JPH01261250A - Admixture for cement concrete and mortar produced by using highly water-absorbing resin - Google Patents

Abstract

PURPOSE:To prevent the generation of bleeding water and prevent the lowering of the adhesivity of the concrete, etc., to a horizontal reinforcing steel and coarse aggregate, by mixing cement concrete and mortar with a water-absorbing polymeric substance having a controllable induction period from the contact with water to the start of water-absorption. CONSTITUTION:A water-absorbing resin composition (A) which is an admixture spending 10-120min from the contact with water to the start of water- absorption is produced by coating the surface of a water-absorbing resin (e.g., Aqualic C3 or Sumikagel S-50) with a slowly water-soluble and/or hydrolyzable resin (e.g. vinyl acetate resin or ethylene-vinyl acetate copolymer). The admixture may be a kneaded composition (B) of a thermoplastic resin and/or a rubber and the above water-absorbing resin or may be a water-absorbing resin composition (C) produced by coating the composition B with a slowly water-soluble and/or hydrolyzable resin at a weight ratio of 100/20.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to cement concrete and mortar admixtures. More specifically, it is an admixture material made of a water-absorbing polymer substance in which the time from contact with water to when it substantially starts absorbing water is controlled.

[Prior Art] A cement composition consists of cement, fine aggregate, coarse aggregate, and other cement-added materials if necessary, and the hardening phenomenon of this cement composition is due to a chemical hydration reaction between cement and water. It is something. The strength of concrete obtained by a hydration reaction generally increases as the water/cement ratio decreases. However, in order to ensure workability during pouring of concrete (particularly in the case of ready-mixed concrete), the amount of water per unit is usually increased.

As a result, (1) breathing water is generated after pouring, and this breathing water forms a water film on the lower surface of horizontal reinforcing bars and coarse aggregate, which inhibits the adhesion of these with mortar; (2)
) Due to the migration of breathing water to the upper layer, the water/cement ratio in the upper layer increases and the strength decreases, resulting in uneven concrete strength. (3) The water path caused by breathing causes the concrete to harden. (4) Along with breathing water, inorganic substances that do not participate in the hydration reaction emerge on the concrete surface and deposit laitance.
5) Since the unit amount of water is increased for the purpose of ensuring workability, various problems arise, such as the need for more time than necessary for the concrete to set.

On the other hand, methods have been proposed in which water-absorbing resins such as polyacrylates, isobutylene-maleic acid copolymers, or saponified vinyl acetate-acrylic ester copolymers are added to cement compositions (for example, JP Showa 56-69257
No. and Japanese Patent Application Laid-Open No. 132747/1983).

[Problems to be Solved by the Invention] However, since the conventional cement-added materials made of water-absorbing resins as described above start absorbing water immediately upon contact with water, especially in the case of ready-mixed concrete, it is difficult to add water to the cement composition. The saturated water absorption amount is reached during mixing or between the time the mixed material is transported by a concrete mixer truck and placed at the pouring site.

Therefore, since the water-absorbing resin that has already reached the saturated water absorption amount does not exhibit any more water absorption power, the problems (1) to (5) above that occur after concrete placement cannot be solved.

[Means for solving the problem 1 The present inventors have developed a cement/concrete and mortar admixture that does not substantially start absorbing water during kneading after adding water to a cement composition or during transportation of the kneaded product. As a result of intensive studies, we have arrived at the present invention. That is, the present invention is a cement/concrete/mortar admixture made of a water-absorbing polymeric material that takes any time between 10 and 120 minutes from contact with water to when it substantially starts absorbing water. be.

In the present invention, water includes all kinds of artificially and naturally obtained water, such as tap water, well water, river water, rainwater, and distilled water. It also includes breathing water generated from concrete and mortar. Preference is given to neutral and alkaline waters with a Pl+ of 6 or more, in view of the fact that the admixtures of the invention are used in cement concrete and mortar. More preferably, it is alkaline water with Pl+ of 10 or more.

The time from contact with water until it actually starts absorbing water is 1
For example, the water-absorbing polymer substance for any time between 0 minutes and 120 minutes can be obtained by coating the surface of a water-absorbing resin with a slowly soluble and/or hydrolyzable resin in water. Water-absorbing resin composition.

