JP2007112664A - Admixture for extruded formed body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an admixture for an extruded formed body by which the extruded formed body free from the deterioration of the dimensional accuracy or the appearance even in the formulation low in water content and the extruded formed body having high strength is produced. <P>SOLUTION: The admixture comprises a phosphoric ester based polymer (A) obtained by copolymerizing a specific monomer 1 having a polyoxy alkylene group, a phosphoric acid monoester based monomer 2 and a phosphoric diester based monomer 3, and a water soluble high polymer compound (B). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an admixture for an extruded product.

  Cement-based extrudates are obtained by molding clay-like ultra-high viscosity substances mainly composed of cementitious materials using an extrusion molding machine. Conventionally, asbestos, carbon fibers, vinylon fibers, nylon fibers, etc. Bending strength is increased by mixing organic and inorganic fibers. A water-kneaded product of a cementitious material as it is, even if it is extruded, has low shape retention and water retention, poor sliding in the cylinder and die of the extruder, and poor mold release at the die outlet. Therefore, a product with a smooth surface cannot be obtained, and a molded product that does not conform to a predetermined shape is obtained.

A water-soluble polymer has been proposed as an agent for reducing resistance during extrusion molding. Furthermore, Patent Document 1 proposes that the combined use of a polycarboxylic acid-based admixture and a water-soluble polymer is excellent in extrusion moldability. Patent Document 2 discloses a cement dispersant mainly composed of a polymer of a monoester or monoether having a polyalkylene glycol chain and a monomer having a phosphate group.
JP 2003-2719 A JP 2000-327386 A

  However, for the purpose of increasing the strength, blending with a reduced amount of mixed water tends to lower the extrusion moldability, which may cause deterioration in dimensional accuracy and appearance. For this reason, an admixture excellent in extrusion moldability is desired even in the case of blending with a low water content.

  An object of the present invention is to provide an admixture for an extruded molded body that can produce a high-strength extruded molded article without deterioration in dimensional accuracy and appearance even in a formulation with a small amount of mixed water.

  The present invention comprises a monomer 1 represented by the following general formula (1), a monomer 2 represented by the following general formula (2), and a monomer 3 represented by the following general formula (3). Phosphoric ester polymer (A) [hereinafter referred to as (A) component] obtained by copolymerization with a mixed monomer, and water-soluble polymer compound (B) [hereinafter referred to as (B) component] The present invention relates to an admixture for extruded products containing:

[Wherein R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom or — (CH ₂ ) q (CO) pO (AO) rR ⁴ , and AO is an oxyalkylene having 2 to 4 carbon atoms. Group or oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R ⁴ is a hydrogen atom or a carbon number of 1 to 18 Represents an alkyl group. ]

[Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 30, M ³ and M ⁴ are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]

[Wherein R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 30 and M ⁵ is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]

  Moreover, this invention relates to the extrusion molded object manufactured using the admixture for extrusion molded objects of the said invention.

  ADVANTAGE OF THE INVENTION According to this invention, even if it mix | blends with few amounts of mixed water, there is no deterioration of a dimensional accuracy and an external appearance, and the admixture for extrusion molded bodies which enables manufacture of a high intensity | strength extruded body is provided. With the admixture of the present invention, the extrusion molded article excellent in the smoothness and dimensional stability of the molded article surface can be obtained without reducing the resistance during molding and reducing the extrusion molding speed.

<(A) component>
The component (A) is represented by the monomer 1 represented by the general formula (1), the monomer 2 represented by the general formula (2), and the general formula (3). It is a phosphoric ester polymer obtained by copolymerizing the monomer 3.

[Monomer 1]
In monomer 1, R ¹ and R ² in general formula (1) are each a hydrogen atom or a methyl group. R ³ is a hydrogen atom or — (CH ₂ ) _q (CO) _p O (AO) _r R ⁴ , preferably a hydrogen atom. R ⁴ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12, more preferably 1 to 4, and further preferably 1 or 2, and particularly preferably a methyl group. When p is 0, AO forms an ether bond with (CH ₂ ) _q, and when p is 1, it forms an ester bond. q is 0 to 2, preferably 0 or 1, and more preferably 0. AO is an oxyalkylene group having 2 to 4 carbon atoms or an oxystyrene group, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, more preferably an ethyleneoxy group (hereinafter referred to as EO group), and an EO group. Is 70 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more. r is an average added mole number of AO, which is a number of 3 to 300, and is 3 to 300 from the viewpoint of reducing the amount of mixed water with respect to the hydraulic composition of the polymer and reducing the resistance during extrusion, preferably 4 to 120, more preferably 4 to 80, still more preferably 4 to 50, and particularly preferably 4 to 30. Moreover, AO is different in an average of r repeating units, and random addition, block addition, or a mixture thereof may be included. For example, AO can contain a propyleneoxy group etc. besides EO group.

