the average weight ratio (X _I ) of the copolymer mixture (A).
The average weight ratio is [total amount of monomers (A2) / total amount of monomers] x
It is represented by 100 (% by weight), and each preferably ranges from 1 to 30 (% by weight). Hereinafter, this average weight ratio may be referred to as “(A2) average weight ratio”. Further, the average weight ratios (X _I ) and (X _II ) are preferably different from each other by at least 1.0 (wt%), more preferably at least 2.0 (wt%), and particularly at least 3.0 (wt%). Incidentally, the copolymer mixture (a) and (a '), the monomers (A1), (A2) used in the production
In the present invention, the average weight ratio (X _I ),
It suffices that (X _II ) be different, but it is preferable to use the same type of monomers (A1) and (A2).

In the present invention, the average weight ratio (X _I ) of the copolymer mixture (A) is 1 to 30% by weight, more preferably 7 to 20% by weight, especially 8%.
It is preferably about 16% by weight. Then, when a blending system is assembled using this copolymer mixture (a) as a main component,
It is possible to obtain an extruded admixture having a good balance of performances.

In the present invention, a plurality of copolymers (A2) obtained from a plurality of monomer mixtures having different average weight ratios can be used as the copolymer mixture (a ′). From a practical point of view, it is preferable to use 1 to 3 copolymer mixtures obtained from 1 to 3 monomer mixtures having different (A2) average weight ratios. When one copolymer mixture is used as the copolymer (a ′), that is, when two copolymer mixtures in total are used, they are conveniently added to the copolymer mixture (A _i ), (A _ii ). And the average weight ratio of these (A2) is (X _i ), (X _ii ), it is preferable that 5 ≦ (X _i ) <8 (wt%) 8 ≦ (X _ii ) ≦ 16. Also, a copolymer mixture (a ')
When using two copolymer mixtures as, i.e., when using a total of three copolymer mixtures, they are conveniently copolymer mixtures (A _i ), (A _ii ), (A _iii ), If these (A2) average weight ratios are (X _i ), (X _ii ), and (X _iii ), then 5 ≦ (X _i ) <8 (wt%) 8 ≦ (X _ii ) ≦ 16 (wt%) ) 16 <(X _iii ) ≦ 30 (wt%) is preferable.

(A2) Due to the presence of a large number of copolymer mixtures having different average weight ratios, good dispersibility and dispersion retention are exhibited over a wide range of W / C and cement temperature. In particular, the dispersion holding property becomes stable for a long time. As a result, it becomes an admixture for an extrusion molded body that can sufficiently cope with fluctuations in W / C and fluctuations in temperature.

As described above, the admixture of the present invention is prepared by reacting the above monomers (A1) and (A2) with each other at a molar ratio preferably in the range of (A1) / (A2) = 0.02-4. The resulting copolymer mixture (a), and preferably further (a ′), is contained, but in any case, the molar ratio (A1) / (A2) thereof is changed at least once during the reaction. The change in the molar ratio is
Either increase, decrease, or a combination thereof may be used.
When the molar ratio is changed stepwise or intermittently, the number of changes is preferably 1 to 10 times, particularly preferably 1 to 5 times. Also,
When the molar ratio is continuously changed, it may be linear change, exponential change, or any other change, but the degree of change is 0.0001 to 0.2 per minute, and further 0.0005 to
0.1, particularly 0.001 to 0.05 is preferred. Further, the molar ratio is at least any one of (A1) / (A2) before and after the change.
It is preferable that the molar ratio (A1) / (A2) before and after the change is both within the range of 0.02 to 4, preferably in the range of 0.02 to 4. Further, as described above, the change in the molar ratio has various modes, but in any case, the difference between the maximum value and the minimum value of the molar ratio (A1) / (A2) in the entire copolymerization reaction is at least 0. .
It is preferably in the range of 05, particularly 0.05 to 2.5.