■ A kneaded composition of a thermoplastic resin and/or rubber and a water-absorbing resin, or if necessary, the surface of the kneaded composition is further coated with the water-slowly soluble and/or hydrolyzable resin. Examples include water-absorbing resin compositions obtained by

Among these, preferred ones are those that can be manufactured at low cost, easy to control the water absorption start time (the time from contact with water until the actual start of water absorption), and after the start of water absorption, conventional water absorbent resins This is a water-absorbing resin composition (2) in that it exhibits a water absorption rate equivalent to that of the water-absorbing resin composition.

Here, the time until water absorption actually starts does not only mean that the water absorption function originally possessed by the water absorbent resin is expressed after an arbitrary period of time has passed, but also means the time until water absorption starts, that is, the water absorption It also includes the time required to reach the saturated water absorption amount of the polymeric substance, usually 30%, preferably about 10%. Note that, once water absorption has started, it is preferable that the resin exhibits a water absorption rate equivalent to that of a normal water absorbent resin.

In the composition (2), the resin that is slowly soluble and/or hydrolyzable in water has a functional group such as an ester group, an amide group, or a nitrile group that becomes a water-soluble group when hydrolyzed under alkaline conditions. [e.g. vinyl acetate resin, ethylene-vinyl acetate copolymer, polyamide resin,
Acrylonitrile resins, (meth)acrylic acid ester copolymer resins, etc.], resins with hydrophilic groups such as hydroxyl groups, carboxyl groups, sulfonic acid groups, and oxyethylene components [e.g. ethylene-acrylic acid copolymers, polyhydroxy Alkyl (meth)acrylate, urethane resin containing ethylene oxide component, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylate, polyethylene oxide, sulfonated polystyrene, styrene-maleic acid copolymer, etc. 1. Hydrophilic semi-synthetic resin [For example, carboxymethyl cellulose, hydroxyethyl cellulose, ethyl cellulose, etc.], hydrophilic natural polymer compounds [For example, gelatin, carrageenan, alginate, mannan, etc.].

Preferred among these are resins with functional groups that become water-soluble groups when hydrolyzed under alkaline conditions and resins with hydrophilic groups, and more preferred are vinyl acetate resins and ethylene-based resins. It is a urethane resin containing vinyl acetate copolymer, polyvinyl alcohol, polyethylene oxide, and ethylene oxide components.

The water-absorbing resin in the composition (2) includes starch or cellulose (a), a water-soluble monomer containing a carboxyl group and/or a sulfonic acid group, and/or a monomer that becomes water-soluble upon hydrolysis) and crosslinking. There is a water-absorbing resin obtained by polymerizing the agent (C) as an essential component and performing hydrolysis if necessary.

The details of (a), (b) and (C), the proportions of (a), b) and (C), the manufacturing method and specific examples of the water absorbent resin used in the production of the above water absorbent resin are disclosed in JP-A-52 -2588
6, Special Publication No. 53-46199, Special Publication No. 53-462
No. 00 and Japanese Patent Publication No. 55-21041.

Water-absorbing resins other than the above resins include those obtained by polymerizing (a) and (b), such as hydrolysates of starch-acrylonitrile graft polymers, hydrolysates of cellulose-acrylonitrile graft polymers; (a) crosslinked products such as crosslinked products of carboxymethyl cellulose; (b
) and (C), such as partial hydrolysates of cross-linked polyacrylamide, cross-linked sulfonated polystyrene, JP-A-52-14689 and JP-A-52-27
Saponified products of vinyl ester-unsaturated carboxylic acid ester copolymers, crosslinked polyacrylates, crosslinked acrylic acid-acrylic acid ester copolymers, crosslinked isobutylene-maleic anhydride copolymers, and Examples include crosslinked carboxylic acid-modified polyvinyl alcohol. Furthermore, the polymer (b) having self-crosslinking property (
For example, self-crosslinking polyacrylates), crosslinked polyethylene oxide, crosslinked polyvinyl alcohol, etc. can also be used.

It is also possible to use a resin in which the above-mentioned water-absorbing resin is further surface-crosslinked with a crosslinking agent to provide a crosslinking gradient.

The above-mentioned water-absorbing resin has a saturated absorption amount of P) 112.5 to alkaline water of at least 10 g/g, preferably 30 g/g or more.