  Monomer 1 includes a half-terminated alkyl-capped polyalkylene glycol such as methoxypolyethylene glycol, methoxypolypropylene glycol, methoxypolybutylene glycol, methoxypolystyrene glycol, ethoxypolyethylenepolypropyleneglycol, (meth) acrylic acid, maleic acid (half ) Esterified products, etherified products with (meth) allyl alcohol, and (meth) acrylic acid, maleic acid, and (meth) allyl alcohol adducts having 2 to 4 carbon atoms are preferably used. In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and (meth) allyl means allyl and / or methallyl (the same applies hereinafter).

  More preferred is an esterified product of alkoxy, particularly methoxypolyethylene glycol and (meth) acrylic acid. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable.

  The monomer 1 used for the production of the component (A) can be obtained, for example, by esterification of an alkoxypolyalkylene glycol and (meth) acrylic acid. From the viewpoint of the required addition amount and viscosity reduction when the esterified product is used in the concrete admixture of the present invention, the unreacted (meth) acrylic acid is 5% by weight based on the monomer 1 in terms of acid type. The following is preferable, 3% by weight or less is more preferable, 1.5% by weight or less is further preferable, and 1% by weight or less is more preferable. Examples of a method for reducing the amount of (meth) acrylic acid remaining during the production of the monomer 1 include topping, steaming, and solvent extraction.

[Monomer 2]
In the monomer (2), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkylene group having 2 to 12 carbon atoms. m1 is a number from 1 to 30, and M ³ and M ⁴ are each a hydrogen atom, an alkali metal, or an alkaline earth metal. 1-20 are preferable, as for m1 in General formula (2), 1-10 are more preferable, and 1-5 are especially preferable.

  Specific examples include phosphoric acid monoesters of organic hydroxy compounds. Specific examples include polyalkylene glycol mono (meth) acrylate acid phosphates. For example, phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid mono-[(2-hydroxyethyl) acrylic acid ester] and the like can be mentioned. Among these, phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester is preferable from the viewpoint of ease of production and product quality stability. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and the like of these compounds may be used.

[Monomer 3]
In the monomer 3, in the general formula (3), R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, and R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms. m2, m3 is a number of each 1 to 30, M ⁵ represents a hydrogen atom, an alkali metal or alkaline earth metal. M2 and m3 in the general formula (3) are each preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

  Specific examples include phosphoric acid diesters of organic hydroxy compounds. Specific examples include polyalkylene glycol di (meth) acrylate acid phosphoric acid diester. Examples include phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid di-[(2-hydroxyethyl) acrylic acid] ester, and the like. Among these, di-[(2-hydroxyethyl) methacrylic acid] ester phosphate is preferable from the viewpoint of ease of production and quality stability of the product. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and the like of these compounds may be used.

  Monomers 2 and 3 can be used as a mixed monomer including monomer 2 and monomer 3. Further, as the monomer 2 and the monomer 3, a phosphate ester obtained by reacting the organic hydroxy compound represented by the general formula (4) with a phosphorylating agent may be used.

  The mixed monomer including the monomer 2 and the monomer 3 is obtained as a reaction product by reacting, for example, an organic hydroxy compound represented by the general formula (4) and a phosphorylating agent at a predetermined charge ratio. It can also be manufactured.

[Wherein, R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents an alkylene group having 2 to 12 carbon atoms, and m4 represents a number of 1 to 30. ]

  1-20 are preferable, as for m4 in General formula (4), 1-10 are more preferable, and 1-5 are especially preferable.

  Examples of the phosphorylating agent include orthophosphoric acid, phosphorus pentoxide (anhydrous phosphoric acid), polyphosphoric acid, phosphorus oxychloride and the like, and orthophosphoric acid and phosphorus pentoxide are preferable. These may be used alone or in combination of two or more. The amount of the phosphorylating agent in the reaction of the organic hydroxy compound and the phosphorylating agent can be appropriately determined according to the target phosphate ester composition.

  Examples of mixed monomers including monomer 2 and monomer 3 include mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate. When the mixture is produced, it can be synthesized by a known technique (for example, JP-A-57-180618).

  As the mixed monomer including the monomer 2 and the monomer 3, a commercial product including a monoester and a diester can be used. For example, Phosmer M, Phosmer PE, Phosmer P (Unichemical) , JAMP514, JAMP514P, JMP100 (all Johoku Chemical), light ester P-1M, light acrylate P-1A (all Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich) Reagent).

  It has been confirmed that the above-mentioned commercial products and reaction products contain compounds other than the monoester (monomer 2) and diester (monomer 3). These other compounds are considered to be a mixture of polymerizable and non-polymerizable compounds, but in the present invention, such a mixture (mixed monomer) can be used as it is.

