JPH1053447A - Cement hardening retarder and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a decorative pattern on a concrete product according to an aggregate exposed finish method by washing by using a cement hardening retarder capable of suppressing elution with moisture and sustaining the high ability to retard the hardening. SOLUTION: This cement hardening retarder comprises a polymer having units of a cement hardening retarding component hydrolyzable by actions of an alkali and is produced by introducing the units of the cement hardening retarding component hydrolyzable by the actions of the alkali into a main chain or a side chain of the polymer through ester bonds or acid amide bonds. The polymer having the hardening retarding component in the side chain is roughly classified into (1a) a homopolymer of a polymerizable monomer having the units of the hardening retarding component (a hydroxy-carboxylic acid, etc.) or a copolymer of the polymerizable monomer and at least either one of a copolymerizable monomer and a copolymerizable polymer (an unsaturated polyester) and (1b) a polymer in which the component having the ability to retard the hardening is bound to a reactive group such as carboxyl group in the side chain of the polymer through the ester bond. The polymer in which the hardening retarding component is introduced into the main chain may be a polyester containing the component having the ability to retard the hardening and at least two hydroxyl groups or carboxyl groups as a diol component or a dicarboxylic acid component. The hardening retarder may be a powdery or a granular material, a film or a sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cement setting retarder useful for delaying setting of cement and a method for producing the same.

[0002]

2. Description of the Related Art A cement setting retarder is a type of cement admixture used for delaying the hydration reaction of cement and, consequently, the setting and setting of mortar and concrete. As described in JP-A-1-172250, conventional cement setting retarders are roughly classified into two types, inorganic and organic, and as inorganic setting retarders,
Lead oxide, boron oxide, borax, zinc chloride, zinc oxide, magnesium silicofluoride, etc. are used, and as the organic curing retarder, sugar, oxycarboxylate, lignin sulfonate, gluconic acid and its salts, Keto acids such as pyruvic acid and α-ketoglutaric acid are used. And
The purpose of use of these hardening retardants is to cope with long-term transportation of ready-mixed concrete in summer and to relieve thermal stress in large-sized concrete structures.

On the other hand, the surface of concrete molded articles and various structures is often decorated using a so-called washing method, which is one of plastering techniques. This washing method is a method in which the mortar of the concrete surface layer is washed out by washing with water immediately before the cement hardens to expose a part of the aggregate. In this method, the timing of washing out is limited to a very narrow range in terms of time in relation to the hardening speed of concrete, so that it is difficult to mass-produce concrete slabs and apply it to large structures. If the hardening of only the concrete surface layer is inhibited by using a cement setting retarder, which is a kind of concrete admixture, the surface of the concrete product can be decorated regardless of the timing of washing out. Specifically, for example, a paper is impregnated with a curing retarder, and the impregnated paper is fixed to the bottom of the mold by pasting or the like, and then a fresh concrete is poured. After hardening of the concrete, the molded article is detached from the mold, and the uncured mortar on the surface in contact with the impregnated paper is washed away, thereby exposing the aggregate and obtaining a concrete product having a natural texture.