There is no particular restriction on the shape of the water-absorbing resin, and it may be in any shape such as powder, flakes, or fibers, but powder is preferable. More preferably, it is a fine powder with an average particle size of 150 μm or less.

Organic powders (e.g., cellulose derivatives, starch derivatives, pulp powders, stearate compounds, etc.) and powders (e.g., pearlite, silica, bentonite, zeolite, shirasu balloons, etc.) are added to the water-absorbing resin as extenders and fillers. ;Hydrophobic fiber etc. can be used together. In addition, a surfactant, a water agent, a crosslinking agent, etc. can be used in combination if necessary, and there is no particular limitation on the amount of these mixed, and the amount that is usually used in combination may be used.

The water-absorbent resin composition (1) is produced by coating, encapsulation, or the like. For example, (a) resins that are slowly soluble and/or hydrolyzable in water and/or alkaline solutions may be mixed with organic solvents (alcohol-based, ketone-based, aliphatic or aromatic hydrocarbon-based, ester-based, etc.); A method of dissolving the water-absorbing resin at a concentration of 0.1 to 30% by weight in a mixed solvent or water-containing solvent, etc., and immersing the water-absorbing resin in this solution and drying it, (0)
A method of dispersing the water absorbent resin in the above resin solution and microencapsulating it by coacervation method or flocculation method, (c) a method of microcapsulating it by a hybridization system, (d) a method of microencapsulating the water absorbent resin on the surface of the water absorbent resin. A method of spraying or applying the above resin solution and drying it; Jie y
(g) a method of directly coating the surface of the water-absorbing resin with the resin in a molten state and cooling it.

The water absorption start time of the water absorbent resin composition obtained as described above can be determined by changing the type of resin to be coated, the amount of coating, the film thickness, and the particle size of the composition, or by adding the following other additives. It can be controlled as appropriate.

The ratio of water-absorbent resin to coating resin is 100% of water-absorbent resin.
The amount of resin to be coated is usually 0.1 to 300 parts by weight, preferably 1 to 200 parts by weight. The thickness of the coating layer is usually 0.005 to 1 mm on average, preferably 0.1 to 0.5 mm.

When producing the above composition, other additives may be added as necessary, such as inorganic or organic fillers (silica, bentonite, asbestos, glass fiber, etc.), surfactants (sorbitan aliphatic ester, calcium stearyl lactate, etc.), wall film forming aids, etc. Agents (dimethylpolysiloxane, etc.) can be used in combination.

Examples of the thermoplastic resin in the composition (2) include polyethylene, polypropylene, polyamide, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, chlorinated polyethylene, chlorosulfonated polyethylene, flexible polyvinyl chloride, and polyurethane. , linear thermoplastic polyester resin, etc.

Examples of the rubber include synthetic rubber (e.g., butyl rubber, isoprene rubber, butadiene rubber, chloroprene rubber, styrene-diene copolymer rubber, acrylonitrile-diene copolymer rubber, isobutylene-isoprene copolymer rubber, etc.), natural rubber, recycled rubber, etc. .

These thermoplastic resins and/or rubbers may be used alone or in combination of two or more.

Among the above thermoplastic resins and/or rubbers, preferred are ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, chlorinated polyethylene, polyurethane, and acrylonitrile-diene copolymer rubber.

Examples of the water-absorbing resin include those similar to the above-mentioned water-absorbing resins.

The blending ratio of the thermoplastic resin and/or rubber to the water absorbent resin is usually 5 to 500 parts by weight, preferably 10 to 400 parts by weight, of the water absorbent resin per 100 parts by weight of the thermoplastic resin.
Parts by weight. If the amount of the water-absorbing resin is less than 10 parts by weight, the resulting kneaded composition will not exhibit sufficient absorbency even after a long period of time when it comes into contact with an alkaline solution. Therefore, in order to achieve the object of the present invention, it is necessary to add a large amount of it to the cement composition, which results in deterioration of the quality of concrete. 500 again
If the amount exceeds 1 part by weight, the water absorption rate of the obtained kneaded composition becomes too high and the object of the present invention is not satisfied.

However, this kneaded composition can also be used as the admixture of the present invention by coating its surface with a slowly soluble and/or hydrolyzable resin in water by the method described above.