  The component (A) according to the present invention is a phosphate ester polymer obtained by copolymerizing the monomer 1, the monomer 2, and the monomer 3. It is also preferable to use a mixed monomer containing monomer 2 and monomer 3.

  In the copolymerization of the monomers, the molar ratio between the monomer 1 and the monomers 2 and 3 is as follows: monomer 1 / (monomer 2 + monomer 3) = 5/95 to 95/5, Furthermore, 10/90 to 90/10 are preferable. The molar ratio of monomer 1, monomer 2 and monomer 3 is as follows: monomer 1 / monomer 2 / monomer 3 = 5 to 95/3 to 90/1 to 80, and further 5 -96 / 3-80 / 1-60 (however, the total is 100) is preferable. In addition, about the monomer 2 and the monomer 3, the molar ratio and mol% shall be calculated based on an acid type compound (hereinafter the same).

  Moreover, in manufacture of (A) component, it is preferable that the ratio of the monomer 3 shall be 1-60 mol% and also 1-30 mol% in all the monomers used for reaction.

  The molar ratio of monomer 2 to monomer 3 is preferably monomer 2 / monomer 3 = 99/1 to 4/96, more preferably 99/1 to 5/95.

  From the viewpoint of suppressing gelation, the monomer solution containing monomer 2 and / or monomer 3 is preferably used for the reaction at a pH of 7 or less.

Hereinafter, more preferable production conditions will be described from the viewpoint of gelation suppression, adjustment of a suitable molecular weight, and performance design of an admixture. From such a viewpoint, at the time of copolymerization, 4 mol% or more, further 6 mol% or more, particularly 8 mol% or more of the chain transfer agent is used with respect to the total number of moles of the monomers 1, 2 and 3. It is preferable. The upper limit of the amount of chain transfer agent used is preferably 100 mol% or less, more preferably 60 mol% or less, still more preferably 30 mol% or less, based on the total number of moles of monomers 1, 2 and 3. Most preferably, it can be 15 mol% or less. More specifically, (1) when r of monomer 1 is 3 to 30,
(1-1) When the total molar ratio of the monomers 1, 2 and 3 of the monomer 2 and the monomer 3 is 50 mol% or more, the chain transfer agent is the monomers 1, 2 and 3 It is preferable to use 6 to 100 mol%, particularly 8 to 60 mol%, based on the total of
(1-2) When the molar ratio in the sum of monomers 1, 2 and 3 of monomer 2 and monomer 3 is less than 50 mol%, the chain transfer agent is monomer 1, 2 and It is preferable to use 4 to 60 mol%, particularly 5 to 30 mol%, based on the total of 3.
(2) When r of monomer 1 used for component (A) is more than 30, the chain transfer agent is used in an amount of 6 to 50 mol%, particularly 8 to 40 mol%, based on monomers 1 to 3. Is preferred.

  The reaction rate of the monomers 2 and 3 is preferably 60% or more, more preferably 70% or more, more preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. It can be selected from the viewpoint. Here, the reaction rate of the monomers 2 and 3 is calculated by the following equation.

In addition, the ratio (mol%) of the ethylenically unsaturated bond of the monomer 2 and the monomer 3 in the phosphorus-containing compound in the reaction system at the start and end of the reaction is measured by the following ¹ H-NMR. It can be calculated based on the result.
[ ¹ H-NMR conditions]
The component (A) dissolved in water and dried under reduced pressure is dissolved in deuterated methanol at a concentration of 3 to 4% by weight, and ¹ H-NMR is measured. The residual ratio of ethylenically unsaturated bonds is measured by an integral value of 5.5 to 6.2 ppm. In addition, the measurement of ¹ H-NMR uses “Mercury 400 NMR” manufactured by Varian, the number of data points is 42052, the measurement range is 6410.3 Hz, the pulse width is 4.5 μs, the pulse waiting time is 10 S, and the measurement temperature is 25.0 ° C. Perform under conditions.

  In the production of the component (A), in addition to the monomers 1, 2, and 3, other monomers that can be copolymerized can be used. Examples of other copolymerizable monomers include allyl sulfonic acid, methallyl sulfonic acid, any of these alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts. In addition, acrylic monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and any one or more of alkali metal salts, alkalis Anhydrous compounds such as earth metal salts, ammonium salts, amine salts, methyl esters, ethyl esters and maleic anhydride may also be used. Furthermore, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-metasulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, Examples include 2- (meth) acrylamide-2-propanesulfonic acid, styrene, styrenesulfonic acid and the like. The total proportion of monomers 1, 2, and 3 in all monomers is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably 75 to 100 mol%, and more than 95 mol% to 100 Mole%, more preferably 97-100 mol% is preferred.