[0004] However, the cement setting retarder is originally a cement (hereinafter, unless otherwise specified, "concrete").
Mortar), and has high solubility in water. When such a cement setting retarder is applied to the above-mentioned washing method, the setting retarder dissolves in the moisture in the concrete when the ready-mixed concrete is poured, and together with the bleed water from the concrete in the formwork or on the surface of the structure. Flow. Therefore, the setting retarder flows to a location where washing is not required, or the curing retarder is locally concentrated in some cases, while the setting retarder flows out at a location where washing is required, and Functions cannot be effectively exhibited. Characters, especially on concrete moldings and structures
When decoration such as a pattern is applied by a washing-out method, it is very difficult to determine a site where the effect of the curing retarder is exhibited.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a cement setting retarder capable of suppressing elution by moisture and effectively exhibiting a high setting delay ability, and a method for producing the same. Another object of the present invention is to
An object of the present invention is to provide a cement setting retarder capable of maintaining high setting delay ability for a long period of time and a method for producing the same. Still another object of the present invention is to provide a cement setting retarder which can form a decorative pattern on a surface of a concrete product with high precision by a washing method, and a method for producing the same.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and have found that a component having a cement setting retarding ability is hydrolytically introduced into a main chain or a side chain of a polymer. In addition, the dissolution property of the setting delay component with respect to water and the setting delay ability can be suppressed, but with the contact with the cement mortar, the strong alkalinity of the cement mortar gradually hydrolyzes the polymer, and the effect of setting delay on the cement is effective. The present invention was completed. That is, the cement setting retarder of the present invention is composed of a polymer having a unit of a cement setting delay component that can be hydrolyzed by the action of an alkali. In this setting retarder, the unit of the cement setting retarding component may be linked by an ester bond or an acid amide bond in the main chain or side chain of the polymer. The polymer may be a homopolymer or a copolymer of a polymerizable monomer having a unit of a hydrolyzable cement setting delay component, and the copolymer may be a unit of a hydrolyzable cement setting delay component. And a copolymer of at least one of a copolymerizable monomer and a copolymerizable monomer and a copolymerizable polymer (such as an unsaturated polyester). The cement setting delay component is a compound having a hydroxyl group or a carboxyl group, for example,
Oxycarboxylic acid, ketocarboxylic acid, polyvalent carboxylic acid,
Sugars, glycosides, polyhydric alcohols and the like may be used. Polymers having a curing delay component introduced into the main chain include a compound having at least two reactive groups selected from a hydroxyl group and a carboxyl group, and an oxycarboxylic acid having at least both a hydroxyl group and a carboxyl group. And polyesters formed by an esterification reaction with a cement setting retarding component selected from the group consisting of: The ratio of the unit of the cement setting retarding component is, for example, about 5 to 60% by weight based on the whole polymer. The form of the curing retarder may be (1) a powder or granule, or (2) a film or sheet. The cement setting retarder is (a) a homopolymer or a copolymer of a polymerizable monomer having a unit of a cement setting delay component that can be hydrolyzed by the action of an alkali, or (b) a cement that can be hydrolyzed by an action of an alkali. It can be produced by introducing a unit of the cement setting delay component into the side chain or main chain of the polymer by esterification or amidation reaction of the setting delay component.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polymer constituting the cement setting retarder of the present invention has units of a cement setting delay component which can be liberated by hydrolysis by the action of an alkali.

[Cement Setting Delay Component] The cement setting delay component is not particularly limited as long as it can be introduced into the main chain or side chain of the polymer, but is usually an active hydrogen atom (hydroxyl group, carboxyl group, or amino group). have.
Examples of such a curing delay component include phosphonic acid compounds having a phosphonic group PO ₃ H ₂ [eg, aminodi (methylenephosphonic acid), aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid] , Ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid), etc.], oxycarboxylic acids (glycolic acid, lactic acid, malic acid, oxymalonic acid, mucus acid, tartaric acid, Citric acid, gluconic acid, hydroxypropanoic acid, glyceric acid, etc., ascorbic acid, isoascorbic acid, ketocarboxylic acid (pyruvic acid, ketoglutaric acid, etc.), organic carboxylic acids (oxalic acid, malonic acid, succinic acid, butanoic acid, etc.) Saturated polyvalent carb Acid, maleic acid, fumaric acid, unsaturated polycarboxylic acids such as itaconic acid, such as gluco cycloheptanone acid), a polyhydroxy compound (sugars, such as glycosides and polyhydric alcohols), such as lignin sulfonate can be exemplified. Sugars include, for example, sucrose, saccharose (sucrose), glucose (glucose), corn syrup, and the like. Glycosides include sugars such as glucose, fructose, mannose, galactose, xylose, arabinose, and hydroxy-C _{2. -4} alkyl group and C _2-4
Examples of the compound to which the alkylene oxide is added and the polyhydric alcohol include pyrogallol, gallic acid,
Aromatic polyhydric alcohols such as 4,6-trihydroxybenzoic acid can be exemplified. These curing retarding components can be introduced into the polymer alone or in combination of two or more.

[0009] Preferred cure retarding components have hydroxyl and / or carboxyl groups. Particularly, an oxycarboxylic acid, particularly an oxycarboxylic acid having two hydroxyl groups or two carboxyl groups in a molecule is preferable.