As a method for producing a kneaded composition (1) of a thermoplastic resin and/or rubber and a water-absorbing resin, for example, (1) blending a predetermined amount of a thermoplastic resin and a water-absorbing resin, and adding an anti-aging agent and a filler as necessary. , plasticizers, release agents, pigments, surfactants, and other additives are blended according to conventional methods, melt-kneaded using equipment such as rolls, Banbury mixers, kneaders, etc., and then extruded or press-molded into desired shapes. How to make the shape and size of rubber, water-absorbing resin, and if necessary, the above additive components in the specified amount, and the usual amount of rubber vulcanizing agent, vulcanization accelerator, vulcanization aid, etc. Examples include a method of vulcanization molding using a polyurethane resin to obtain a predetermined shape and size.

The admixture of the present invention comprises cement and, if necessary, aggregate,
It is used by blending it into a cement composition consisting of other cement additive materials. It can also be mixed into concrete or mortar.

Examples of the cement include portland cement [for example, ordinary portland cement, early-strength portland cement, moderate heat portland cement, sulfate-resistant portland cement, etc.1]; mixed cements [for example, blast furnace cement, fly ash cement, silica cement, etc.]. Other special cements such as alumina cement and white cement are also included.

As aggregates, for example, ordinary aggregates such as river sand, sea sand, gravel, crushed stone; lightweight aggregates: ultra-light aggregates; heavy aggregates; and other slag, whitebait, fly ash, perlite, asbestos, rock wool and Examples include mixtures thereof. The blending amount of these components is usually 50 to 1000 parts by weight per 100 parts by weight of cement.

Other cement additive materials include water-soluble polymers [
For example, cellulose derivatives such as methylcellulose, polyvinyl alcohol, synthetic resin emulsions [e.g. EVA emulsion, vinyl acetate emulsion, etc.]
, natural or synthetic comb latex [such as 5BIl latex], organic sulfonic acid compounds [sodium ligninsulfonate, sodium allylsulfonate, etc.], quick-setting agents [such as alkali aluminates and alkali carbonates alone or in combination, water glass-based, Calcium aluminate quick setting agents, etc.], inorganic fibers (e.g. glass fibers, asbestos, rock wool, etc.), water reducers, fluidizers, anti-efflorescence agents, and other known additives improve the workability and adhesion of cement compositions. , used as appropriate for purposes such as reinforcement.

The amount of these other cement additive materials may be the amount normally added.

The amount of the water-absorbing polymer substance to be mixed into the cement composition can be appropriately selected depending on the type of cement, water/cement ratio, unit water amount, type and amount of aggregate, etc., but it is usually 0.01 to 20% relative to the cement. % by weight, preferably from 0.1 to
It is 10% by weight. If the blending amount is less than 0.01% by weight, prevention of breathing water generation, laitance generation, etc. will be incomplete, and the object of the present invention will not be achieved.

On the other hand, if the amount exceeds 20% by weight, the strength of the concrete will be impaired and it will also be economically disadvantageous.

The method of applying the admixture of the present invention to a cement composition is as follows: (1) Mix a predetermined amount into the above cement composition, and use a mixing device such as a concrete mixer, mortar mixer, ribbon blender, conical blender, or screw type conhair. There is a way to mix it up.

Usually, concrete or mortar is obtained by adding a predetermined amount of water to this premixed dry cement composition and kneading it.

(2) A method in which water is added to a cement composition to produce concrete or mortar, and (3) a method in which it is mixed in with concrete or mortar before pouring.

[Examples] The present invention will be explained in more detail below using Examples and Usage Examples, but the present invention is not limited thereto. Note that parts in the examples are parts by weight.

The water absorption start time of the admixture material (the time from when it comes into contact with water until it actually starts absorbing water) was determined by the following measurement method.

Measuring method> The saturated absorption (Ag/g) of the admixture with alkaline water adjusted to pH 12.5 in advance is measured by the tea-hang method. Add the above-mentioned alkaline water containing Ag to a graduated cylinder, then add 1 g of the sample, and measure the time until the volume of the absorbed and swollen product reaches 20% of the initial alkaline water volume. The time required was defined as the water absorption start time.