  In the production of component (A), the monomer is preferably copolymerized in the presence of a predetermined amount of chain transfer agent. Moreover, you may use the other monomer, polymerization initiator, etc. which can be copolymerized.

  The reaction temperature of the monomers 1, 2 and 3 is preferably 40 to 100 ° C., more preferably 60 to 90 ° C., and the reaction pressure is 101.3 to 111.5 kPa (1 to 1.1 atm) in gauge pressure. 3-106.4 kPa (1-1.05 atm) is preferred.

  The pH of the reaction system can be adjusted with an inorganic acid (phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc.), NaOH, KOH, triethanolamine, or the like, if necessary.

  Here, the monomer solution containing the monomer 2 and / or the monomer 3 is preferably a water-containing system (that is, the solvent contains water) for pH measurement. May be measured by adding the required amount of water. From the viewpoint of uniformity of the monomer solution, prevention of gelation, and suppression of performance degradation, the pH is preferably 7 or less, more preferably 0.1 to 6, and further preferably 0.2 to 4.5. Monomer 1 is also preferably used as a monomer solution having a pH of 7 or less. This pH is at 20 ° C.

  In the present invention, the pH at 20 ° C. of the reaction solution collected during the reaction (from the start of the reaction to the end of the reaction) is defined as the pH during the reaction. It is preferable to start the reaction under conditions that clearly show that the pH during the reaction is 7 or less (monomer ratio, solvent, other components, etc.).

  When the reaction system is non-aqueous, it can be measured by adding an amount of water capable of measuring pH to the reaction system.

In the method for producing the component (A), the monomers 1, 2 and 3 are reacted under the conditions exemplified in the following (1) and (2), usually under consideration of other conditions, The pH during the reaction is considered to be 7 or less.
(1) A monomer solution having a pH of 7 or less containing all of the monomers 1, 2 and 3 is used for the copolymerization reaction of the monomers 1, 2 and 3.
(2) The copolymerization reaction of the monomers 1, 2 and 3 is started at pH 7 or less. That is, the reaction is started after the reaction system containing the monomers 1, 2 and 3 is brought to pH 7 or lower.

[Chain transfer agent]
The chain transfer agent has a function of causing a chain transfer reaction in radical polymerization (a reaction in which a growing polymer radical reacts with another molecule to move a radical active site). It is a substance to be added.

  Examples of chain transfer agents include thiol chain transfer agents and halogenated hydrocarbon chain transfer agents, and thiol chain transfer agents are preferred.

As the thiol chain transfer agent, those having a —SH group are preferable, and in particular, the general formula HS—R—Eg (wherein R represents a hydrocarbon-derived group having 1 to 4 carbon atoms, and E is − OH, —COOM, —COOR ′ or —SO ₃ M group, M represents a hydrogen atom, monovalent metal, divalent metal, ammonium group or organic amine group, and R ′ represents an alkyl having 1 to 10 carbon atoms. In which g represents an integer of 1 to 2, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, Examples include octyl thioglycolate, octyl 3-mercaptopropionate, and the like from the viewpoint of chain transfer effect in a copolymerization reaction including monomers 1 to 3. Mercaptoethanol are preferable, more preferably mercaptopropionic acid. These 1 type (s) or 2 or more types can be used.

  Examples of the halogenated hydrocarbon chain transfer agent include carbon tetrachloride and carbon tetrabromide.

  Examples of other chain transfer agents include α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, 2-aminopropan-1-ol and the like. A chain transfer agent can use 1 type (s) or 2 or more types.

[Polymerization initiator]
In the method for producing the component (A), it is preferable to use a polymerization initiator. %, Particularly 10 to 30 mol% is preferred.

  Examples of aqueous polymerization initiators include ammonium persulfate salt or alkali metal salt, hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) dihydrate, etc. These water-soluble azo compounds can be used. In addition, an accelerator such as sodium bisulfite and an amine compound can be used in combination with the polymerization initiator.

[solvent]
In the production of the component (A), it can be carried out by a solution polymerization method, and the solvent used at that time contains water or water and methyl alcohol, ethyl alcohol, isopropyl alcohol acetone, methyl ethyl ketone or the like. And hydrous solvent solvents. In view of handling and reaction equipment, water is preferred. In particular, when an aqueous solvent is used, the pH of the monomer solution containing the monomer 2 and / or the monomer 3 is preferably 7 or less, more preferably 0.1 to 6, particularly 0.2 to 4. A copolymerization reaction is preferably used for the reaction in terms of uniformity of the monomer mixture (handleability), monomer reaction rate, and suppression of crosslinking by hydrolysis of the pyro compound of the phosphoric acid compound.