Such a copolymer mixture can be obtained by a production method having a step of polymerizing by changing the (A1) / (A2) molar ratio at least once. Specifically, the monomer mixture (A1) Simultaneously with the start of dropping the aqueous solution, start dropping the monomer (A2),
A method of changing the dropping flow rate (parts by weight / minute) so that the respective molar ratios fall within a predetermined range and dropping for a predetermined time may be mentioned. In this method, the amount of change in the monomer (A1) / (A2) molar ratio (difference between the maximum value and the minimum value) is preferably 0.05 to 2.5, and more preferably 0.1 to 2. The copolymer mixture obtained by changing the molar ratio even once in the reaction as in this method has a higher (A1) / (A2) molar ratio than the copolymer obtained by the reaction. ) / (A2) molar ratio distribution is presumed to be a mixture of a large number of copolymers.

Incidentally, 30% or more of the total weight of the monomers, especially
It is preferable to manufacture 50 to 100% by changing the dropping flow rate as described above.

The polymerization reaction may be carried out in the presence of a solvent.
As the solvent, water, lower alcohols such as methanol, ethanol, isopropanol, butanol; benzene,
Examples thereof include aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane; aliphatic hydrocarbons such as n-hexane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone. Among these, water and lower alcohols are preferable from the viewpoints of easy handling and solubility of the monomer and polymer.

In the copolymerization reaction, a polymerization initiator can be added. As the polymerization initiator, organic peroxides, inorganic peroxides, nitrile compounds, azo compounds,
Examples thereof include diazo compounds and sulfinic acid compounds. The amount of the polymerization initiator added is monomer (A1), monomer
It is preferably 0.05 to 50 mol% based on the total of (A2) and other monomers.

In the copolymerization reaction, a chain transfer agent can be added. Examples of the chain transfer agent include lower alkyl mercaptan, lower mercapto fatty acid, thioglycerin, thiomalic acid and 2-mercaptoethanol. The reaction temperature of the copolymerization reaction is preferably 0 to 120 ° C.

The obtained polycarboxylic acid type polymer can be subjected to a deodorizing treatment, if necessary. In particular, when a thiol such as mercaptoethanol is used as a chain transfer agent, an unpleasant odor tends to remain in the polymer, and therefore deodorizing treatment is desirable.

The polycarboxylic acid-based polymer obtained by the above-mentioned production method can be applied as an admixture for an extrusion molded product even in the acid form, but from the viewpoint of suppressing hydrolysis of the ester due to acidity, The salt form is preferred by neutralization with. Examples of the alkali include hydroxides of alkali metals or alkaline earth metals, ammonia, mono-, di-, tri-alkyl (C 2-8) amines, mono-, di-, trialkanols (C 2-8) amines and the like. Can be mentioned. When the (meth) acrylic acid-based polymer is used as an admixture for an extrusion-molded product, it is preferably partially or completely neutralized. Further, from the viewpoint of protecting the material of the container when storing the admixture of the present invention, the obtained polycarboxylic acid-based polymer has a 5 wt% aqueous solution having a pH (20 ° C.) of 4 to 9, particularly pH 5 It is preferable to adjust to ~ 8.

The weight average molecular weight of the polycarboxylic acid polymer obtained by the above production method [gel permeation chromatography method, polyethylene glycol conversion, column: G4000PWXL + G2500PWXL (Tosoh Corporation)
Manufactured), eluent: 0.2M phosphate buffer / acetonitrile = 7
/ 3 (volume ratio)] is preferably 10,000 to 200,000 in order to obtain sufficient dispersibility as an admixture for an extrusion molded body,
Particularly preferred is 0000 to 100,000.

Furthermore, acrylonitrile, (meth)
A copolymerizable monomer such as acrylamide, styrene, an alkyl (meth) acrylate (having 1 to 12 carbon atoms which may have a hydroxyl group) ester, or styrene sulfonic acid may be used in combination. These can be used in a proportion of 50% by weight or less, more preferably 30% by weight or less, based on the total monomers, but 0% by weight is preferable.