Examples 1 to 4 Commercially available powdered water absorbent resin [Aqualic C34 (manufactured by Nippon Shokubai Kagaku Kogyo σ grade, crosslinked sulfonate water absorbent resin, water absorption start time within 1 minute), "Sumikagel S-50J (
Manufactured by Sumitomo Chemical ■, saponified vinyl acetate-acrylic acid ester copolymer, water absorption start time within 1 minute), rKI gel (
(manufactured by Kuraray ■, isobutylene-maleic acid copolymer crosslinked product, water absorption start time within 1 minute) or "Sunwet IM-
5% toluene of ethylene-vinyl acetate copolymer (vinyl acetate content 45%) was applied to the surface of 1000MPSJ (manufactured by Sanichi Kasei Kogyo ■, starch-acrylate graft copolymer crosslinked product, water absorption start time approximately 3 minutes). /Ethyl acetate? 9
't(l) was coated and dried by a spray drying method, and the weight ratio of water absorbent resin/ethylene-vinyl acetate copolymer was 1.
A water absorbent resin composition of 00/20 was obtained. These are referred to as admixture materials (A), (B), (C) and (D) of the present invention. The water absorption start time was about 60 minutes in all cases.

Example 5 Ethylene-vinyl acetate copolymer (vinyl acetate content 45%)
) 40 parts and water absorbent resin “Sunwet LM-1000”
60 parts of MPS were melt-kneaded in a Banbury mixer and extruded into chips with a particle size of about 0.5 mm to obtain a kneaded composition. This is referred to as the admixture material (E) of the present invention. The water absorption start time of this product was about 30 minutes.

Usage examples 1 to 4 Ordinary bolt punt cement 17250 g, tap water 93
00 g, fine aggregate (river sand) 38900 g, coarse aggregate (river gravel) 4850 g, and AE freezing agent 34.5 g, were mixed with the admixtures (A) of Examples 1 to 4.
120 g of each of B), (C), or (D) were mixed.

JIS A 1138 except that the kneading time is 1 hour.
Concrete was prepared according to How to Make Concrete in a Test Room J, and the amount of breathing, breathing rate, and compressive strength were measured. These results are shown in Table 1.

In addition, for the freezing test, JIS A1
Samples were collected according to JIS A 115r Sample collection method for unhardened concrete and measured according to JIS A 1123r Concrete breathing test method. In addition, for compressive strength testing, JIS A 113
A specimen was prepared according to 2 [How to make a concrete strength test specimen] and measured according to JIS A 1108 r Concrete compression test method.

Comparative Examples 1 to 5 The results obtained when the admixture of the present invention was not added are also listed in Table 1 as Comparative Example 1.

On the other hand, as Comparative Examples 2 to 5, the above-mentioned commercially available water absorbent resins "Aqualink C3", "Sumikagel 5-50", rK
I gel" or [Sunwet M-1000MI'S
When the same amount of J was used, the concrete lost its fluidity completely after about 5 minutes of mixing, and subsequent tests could not be performed.

(Unit of compressive strength: kgf/c+a) By adding the admixture material of the present invention, breathing was clearly reduced. Further, no decrease in compressive strength was observed.

Usage examples 5 to 7: 520g of ordinary Portland cement, 338g of tap water,
4.3 g of each of the admixtures (A), (B), or CD) of the present invention were mixed into a mortar containing 1040 g of Toyoura standard sand and kneaded. A length change test was conducted on this mortar. The results are shown in Table 2.

The test method was in accordance with JIS A 1129 r Mortar and Concrete Length Change Test Method (Comparator Method). Test conditions are temperature 20±1°C, humidity 6
0±5%R)l.

Comparative Example 6 In Use Examples 5 to 7, the results obtained when the admixture of the present invention was not added are also listed as Comparative Example 6 in Table 2.

By adding the admixture of the present invention, the length change rate was clearly reduced.

Usage examples 8 to 10 Ordinary Portland cement 345 kg/rrr, tap water 186 kg/n, fine aggregate (river sand) 778 kg/r
rf, coarse aggregate (river gravel) 970kg/rrr, AE
i solution 0.69 kg/nr and the admixture material of the present invention (C
), (D) or (IE) with a mix of 2°4 kg/n (each) was poured into a rectangular parallelepiped formwork of N 1 m x width 1 m x length 3 m, and the generation status of breathing water and laitance were measured. After 28 days, core specimens were cut out at right angles to the pouring direction from the bottom at positions 0.3 m, 1.5 m, and 2.7 m in the height direction using a concrete core drill. The compressive strength was measured.The results are shown in Table 3.