  (A) An example of the manufacturing method of a component is shown. A predetermined amount of water is charged into a reaction vessel, the atmosphere is replaced with an inert gas such as nitrogen, and the temperature is raised. Prepare monomer 1, monomer 2, monomer 3, chain transfer agent mixed and dissolved in water, and polymerization initiator dissolved in water, and take 0.5 to 5 hours. Drip into the reaction vessel. At that time, each monomer, chain transfer agent and polymerization initiator may be dropped separately, or a mixed solution of monomers can be charged in a reaction vessel in advance and only the polymerization initiator can be dropped. is there. That is, the chain transfer agent, the polymerization initiator, and other additives may be added as an additive solution separately from the monomer solution, or may be added to the monomer solution after being added. From the viewpoint of stability, it is preferable to supply the reaction system as an additive solution separately from the monomer solution. In any case, the pH of the solution containing the monomer 2 and / or the monomer 3 is preferably 7 or less. Further, the copolymerization reaction is preferably performed with an acid agent or the like while maintaining the pH at 7 or less, and preferably aging is performed for a predetermined time. The polymerization initiator may be added dropwise at the same time as the monomer, or may be added in portions, but it is preferable to add in portions in terms of reducing unreacted monomers. For example, in the total amount of the polymerization initiator to be finally used, 1/2 to 2/3 polymerization initiator is added simultaneously with the monomer, and the remainder is aged for 1 to 2 hours after the completion of the monomer dropping, It is preferable to add. If necessary, it is further neutralized with an alkali agent (such as sodium hydroxide) after completion of ripening to obtain the phosphate ester polymer according to the present invention. This production example is suitable as a method for producing the component (A) according to the present invention.

  The total amount of monomers 1, 2 and 3 in the reaction system and other copolymerizable monomers is preferably 5 to 80% by weight, more preferably 10 to 65% by weight, and particularly preferably 20 to 50% by weight. .

  The component (A) preferably has a weight average molecular weight (Mw) of 10,000 to 150,000. This component (A) has a Mw of 10,000 or more, preferably 12,000 or more, more preferably 13,000 or more, and more preferably 14 from the viewpoint of reducing the amount of mixed water and reducing resistance during extrusion molding. 15,000 or more, particularly preferably 15,000 or more, and from the viewpoint of high molecular weight by crosslinking, suppression of gelation and performance, from the viewpoint of reducing the amount of mixed water and relaxing resistance during extrusion, preferably 150,000 or less. Is 130,000 or less, more preferably 120,000 or less, more preferably 110,000 or less, and particularly preferably 100,000 or less. From the above viewpoint, preferably 12,000 to 130,000, more preferably 13,000 to 120,000, more preferably 14,000 to 110,000, particularly preferably 15,000 to 10 , It is 000. It is preferable to have Mw in this range and Mw / Mn is 1.0 to 2.6. Here, Mn is a number average molecular weight.

(A) Mw and Mn of a component are measured by the gel permeation chromatography (GPC) method of the following conditions.
[GPC conditions]
Column: G4000PWXL + G2500PWXL (Tosoh)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2mg / mL
Reference material: Polyethylene glycol equivalent

  Further, in the chart pattern showing the molecular weight distribution obtained by the GPC method under the above conditions, the area having a molecular weight of 100,000 or more is 5% or less of the total area of the chart, so that dispersibility (required addition amount reduction) It is more preferable in terms of the viscosity reducing effect.

  The component (A) is preferable in terms of reducing the amount of mixed water and using the component (B) in combination, particularly in terms of relaxation of resistance during extrusion molding.

<(B) component>
The water-soluble polymer compound (B) is a water-soluble polymer other than the component (A), and has a weight average molecular weight of 10,000 or more with a viscosity of 10 mPa · s or more when 0.5% by weight is dispersed in water. It is a compound of this. This viscosity is a 0.5% dispersion measured by a B-type rotational viscometer (25 ° C., rotation speed 30 rpm, rotor No. 1). The component (B) contributes to shape retention of the molded body before curing and resistance reduction during extrusion molding. Specifically, at least one selected from the group consisting of nonionic cellulose ethers, acrylic acid polymers, polyalkylene glycols, and polysaccharides obtained by fermentation is preferable.

  Examples of nonionic cellulose ethers include methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, and the like. The viscosity of these preferable dispersions is preferably 10 mPa · s or more, and more preferably 100 to 10,000 mPa · s. This viscosity is a 0.5% dispersion measured by a B-type rotational viscometer (25 ° C., rotation speed 30 rpm, rotor Nos. 1 to 4 are appropriately used corresponding to the viscosity).

  As the acrylic polymer, the viscosity of the non-neutralized dispersion is preferably 20 mPa · s or more, and more preferably 30 to 300 mPa · s. Specific examples include polyacrylic acid or a salt thereof, polyacrylamide and the like. This viscosity is measured with a B-type rotational viscometer (25 ° C., rotation speed: 60 rpm, rotor Nos. 1 to 3 are appropriately used corresponding to the viscosity) for the 0.5% dispersion.