[0010] For example, when 0.1% by weight of the setting delay component is added to the cement, the setting delay component is 1.5 times or more the setting time of the cement mortar not added (for example, 1. 5 to 100 times), preferably 1.8 times or more (for example, about 2 to 100 times). More specifically, a hardening retarder for Portland cement using ordinary Portland cement, fine aggregate (sand) having a coarse grain ratio of 2.35 and 99% by weight of the whole passing through a 2.5 mm sieve, and water. Mortar composition prepared by kneading at a ratio of 0.1% by weight, a water / cement ratio = 0.50, and a sand / cement ratio = 2.75 with a Hobart mixer for 3 minutes. Setting test 21
In a mortar setting test according to ASTM C403, the setting start time T of mortar to which 0.1% by weight of a cement was added with respect to cement when the test was carried out in a constant temperature chamber at a temperature of 0 ° C.
1 is at least 1.5 times (T = T1 / T0 ≧) the setting start time T0 of the mortar to which no setting retarder is added.
1.5), and preferably 1.8 times or more (T ≧ 1.8).

[Polymer] The polymer includes (I) a polymer in which the unit of the curing retarding component is an ester bond or an acid amide bond in the side chain, and (II) a unit in which the curing retarding component in the main chain is an ester bond or They are roughly classified into acid amide-bonded polymers.

(I) The unit of the curing retarding component is bonded to the side chain.
And the polymer units are bonded curing delay component in the polymer side chain, (I
a) A homopolymer or copolymer of a polymerizable monomer having a unit of a hydrolyzable cement setting delay component, (Ib) The setting delay component can be hydrolyzed to a reactive group located on a side chain of the polymer. And a polymer bonded thereto.

(Ia) Homogenous or Copolymer of Polymerizable Monomer As the polymerizable monomer, a monomer in which the above-mentioned curing retardant and a polymerizable compound are hydrolysably bonded can be used. The curing retarding component and the polymerizable compound are linked by an ester bond or an amide bond (particularly, an ester bond). The polymerizable monomer includes a polymerizable compound having at least one hydroxyl group, a carboxyl group, an acid anhydride group, at least one reactive group selected from an epoxy group and an amino group,
An ester compound or an amide compound with a cement setting retarding component having a hydroxyl group or a carboxyl group is included. More specifically, the polymerizable monomer having a unit of the curing retarding component includes, for example, the following compounds.

(I) Ester of a hydroxyl group-containing polymerizable compound with a carboxyl group-containing curing retarder Examples of the hydroxyl group-containing polymerizable compound include allyl alcohol or a derivative thereof [allyl alcohol, alkylene oxide (ethylene oxide) Adduct to which C _2-4 alkylene oxide such as propylene oxide is added], 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, C _4-10 alkylene glycol mono (meth) acrylate, Polyoxy C _2-4 alkylene glycol mono (meth) acrylate, glycerin mono (meth) acrylate, glycerin di (meth) acrylate and the like are included. The ester is prepared by a conventional method,
For example, it can be obtained by esterifying a hydroxyl group-containing polymerizable compound and a carboxyl group-containing curing retardant in the presence of a catalyst and / or an organic solvent, if necessary.

(Ii) Ester of carboxyl group or acid anhydride group-containing polymerizable compound with hydroxyl group-containing curing retarder The carboxyl group or acid anhydride group-containing polymerizable compound includes, for example, (meth) acrylic acid and the like. Examples thereof include polymerizable polycarboxylic acids such as polymerizable monocarboxylic acid, maleic acid, maleic anhydride, fumaric acid, and itaconic acid, and acid anhydrides thereof. The ester can be obtained by a conventional method, for example, by esterifying a carboxyl group or an acid anhydride group-containing polymerizable compound and a hydroxyl group-containing curing retarder in the presence of a catalyst and / or an organic solvent, if necessary. Can be. Examples of such a compound include a compound in which a hydroxy-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate is ether-linked to a sugar such as glucose [for example, Nippon Seika Co., Ltd., trade name “Sucraph-GEMA” ] Is also included.

(Iii) Ester of Epoxy Group-Containing Polymerizable Compound and Carboxyl Group-Containing Curing Retarding Component Examples of the epoxy group-containing polymerizable compound include allyl glycidyl ether and glycidyl (meth) acrylate. The ester can be obtained by a conventional method, for example, by esterifying an epoxy group-containing polymerizable compound and a carboxyl group-containing curing retardant in the presence of a catalyst and / or an organic solvent, if necessary.

(Iv) Amide of Amino Group-Containing Polymerizable Compound and Carboxyl Group-Containing Cure Delay Component Examples of the amino group-containing polymerizable compound include aminostyrene and vinylamine (eg, vinyldimethylamine, vinyldiethylamine, etc.). No. The amide compound comprises an amino group-containing polymerizable compound and a carboxyl group-containing curing retarder, and optionally a catalyst and / or
Alternatively, it can be obtained by reacting in the presence of an organic solvent.