[Water-soluble polymer (b)] In order to alleviate the resistance during extrusion molding and make the extrusion rate more stable, it is necessary to impart an appropriate viscosity to the cement composition for extrusion molding. . In the polymer mixture (a), the following (B1) ~ (B8)
It has been found that the temperature dependence of the extrusion rate is remarkably stable by using at least one water-soluble polymer (b) selected from (B1) Nonionic cellulose ether (B2) Acrylic acid copolymer (B3) Polyalkylene glycol (B4) Polysaccharide obtained by fermentation (B5) Xanthan gum (B6) C6-30 monohydric alcohol or carbon number 6-30 monovalent mercaptans, alkylphenols having 6-30 carbon alkyls, amines having 6-30 carbons or carboxylic acids having 6-30 carbons are averaged with alkylene oxides.
Alkylene oxide derivative (B7) having 10 to 1000 moles added thereto has an average of 10 alkylene oxides in a monohydric alcohol having 6 to 30 carbon atoms, a monohydric mercaptan having 6 to 30 carbon atoms or an alkylphenol having an alkyl having 6 to 30 carbon atoms.
The reaction product of the alkylene oxide derivative added with ˜1000 mol and the compound having one or more epoxy groups (B8) The hydrogen atom of all or part of the hydroxyl groups of the polysaccharide or its alkylated or hydroxyalkylated derivative is carbon. A hydrophobic substituent (P) having a hydrocarbon chain of the number 8 to 40 as a partial structure, and one or more groups selected from the group consisting of sulfonic acid groups, carboxyl groups, phosphoric acid groups, sulfuric acid ester groups and salts thereof. A polysaccharide derivative which is substituted with an ionic hydrophilic group (Q) having a partial structure of.

Examples of (B1) include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose and the like.

Examples of (B2) include polyacrylic acid or salts thereof, such as sodium polyacrylate, potassium polyacrylate, and polyacrylic acid amide.

As the (B3) polyalkylene glycol,
Examples thereof include polyethylene glycol having a weight average molecular weight of 10,000 to 50,000.

Examples of (B4) include yeast glucan, linear or branched β-1,3 glucan, and the like.

As (B6), an ethylene oxide (hereinafter referred to as EO) adduct of oleyl alcohol [average number of added moles (hereinafter referred to as EOp) is preferably 30 to 500, more preferably 30 to 300. . ], Nonylphenol E
O adducts (EOp is preferably 30 to 500, more preferably 30 to 300) and the like. Further, those described in JP-A 8-73250 can be mentioned.

As (B7), a reaction product of EO adduct of oleyl alcohol (EOp is preferably 30 to 500, more preferably 30 to 300) and vinylcyclohexene diepoxide, EO / propylene oxide block of stearyl alcohol. Examples thereof include a reaction product of an adduct and vinylcyclohexene diepoxide. Further, those described in JP-A 8-73250 can be mentioned.

Examples of (B8) include the polysaccharide derivatives described in claims 1 to 3 of JP-A No. 11-1355.

The molecular weight and degree of substitution of these water-soluble polymers (B) are not limited as long as they are water-soluble.

[Admixture for Extrusion Molded Article] In the cement-based admixture for extrusion molded article of the present invention, the weight ratio of the copolymer mixture (a) and the water-soluble polymer (b) is (a) /
(B) = 100/10 to 100/1000, and further 100/50 to 100/50
0, particularly 100/100 to 100/300 is preferable.

Further, the admixture for a cement-based extrusion molded article of the present invention is characterized in that the copolymer mixture (a) is added to the cement active ingredient in the water-kneaded product mainly composed of the cementitious material.
It is preferable to use the water-soluble polymer (II) in an amount of from 05 to 1.0% by weight and from 0.001 to 0.2% by weight (both in terms of solid content).

The cement-based admixture for extrusion molded products of the present invention can be used in combination with a known defoaming agent or additive (material). For example, AE agent, AE water reducing agent, superplasticizer, high-performance water reducing agent, retarder, early strengthening agent, accelerator, foaming agent, foaming agent, water retention agent, thickener, waterproofing agent, blast furnace slag, Examples include fly ash and silica fume.

The cement-based mild agent for extruded products of the present invention is added to a water kneaded product containing a cementitious material as a main raw material. Examples of the cementitious material used here include ordinary Portland cement and blast furnace cement. , Fly ash cement, etc. can also be used and are not particularly limited. Further, silica sand or the like is used as an aggregate, and inorganic fibers such as asbestos, rock wool, glass fibers and steel fibers, organic fibers such as carbon fibers, nylon fibers, vinylon fibers, polypropylene fibers and aramid fibers are used as bending reinforcing fibers. Can also be used.
Furthermore, polyvinyl alcohol as a plasticizer for the water kneaded product,
Water-soluble polymers other than the water-soluble polymer (b) such as gelatin and sodium alginate may be used.