  Examples of the polyalkylene glycol include those having a weight average molecular weight of 20,000 or more, and further 20,000 to 5,000,000. This weight average molecular weight is calculated from OHV (hydroxyl value) measured by the pyridine phthalic anhydride method according to ASTM, D1638-59T, and Hydroxynumer method-B. As the polyalkylene glycol, polyethylene glycol is preferable.

  Examples of the polysaccharide obtained by fermentation include yeast glucan, linear or branched β-1,3 glucan, and xanthan gum.

  As the component (B), nonionic cellulose ether is preferable because of its excellent resistance relaxation effect during extrusion molding and excellent shape retention after extrusion molding.

<Admixture for extrusion molding>
In the admixture of the present invention, the weight ratio of the component (A) to the component (B) is preferably (A) / (B) = 100/10 to 100/1000, more preferably 100/10 to 100/500, 100/10 to 100/300 is preferable because of its excellent resistance relaxation effect during extrusion molding.

  The admixture of the present invention is preferably in the form of a two-component kit comprising an agent containing the component (A) and an agent containing the component (B). The kit can include means for separating and holding the two agents (for example, a packaging container). In the form of a two-component kit, a method of using both of the two agents as a material for kneading the cementitious material and water, or adding to a kneaded material such as the cementitious material and water is preferable. In addition, although 2 agents can be mixed and used beforehand, since the aqueous solution containing (B) component tends to increase in viscosity, it is preferable to use separately from viewpoints, such as workability | operativity.

  In the form of a two-component kit, the agent containing the component (A) is preferably an aqueous solution from the viewpoint of ease of production and workability. It is preferable to contain 5 to 40 weight% of (A) component in this aqueous solution, 10 to 40 weight% is more preferable, and 20 to 35 weight% is further more preferable.

  Moreover, in the form of a two-component kit, the agent containing the component (B) is preferably a powder from the viewpoints of manufacturability and workability. The powder preferably contains 70 to 100% by weight of component (B), more preferably 90 to 100% by weight, and still more preferably 100% by weight.

  The admixture for extrusion molding of the present invention can be used in combination with known antifoaming agents and additives (materials). For example, AE agent, AE water reducing agent, fluidizing agent, high performance water reducing agent, retarder, early strengthening agent, accelerator, foaming agent, foaming agent, water retention agent, thickener other than (B) component, waterproofing agent , Blast furnace slag, fly ash, silica fume and the like.

  The admixture for extrusion molding according to the present invention is added to a material used when kneading a cementitious material and water or a water kneaded material (hydraulic composition) using a cementitious material as a main raw material. As the cementitious material, blast furnace cement, fly ash cement and the like can be used in addition to ordinary Portland cement, and are not particularly limited. In addition, as the fibers for bending reinforcement, inorganic fibers such as asbestos, rock wool, glass fibers and steel fibers, and organic fibers such as carbon fibers, nylon fibers, vinylon fibers, polypropylene fibers and aramid fibers can be used. For example, the admixture for extrusion molding of the present invention, a cementitious material, an aggregate (for example, cinnabar, fly ash, silica fume, etc.), fibers and water are mixed in a mixer to prepare a kneaded product, An extruded product can be obtained by molding and curing with an extrusion molding machine.

  In the admixture of the present invention, the component (A) is 0.01 to 5.0 parts by weight, further 0.05 to 1.0 parts by weight, and the component (B) is 0 with respect to 100 parts by weight of the cementitious material. .1 to 10.0 parts by weight, more preferably 0.1 to 3.0 parts by weight. The admixture of the present invention is good even in a hydraulic composition for an extruded product obtained by using water in a low water content of 40 to 70 parts by weight and further 40 to 50 parts by weight with respect to 100 parts by weight of cement. Extrudability can be obtained.

  The cement-based extruded molded product that is the target of the admixture for extruded molded product of the present invention can be suitably used as a formwork for building materials and concrete in terms of excellent dimensional accuracy and good appearance. it can. In particular, the extruded product of the present invention is suitable for applications that require a bending strength of 25N or more, particularly 28 to 36N.

Production Example A1
366 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, and was purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. 450 g of ω-methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) (effective part 60.8% by weight, moisture 35% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 71.6 g of phosphoric acid ester (A), which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 4.5 g of 3-mercaptopropionic acid, and 8.4 g of ammonium persulfate in water Two of those dissolved in 48 g were added dropwise over 1.5 hours. After aging for 1 hour, 1.8 g of ammonium persulfate dissolved in 10 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 44.4 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-1 having a weight average molecular weight of 35,000. (Monomer polymerization pH: 1.0, reaction rate 100%)

The phosphoric acid ester (A) used in this production example was prepared by charging 200 g of 2-hydroxyethyl methacrylate and 36.0 g of 85% phosphoric acid (H ₃ PO ₄ ) in a reaction vessel. Phosphoric acid) (P ₂ O ₅ ) 89.1 g was gradually added while cooling so that the temperature did not exceed 60 ° C. After completion, the reaction temperature was set to 80 ° C., reacted for 6 hours, and cooled. This phosphate esterified product (A) was also used in some of the following production examples.