These polymerizable monomers can be used alone or in combination of two or more. Preferred polymerizable monomers include a polymerizable compound having a carboxyl group or an acid anhydride group (e.g., (meth) acrylic acid or maleic acid or an acid anhydride thereof) and a hydroxyl group-containing cement setting retarder (e.g., Esters with oxycarboxylic acids).

Polymerizable monomer having a unit of a curing delay component
May be polymerized alone, other copolymerizable monomers and copolymers
Even if copolymerized with at least one component of the polymer
Good. Copolymerizable monomers and copolymerizable polymers may be used in combination.
No. The copolymerizable monomer includes a polymer having the curing retarding component.
Various vinyl monomers copolymerizable with the compatible monomer,
For example, styrene monomers (for example, styrene, α-me
Styrene, vinyltoluene, etc.), acrylic monomer
Body [eg, (meth) acrylic acid, ethyl acrylate,
Butyl acrylate, 2-ethylhexyl acrylate,
(Meth) such as methyl methacrylate and butyl methacrylate
Acrylic acid C _1-18Alkyl ester, 2-hydroxyd
Tyl (meth) acrylate, 2-hydroxypropyl
Hydroxy C such as (meth) acrylate_2-6Alkyl
(Meth) acrylate, glycidyl (meth) acrylate
, (Meth) acrylonitrile, etc.], vinyl esters
Monomer (eg, vinyl acetate, vinyl propionate)
Etc.), vinyl ether monomers (methyl vinyl ether)
, Isobutyl vinyl ether, etc.), allyl ether
Monomer (allyl alcohol, allyl alcohol
Len oxide or propylene oxide adduct)
And so on. These copolymerizable monomers may be used alone or
Two or more can be used in combination. Preferred copolymerizable monomers
Means styrene monomer (especially styrene), acrylic
[Especially, (meth) acrylic acid, (meth) acrylic acid
C_1-10Alkyl ester, hydroxy C_2-4Alkyl
(Meth) acrylate, glycidyl (meth) acrylate
Etc.].

The copolymerizable polymer includes various polymers having a polymerizable unsaturated bond, for example, unsaturated polyester, epoxy (meth) acrylate formed by the reaction of an epoxy resin with (meth) acrylic acid, and the like. Vinyl ester resin, polyester (meth) acrylate using hydroxy C _2-6 alkyl (meth) acrylate such as (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate; Urethane (meth) acrylate using C _2-6 alkyl (meth) acrylate and the like are included. These copolymer polymers can be used alone or in combination of two or more. Preferred copolymerizable polymers are unsaturated polyesters. This unsaturated polyester exhibits a cement setting retarding ability by hydrolysis. for that reason,
When a copolymer of a polymerizable monomer having a unit of the curing delay component and an unsaturated polyester is used, a curing retarding ability is expressed by hydrolysis of a side chain, and also by hydrolysis of an ester bond of a main chain. As the curing retarding ability appears,
The curing retarding ability can be maintained for a long time.

The proportion of the polymerizable monomer having a unit of the curing retarding component is such that the proportion of the unit of the curing retarding component is 5 to 60% by weight, preferably 10 to 50% by weight, more preferably 20 to 50% by weight of the whole polymer. Can be selected from the range of about 50% by weight. The ratio of the polymerizable monomer having the unit of the curing retarding component is, for example, 10 to 1000 parts by weight, preferably 25 to 750 parts by weight, based on 100 parts by weight of the copolymerizable monomer and / or the copolymerizable polymer. Parts by weight, more preferably 50 to 50
The range may be about 0 parts by weight. In addition, when the copolymerizable polymer is an unsaturated polyester, the ratio of the polymerizable monomer having a unit of the curing delay component is, for example, 5 to 1000 parts by weight, preferably 100 parts by weight of the unsaturated polyester, preferably May be in the range of 10 to 750 parts by weight, more preferably about 20 to 500 parts by weight.

(Ib) A polymer in which a setting delay component is bonded to a reactive group on the side chain of the polymer In this polymer, a cement setting delay component is introduced into the side chain by a polymer reaction. That is, as a polymer,
Using a polymer having at least one type of reactive group selected from a hydroxyl group, a carboxyl group, an acid anhydride group and an amino group on the side chain, and cementing the cement by forming an ester or amide bond to the reactive group. A delay component is introduced.