The admixture for cement-based extrusion molded article of the present invention, the cementitious material, the aggregate and the fibers are mixed by a kneader,
By preparing a kneaded product and molding with an extruder,
A cement-based extruded product is obtained.

The cement-based extruded product, which is the target of the admixture for the cement-based extruded product of the present invention, can be used as an embedded mold for building members and concretes.

[0049]

EXAMPLES [Production Example of Copolymer Mixture (a)] Production Example 1: Production of Copolymer Mixture No. 1 Glass equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introducing pipe, and a reflux condenser The reaction vessel was charged with 423 parts by weight of water and purged with nitrogen. Then, after raising the temperature to 70 ° C. in a nitrogen atmosphere, 44.9 parts by weight of the monomer E-1 (EOp = 9) shown in Table 2 and 18.2 parts by weight of methacrylic acid were mixed with the dropping monomer liquid (1). 3 liquids of 14.2 parts by weight of 5% -2-mercaptoethanolic acid aqueous solution and 13.8 parts by weight of 5% aqueous ammonium persulfate solution were simultaneously added dropwise over 15 minutes, and then monomer E-1 in Table 2 (EOp = 9)
250.5 parts by weight of methacrylic acid and 65.2 parts by weight of methacrylic acid were mixed, and 59.2 parts by weight of a 5% -2-mercaptoethanolic acid aqueous solution and 5% ammonium persulfate aqueous solution were added.
7.6 parts by weight of 3 liquids were added dropwise in 75 minutes, and the addition was completed in 90 minutes in total. After completion of the dropping, the mixture was aged at the same temperature for 1 hour, 21.4 parts by weight of 5% ammonium persulfate aqueous solution was added dropwise over 10 minutes, and then aged at 70 ° C. for 2 hours to complete the polymerization reaction. Further, 57 parts by weight of a 48% sodium hydroxide aqueous solution was added for neutralization to obtain a copolymer mixture No. 1 shown in Table 3. The pH of a 5% by weight aqueous solution of this copolymer mixture No. 1 was 6.0 (20 ° C).

Among the copolymer mixtures shown in Table 3, (A1)
The one obtained by changing the molar ratio of / (A2) once is the same as in Production Example 1
It was manufactured according to.

Production Example 2: Production of Copolymer Mixture No. 6 A glass reaction vessel was charged with 329.9 parts by weight of water and, after purging with nitrogen, the temperature was raised to 78 ° C. in a nitrogen atmosphere. Next, 216.4 parts by weight of a 60% aqueous solution of the monomer E-2 shown in Table 2 and the monomer shown in Table 2
A mixed solution of 75.5 parts by weight of 90% aqueous solution of E-1, 38.3 parts by weight of methacrylic acid, 27.7 parts by weight of 5% ammonium persulfate aqueous solution and 30.8 parts by weight of 5% -2-mercaptoethanol aqueous solution.
Dropwise over 55 minutes, then 78.7 parts by weight of 60% aqueous solution of monomer E-2 shown in Table 2 and 90% aqueous solution of monomer E-1 shown in Table 332.
20 parts by weight of a mixed solution of 9.7 parts by weight of methacrylic acid, 8.2 parts by weight of an aqueous solution of 5% ammonium persulfate and 9.2 parts by weight of an aqueous solution of 5% -2-mercaptoethanol are added dropwise over 20 minutes, and the monomer E-shown in Table 2 is added. 59.0 parts by weight of a 60% aqueous solution of 2, 26.0 parts by weight of a 90% aqueous solution of the monomer E-1 shown in Table 2, methacrylic acid 5.6
A mixed solution of 5 parts by weight, 5.4 parts by weight of a 5% ammonium persulfate aqueous solution and 6.0 parts by weight of a 5% -2-mercaptoethanol aqueous solution were added dropwise over 15 minutes. Molar ratio (A1) / (A
2) is shown in Table 3. After the dropping was completed, the mixture was aged for 60 minutes at 78 ° C., and then 20.7 parts by weight of a 5% ammonium persulfate aqueous solution was added in 5 minutes. The mixture was aged for 120 minutes at 78 ° C., and 20.8 parts by weight of 48% aqueous sodium hydroxide solution was added to obtain a copolymer mixture No. 6 shown in Table 3. The pH (20 ° C.) of a 5 wt% aqueous solution of this copolymer mixture No. 6 was 5.9. Incidentally, the copolymer mixture No. 7 in Table 3 was also produced according to this Production Example 2.