Production Example A2
371 g of water was charged into a glass reaction vessel with a stirrer (four-necked flask), purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 500 g of ω-methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) (effective part 60.8% by weight, moisture 35% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 34.1 g of phosphoric acid ester (A), which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 2.8 g of 3-mercaptopropionic acid, and 7.2 g of ammonium persulfate in water Two of those dissolved in 41 g were added dropwise over 1.5 hours. After aging for 1 hour, 1.6 g of ammonium persulfate dissolved in 9 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of the aging, the mixture was neutralized with 21.2 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-2 having a weight average molecular weight of 34,000. (Monomer polymerization pH: 1.1, reaction rate 100%)

Production Example A3
A glass reaction vessel (four-necked flask) with a stirrer was charged with 381 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 520 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 23) (effective part 60.8% by weight, moisture 35% by weight), mono-[(2-hydroxyethyl) methacrylic acid] phosphate and phosphorus A mixture of 28.6 g of phosphoric acid ester (A) which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 2.8 g of 3-mercaptopropionic acid, and 7.2 g of ammonium persulfate in water Two of those dissolved in 41 g were added dropwise over 1.5 hours. After aging for 1 hour, 1.6 g of ammonium persulfate dissolved in 9 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 17.7 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-3 having a weight average molecular weight of 36000. (Monomer polymerization pH: 1.1, reaction rate 100%)

Production Example A4
A glass reaction vessel (four-necked flask) equipped with a stirrer was charged with 471 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 290 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 9) (effective content 84.4% by weight, moisture 10% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 93.8 g of phosphoric acid ester (A), which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 11.3 g of 3-mercaptopropionic acid, and 8.2 g of ammonium persulfate in water Two of those dissolved in 46 g were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 3.3 g of ammonium persulfate in 19 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the solution was neutralized with 58.2 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-4 having a weight average molecular weight of 25,000. (Monomer polymerization pH: 1.0, reaction rate 99%)

Production Example A5
489 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 290 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 9) (effective content 84.4% by weight, moisture 10% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 53.2 g of phosphoric acid ester (A) which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 9.1 g of 3-mercaptopropionic acid and 7.8 g of ammonium persulfate in water Two of those dissolved in 44 g were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 3.1 g of ammonium persulfate in 18 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 33.0 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-5 having a weight average molecular weight of 21,000. (Monomer polymerization pH: 1.1, reaction rate 98%)

Production Example A6
A glass reaction vessel (four-necked flask) with a stirrer was charged with 189 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 40 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 9: NK ester M90G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2- Hydroxyethyl) methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 43.8 g and 3-mercaptopropionic acid 1.6 g in water 40 g and ammonium persulfate 5.4 g in water 62 g Two of the dissolved ones were added dropwise over 1.5 hours. After aging for 1 hour, 2.7 g of ammonium persulfate dissolved in 31 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 54.4 g of a 20% aqueous sodium hydroxide solution to obtain a polymer a-6 having a weight average molecular weight of 51,000. (Monomer polymerization pH: 1.1, reaction rate 100%)

Production Example A7
A glass reaction vessel (four-necked flask) with a stirrer was charged with 218 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 55 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2- Hydroxyethyl) methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 32.3 g and 3-mercaptopropionic acid 1.1 g dissolved in water 55 g and ammonium persulfate 3.8 g in water 43 g Two of the dissolved ones were added dropwise over 1.5 hours. After aging for 1 hour, 1.9 g of ammonium persulfate dissolved in 22 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 40.1 g of a 20% aqueous sodium hydroxide solution to obtain a polymer a-7 having a weight average molecular weight of 51,000. (Monomer polymerization pH: 1.3, reaction rate 100%)

Production Example C1
A glass reaction vessel with a stirrer (four-necked flask) was charged with 281.4 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethyleneglycol methacrylate (added mole number of ethylene oxide 120) 336.5g, methacrylic acid 22.2g and 2-mercaptoethanol 1.89g dissolved in water 238.2g, and ammonium persulfate 3.68g dissolved in water 45g The two were added dropwise over 1.5 hours each. Subsequently, 1.47 g of ammonium persulfate dissolved in 15 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1 hour. After completion of aging, the mixture was neutralized with 18.7 g of 48% sodium hydroxide to obtain a copolymer c-1. (Weight average molecular weight 79000)