In addition, when cutting the core from concrete, use J.
According to ISA 1107.

Comparative Example 7 In Use Examples 8 to 10, the results obtained when the admixture of the present invention was not added are also listed as Comparative Example 7 in Table 3.

By adding the admixture of the present invention, there was almost no breathing water and almost no laitance deposition was observed. In addition, the core compressive strength was uniform with almost no difference observed between the upper layer and the lower layer. On the other hand, in Comparative Example 7, the compressive strength of the upper layer decreased.

[Effects of the Invention] The admixture material of the present invention has the following effects when mixed with cement/concrete and mortar.

(1) Almost no breathing water is generated.

The admixture of the present invention requires 10 to 120 minutes to transport concrete produced using a ready-mixed concrete brand to a construction site using a mixer truck, etc.)1. It has sufficient water absorption capacity even after pouring is completed. Therefore, the breathing water generated after concrete placement can be absorbed inside the concrete, so that the generation of breathing water on the concrete surface can be reduced.

(2) There is no need to worry about breathing water accumulating on the lower surfaces of horizontal reinforcing bars, coarse aggregate, etc., forming a water film, and reducing adhesion to mortar.

Breathing water migrates to the upper layer over time after concrete is placed, but during this process, breathing water often forms a water film on the lower surface of horizontal reinforcing bars and coarse aggregate, reducing the adhesion of mortar. . However, since the admixture material of the present invention absorbs breathing water inside the concrete structure, the above-mentioned problem of poor adhesion to mortar due to a water film does not occur.

(3) The water path generated by the upward migration of breathing water remains as it is even after the concrete has hardened, and there is no problem of lowering the strength and durability of the concrete structure.

(4) Uniform quality of the structure can be achieved.

(5) There is almost no deposition of laitance.

Therefore, there is no fear that the laitance deposited on the concrete surface will scatter and harm human health, and in addition, concrete with excellent appearance and surface smoothness can be obtained.

Furthermore, when pouring new and old concrete, there is no need to remove laitance, leading to labor savings and shorter construction times.

(6) There is no reduction in workability when placing concrete.

As described in Comparative Examples 2 to 5, when a conventional water-absorbing resin is used as an admixture, water absorption starts too quickly, resulting in extremely low concrete fluidity and poor workability during pouring.

However, since the admixture material of the present invention controls the water absorption start time, it is possible to ensure workability close to that obtained without additives.

(7) Low drying shrinkage of concrete and prevention of cracks.

Water absorbed by the water-absorbing polymer inside the concrete gradually transfers to the concrete side, keeping the concrete moist for a longer period than usual, reducing drying shrinkage and preventing the occurrence of cranks.

Because of the above effects, cement concrete and mortar mixed with the admixture material of the present invention are particularly effective when concrete is manufactured in a ready-mixed concrete plant and transported to a construction site in a mixer truck or the like. Therefore, it can be applied to housing construction sites; dam construction sites; concrete paved surfaces such as roads; bridge support construction sites, etc. In addition, box culverts; secondary concrete products such as precast materials, piles, blocks, U-shaped grooves, tetrapods, shield segments, and bridges; Effective in all situations requiring admixtures.

Patent applicant: Tsuruga Cement Co., Ltd.

Claims (1)

[Claims] 1. Cement/concrete and mortar made of a water-absorbing polymeric material whose time from contact with water to when it substantially starts absorbing water is any time between 10 minutes and 120 minutes. Admixture material. 2. The admixture material according to claim 1, wherein the water-absorbing polymeric substance is a water-absorbing resin composition obtained by coating the surface of a water-absorbing resin with a slowly soluble and/or hydrolyzable resin in water. 3. The water-absorbing polymer substance is a kneaded composition of a thermoplastic resin and/or rubber and a water-absorbing resin, and if necessary, the surface of the kneaded composition is made slowly soluble in water and/or hydrolyzable. The admixture material according to claim 1, which is a water-absorbing resin composition obtained by coating with a resin. 4. Claims 1 and 2, wherein the water is alkaline water with a pH of 10 or higher.
or the admixture material described in 3.