As the polymer having a reactive group, for example, a hydroxyl group-containing polymer [derived from a cellulose derivative such as cellulose ester or cellulose ether, or a vinyl acetate polymer such as polyvinyl alcohol or ethylene-vinyl alcohol] is used. Polymers, homopolymers of the above hydroxyhydroxy C _2-6 alkyl (meth) acrylates and copolymers with other copolymerizable monomers (such as C _1-10 alkyl (meth) acrylate, styrene, etc.) ], A carboxyl group-containing polymer [a homopolymer of (meth) acrylic acid or a copolymer with another copolymerizable monomer (C _1-10 alkyl (meth) acrylate, styrene, etc.), maleic acid] , A copolymer of fumaric acid with a copolymerizable monomer (C _1-10 alkyl (meth) acrylate, styrene, etc.)] , Acid anhydride group-containing polymers [styrene-maleic anhydride copolymer, alkyl vinyl ether-maleic anhydride copolymer, etc.], amino group-containing polymers [substituted amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, etc.] And other copolymerizable monomers (e.g., C _1-10 alkyl (meth) acrylate, styrene, etc.). These polymers having a reactive group can be used alone or in combination of two or more.

The cement setting delay component located on the side chain of the polymer can be introduced by a conventional method, for example, by esterification with a carboxyl group-containing setting delay component in the case of a hydroxyl group-containing polymer. And acid anhydride group-containing polymers can be introduced by an esterification reaction with a hydroxyl group-containing curing retarder, and amino group-containing polymers can be introduced by an amidation reaction with a carboxyl group-containing curing retarder. The amount of the curing retardant to be introduced is, for example, about 5 to 60% by weight, preferably about 10 to 30% by weight, and more preferably about 15 to 30% by weight, based on the whole polymer into which the curing retarding component has been introduced.

(II) A polymer in which the unit of the curing retarding component is bonded to the main chain of the polymer. In this polymer, the unit of the curing retarding component is hydrolyzed into the main chain of the polymer by an esterification reaction. I have. That is, in this polymer, a curing retarding component selected from oxycarboxylic acids having at least both a hydroxyl group and a carboxyl group is used as a curing retarding component,
A curing delay component is introduced into the polyester main chain by an esterification reaction with a compound having at least two reactive groups selected from a hydroxyl group and a carboxyl group (such as a glycol component and a dicarboxylic acid component). The polyester may be linear, three-dimensionally branched or cross-linked. As the oxycarboxylic acid constituting the curing delay component, the compounds exemplified above can be used. Preferred examples of the curing retardant include dicarboxylic compounds (lactic acid, tartronic acid, malic acid, tartaric acid, citric acid, oxymalonic acid, etc.) and dihydroxy compounds (gluconic acid, glyceric acid, etc.).

The curing retarding component is introduced into the polyester by subjecting it to a dehydration condensation reaction (esterification reaction) as part or all of the glycol component or dicarboxylic acid component, and the resulting polyester may be a saturated polyester. It may be a saturated polyester. The unsaturated polyester can be prepared by using at least maleic anhydride (or maleic acid) as the dicarboxylic acid component.

As the glycol component for the curing delay component, ethylene glycol, propylene glycol,
1,3-butanediol, tetramethylene glycol,
C such as hexanediol and neopentyl glycol
_2-6 alkylene glycol; diethylene glycol, triethylene glycol, polyethylene glycol (hereinafter collectively referred to simply as polyethylene glycol unless otherwise specified), dipropylene glycol, tripropylene xericol, and polypropylene glycol (hereinafter unless otherwise specified) And these are simply referred to as polypropylene glycol), and polyoxyalkylene glycols such as polytetramethylene glycol. These glycol components may be used alone or in combination.

Examples of the dicarboxylic acid component with respect to the curing retardant component include aliphatic saturated dicarboxylic acids having about 2 to 10 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid and sebacic acid; Maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other aliphatic unsaturated dicarboxylic acids having about 4 to 6 carbon atoms, phthalic acid, phthalic anhydride, terephthalic acid Acids and aromatic dicarboxylic acids such as isophthalic acid are included. These polycarboxylic acids can be used alone or in combination of two or more.