Production Example C2
A glass reaction vessel with a stirrer (four-necked flask) was charged with 246.4 g of water, purged with nitrogen while stirring, and heated to 56 ° C. in a nitrogen atmosphere. The mixture of 148.8 g of ω-methoxypolyethyleneglycol methacrylate (ethylene oxide addition mole number 10), 39.2 g of methacrylic acid and 2.32 g of 3-mercaptopropionic acid and 43.3 g of 5% aqueous solution of ammonium persulfate for 1.5 hours each It was dripped over. Thereafter, aging was performed at the same temperature (56 ° C.) for 3 hours. After completion of aging, the mixture was neutralized with 48% sodium hydroxide to pH = 6 to obtain a copolymer c-2. (Molecular weight 34000)

Examples 1-14 and Comparative Examples 1-4
When an extruded product is produced from the following blend for an extruded product using the copolymer obtained above (collectively referred to as component (A) for convenience) and the component (B) shown below. Was evaluated. The results are shown in Table 1.

(1) (B) component, b-1: methyl cellulose (High Metros 65SH, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-2: Hydroxyethyl cellulose (Unicel QP-4400H, manufactured by Daicel Chemical Industries, Ltd.)
B-3: Polyacrylamide (Hibiswako 103, manufactured by Wako Pure Chemical Industries, Ltd.)
B-4: Polyethylene glycol (PEO-8, manufactured by Sumitomo Seika Co., Ltd.)
B-5: β-1.3 glucan (Biopoli, Takeda Pharmaceutical Company Limited)
B-6: Xanthan gum (Kelzan, manufactured by Sanki Co., Ltd.)

(2) Component and blending amount of water kneaded product for extruded molded body-Ordinary Portland cement (manufactured by Taiheiyo) 100 parts by weight-Touraura sand 50 parts by weight-Vinylon fiber 20 parts by weight-Component (A) Addition amount ( Parts by weight per 100 parts by weight of cement)
-(B) component Addition amount of Table 1 (parts by weight relative to 100 parts by weight of cement)

(3) Manufacture of Extruded Molded Body (A) Component, (B) Component, Component of Water Kneaded Product for Extruded Molded Body, and Water Amount shown in Table 1 by kneading machine (Miyazaki Tekko Co., Ltd .: KHS-80) A kneaded product was prepared by mixing with an extrusion molding machine (Miyazaki Tekko Co., Ltd. model: FM-301) with a die having a width of 60 mm and a thickness of 8 mm attached to the tip to produce a molded plate. Next, 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 of the molding machine, the bending strength, appearance, and dimensional accuracy of the resulting molded plate were measured and evaluated as follows. The results are shown in Table 1. In addition, the amount of mixed water of Table 1 is the weight part of water with respect to 100 weight part of cement.

(4) Evaluation method (4-1) Extrusion speed The length of the molded body per minute when extrusion molding was measured.

(4-2) Bending strength Measured according to JIS-R5201.

(4-3) Appearance The appearance of the surface of the molded product as a final product was visually observed and evaluated according to the following criteria.
A: The surface is extremely smooth and has no scratches.
○: The surface is smooth and there are no scratches.
Δ: Slight scratch on the surface ×: Many scratches on the surface

(4-4) Dimensional accuracy The molded product as the final product was evaluated according to the following criteria.
◎: Both width and thickness errors are less than 0.1mm ○: Both width and thickness errors are 0.1mm to less than 0.2mm △: Both width and thickness errors are 0.2mm to less than 0.3mm ×: Width and thickness errors Both 0.3mm or more

  Even when the amount of mixed water was 45 parts by weight with respect to 100 parts by weight of cement, the admixtures of the examples gave good results in extrusion speed, bending strength, dimensional accuracy and appearance. It can be seen that the admixtures of the comparative examples are all inferior.

Claims (3)

Monomer 1 containing monomer 1 represented by the following general formula (1), monomer 2 represented by the following general formula (2) and monomer 3 represented by the following general formula (3) An admixture for an extrusion-molded product comprising a phosphate ester polymer (A) obtained by copolymerizing a body and a water-soluble polymer compound (B).

[Wherein R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom or — (CH ₂ ) q (CO) pO (AO) rR ⁴ , and AO is an oxyalkylene having 2 to 4 carbon atoms. Group or oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R ⁴ is a hydrogen atom or a carbon number of 1 to 18 Represents an alkyl group. ]

[Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 30, M ³ and M ⁴ are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]

[Wherein R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 30 and M ⁵ is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ] The extrusion according to claim 1, wherein the water-soluble polymer compound (B) is at least one selected from the group consisting of nonionic cellulose ethers, acrylic acid polymers, polyalkylene glycols, and polysaccharides obtained by fermentation. Admixture for molded products. The extrusion molded object manufactured using the admixture for extrusion molded articles of Claim 1 or 2.