[Evaluation method] The copolymer mixture (a) of Table 3 and the water-soluble polymer (b) of Table 4 obtained by using the monomers of Table 2 in the cement mixture for extrusion molding of Table 1 Was mixed in an amount shown in Table 5 with a kneading machine (Miyazaki Iron Works Co., Ltd .; NHS-80) to prepare a kneaded product, and an extrusion molding machine (Miyazaki Iron Works Co., Ltd.) attached to the tip of a die having a width of 60 mm and a thickness of 8 mm. An extruded plate was formed by a product (FM-301 type). Then, the molded product was subjected to high temperature and high pressure curing (180 ° C., 10 kg / cm ² ) to obtain a product. The extrusion speed, bending strength, appearance and dimensional accuracy during molding were measured and evaluated as follows. The results are shown in Table 5.

(1) Extrusion rate At the concrete temperature of 20 ° C. or 30 ° C., the length of the molded body per minute in the case of the above extrusion molding was measured.

(2) Bending strength At a concrete temperature of 20 ° C. or 30 ° C., the bending strength of the extruded product was measured according to JIS R5201.

(3) Appearance The appearance of the extrusion-molded product extruded at a concrete temperature of 20 ° C. was visually observed and evaluated according to the following criteria. ⊚: Surface is extremely smooth and has no scratches ○: Surface is smooth and has no scratches Δ: Slightly streaky scratches occur on the surface ×: Many streaky scratches occur on the surface

(4) Dimensional accuracy At the concrete temperature of 20 ° C. or 30 ° C., the dimensional accuracy of the extruded molded article was evaluated according to the following criteria. ∙ Both width and thickness errors are less than 0.1 mm ○… Width and thickness errors are both 0.1 mm or more and 0.2 mm or less △… Width and thickness errors are both 0.2 mm or more and 0.3 mm or less ×… Width and thickness errors are Both over 0.3 mm

[0057]

[Table 1]

[0058]

[Table 2]

[0059]

[Table 3]

[0060]

[Table 4]

(Note) In Table 4, W-10 is a hydroxyethyl cellulose derivative obtained by the following method.

(1) 100 equipped with stirrer, thermometer and cooling pipe
In a 0 ml glass separable reaction vessel, a weight average molecular weight of about 800,000, hydroxyethyl group substitution degree 1.8 hydroxyethyl cellulose (HEC-QP15000H, Union Carbide Co., Ltd.) 50 g, 85% isopropyl alcohol 260 g and 48% sodium hydroxide aqueous solution. 3.3g is added to adjust the slurry liquid,
The mixture was stirred at room temperature under a nitrogen atmosphere for 30 minutes. To this, 1.21 g of stearyl glycyl ether was added and reacted at 80 ° C. for 9 hours to make it hydrophobic. After the completion of the hydrophobization reaction, the reaction solution was neutralized with acetic acid, and the reaction product was filtered off. The reaction product was washed twice with 500 g of 80% acetone, dried under reduced pressure at 70 ° C. for 1 day, and hydroxyethyl cellulose (HEC) derivative 48 with a hydrophobicity of 0.0032.
I got 7g.

(2) A 500 ml four-necked flask equipped with a stirrer, a thermometer and a Dimroth condenser was replaced with nitrogen and charged with 10 g of the hydrophobized HEC derivative obtained above and 80 g of 80% isopropyl alcohol (IPA). The mixture was stirred at room temperature in the atmosphere as follows. First, 0.68 g of 48% aqueous sodium hydroxide solution was added and stirred for 15 minutes. After heating to 50 ° C, deionized water is reduced to 0.
7 g, 13.55 g of 30% sodium 3-chloro-2-hydroxypropanesulfonate (CHPS) aqueous solution, and 1.71 g of 48% sodium hydroxide aqueous solution were charged. After stirring for 1 hour at 50 ° C, further IPA2
4.23 g, 30% CHPS aqueous solution 13.55 g, and 48% sodium hydroxide aqueous solution 1.71 g were charged. After stirring at 50 ° C for 1 hour, further IP
A24.23 g, 30% CHPS aqueous solution 13.55 g, and 48% sodium hydroxide aqueous solution 1.71 g were charged. Further, after stirring at 50 ° C. for 3 hours, the reaction solution was cooled to room temperature or lower with ice water, neutralized with hydrochloric acid, and then filtered off. The product separated by filtration is washed 3 times with 70% IPA, and then twice with 100 g of IPA, and at 70 ° C under reduced pressure.
After drying for 1 day and night, 10.44 g of a hydroxyethyl cellulose derivative substituted with an octadecyl group and a 3-sulfo-2-hydroxypropyl group was obtained.

(3) The degree of substitution of octadecyl group in the obtained hydroxyethyl cellulose derivative was 0.0032, 3-sulfo-2
-The degree of substitution of hydroxypropyl group was 0.332.

[0065]

[Table 5]

(Note) The addition amount in Table 5 is the solid content weight% with respect to the cement. Moreover,% in Examples 1-4, 1-5, and 1-6 is% by weight in the total of the copolymer mixture (a). Moreover, the part of the amount of mixed water is a weight part.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C04B 24/32 C04B 24/32 A 24/38 24/38 D Z 28/02 28/02 C08F 290/06 C08F 290/06 // C04B 103: 30 C04B 103: 30 103: 40 103: 40 F term (reference) 4G012 PB31 PC01 4G054 AA01 BD00 4J027 AC01 AC02 AC06 AC07 AJ08 BA06 CB02 CC02 CD01

Claims (2)

[Claims] 1. At least one monomer (A1) represented by the following general formula (a1) and at least one monomer (A2) represented by the following general formula (a2): A copolymer mixture (a) obtained by copolymerization and in which the molar ratio (A1) / (A2) of the monomers (A1) and (A2) is changed at least once during the reaction; An admixture for an extrusion-molded product, which contains at least one water-soluble polymer (B) selected from (B1) to (B8). [Chemical 1] (In the formula, R ¹ and R ² : hydrogen atom or methyl group R ³ : hydrogen atom or -COO (AO) _m1 X m: number of 0-2 p: number of 0 or 1 n: number of 2-300 AO : C2-4 oxyalkylene group or oxystyrene group X: represents a hydrogen atom or a C1-18 alkyl group.) (In the formula, R ^{4 to} R ^{6 are a} hydrogen atom, a methyl group or (CH ₂ ) _{m 1} COOM ² ,
(CH _{²⁾ m1} COOM ₂ may form a COOM ¹ or another (CH _{²⁾ m1} COOM ₂ and anhydride, in which case, M ^1, M ² in these groups are not present. M ¹ , M ² : hydrogen atom, alkali metal, alkaline earth metal,
An ammonium group, an alkylammonium group, or a substituted alkylammonium group m1: represents the number of 0 to 2. ) (B1) Nonionic cellulose ether (B2) Acrylic acid copolymer (B3) Polyalkylene glycol (B4) Polysaccharide obtained by fermentation (B5) Xanthan gum (B6) Monohydric alcohol or carbon having 6 to 30 carbon atoms Average of alkylene oxide to C6 to C30 monovalent mercaptan, C6 to C30 alkyl-containing alkylphenol, C6 to C30 amine or C6 to C30 carboxylic acid
Alkylene oxide derivative (B7) having 10 to 1000 moles added thereto has an average of 10 alkylene oxides in a monohydric alcohol having 6 to 30 carbon atoms, a monohydric mercaptan having 6 to 30 carbon atoms or an alkylphenol having an alkyl having 6 to 30 carbon atoms.
The reaction product of the alkylene oxide derivative added with ˜1000 mol and the compound having one or more epoxy groups (B8) The hydrogen atom of all or part of the hydroxyl groups of the polysaccharide or its alkylated or hydroxyalkylated derivative is carbon. A hydrophobic substituent (P) having a hydrocarbon chain of the number 8 to 40 as a partial structure, and one or more groups selected from the group consisting of sulfonic acid groups, carboxyl groups, phosphoric acid groups, sulfuric acid ester groups and salts thereof. Derivatives Substituted by Ionic Hydrophilic Group (Q) Having a Substrate 2. An extruded body produced by using the admixture for an extruded body according to claim 1.