The saturated or unsaturated polyester into which the curing delay component has been introduced may be used to adjust properties such as strength, elongation, flexibility, flexibility and resistance. May be modified by the following components. For example, instead of part of at least one of the glycol component and the dicarboxylic acid component, a polyhydric alcohol (for example, glycerin, trimethylolpropane, pentaerythritol, etc.), a polyhydric carboxylic acid (for example, trimellitic acid, (E.g., merit acid) can be copolymerized. A polycarboxylic acid component containing an aromatic dicarboxylic acid or a derivative thereof selected from phthalic acid, terephthalic acid, and isophthalic acid adjusts properties such as strength, elongation, flexibility, flexibility, and water resistance of the polyester. Useful for

Although the molecular weight of the saturated or unsaturated polyester is not particularly limited, for example, the weight average molecular weight is 300-2.
It is 5000, preferably about 500-15000.
The polyester into which the curing delay component has been introduced may be a gelled product. Further, the unsaturated polyester into which the curing delay component has been introduced may be a crosslinked cured product. Crosslinked cured product of unsaturated polyester, unsaturated polyester resin alone,
Alternatively, it can be obtained by polymerizing a polymerizable composition of an unsaturated polyester and a reactive diluent (polymerizable vinyl monomer) with a polymerization initiator such as an organic peroxide and curing. As the reactive diluent, a polymerizable vinyl monomer, for example, a styrene-based monomer such as styrene, an alkyl group such as methyl (meth) acrylate, ethyl (meth) acrylate, or butyl (meth) acrylate having about 1 to 10 carbon atoms is used. Examples include monomers having a functional group such as alkyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, (meth) acrylic acid, and glycidyl (meth) acrylate. One or more of these reactive diluents can be used. The amount of the reactive diluent can be selected according to the desired properties.
10 to 500 parts by weight, preferably 2 parts by weight, per 0 parts by weight
It is about 5 to 200 parts by weight.

Examples of the organic peroxide include methyl ethyl ketone peroxide, cumene hydroperoxide, benzoyl peroxide, t-butylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, dicumyl peroxide. And the like. The unsaturated polyester can be cured at room temperature, but in order to cure it in a short time (for example, about 0.5 to 50 minutes), it is advantageous to perform the curing at a temperature of about 60 to 200 ° C. In order to accelerate curing, if necessary, a curing accelerator,
For example, organic salts of cobalt such as cobalt naphthenate and cobalt octylate, β-diketones such as acetylacetone and ethyl acetoacetate, aromatic tertiary amines, and mercapto compounds may be used in combination.

The ratio of the unit of the curing retarding component is 5 to 60% by weight, preferably 10 to 50% by weight based on the whole polyester.
%, More preferably about 20 to 50% by weight.

The cement setting retarder of the present invention includes, in addition to other setting delay components, various additives such as coloring agents such as pigments and dyes, stabilizers such as ultraviolet absorbers and antioxidants, plasticizers, It may contain an antifoaming agent, an emulsifier, a filler and the like. [Form of Cement Setting Retarder] The form of the setting retarder of the present invention may be (1) a granular material or (2) a film or a sheet (hereinafter sometimes simply referred to as a setting retarder). The (1) powder may be (1a) a powder formed of the polymer, or (1b) a powder coated with the polymer.

The powder (1a) can be obtained by a conventional method, for example, a method such as pulverization, classification, granulation, spray drying, or a method such as suspension polymerization and drying, and is coated with a polymer. The powder (1b) can be obtained by coating an organic or inorganic powder with a method such as spraying or dipping, a fluidized bed coating, or a microencapsulation method. Organic powders include, for example, wood, thermoplastic resin (vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, styrene resin, (meth) acrylic resin,
Olefin resins, polyamides, polyacetals, polycarbonates, saturated polyesters, cellulose resins, etc.) and thermosetting resins (phenol resins, epoxy resins,
Urea resin, polyurethane, etc.), and inorganic powders include, for example, metals (iron, aluminum, etc.),
Inorganic compounds (diatomaceous earth, kaolin, talc, bentonite, clay, silica, alumina, zinc oxide, iron oxide,
Titanium oxide, glass, cement, calcium sulfate, calcium carbonate, barium sulfate, lime, etc.), sand and gravel, ceramics, carbon (carbon black, graphite, etc.). Organic or inorganic powders can be obtained by conventional methods such as pulverization, classification, cutting, granulation, molding and suspension polymerization.

The coating amount of the polymer having a curing retarding ability can be in a wide range, for example, 1 to 500 parts by weight, preferably 1 to 250 parts by weight, per 100 parts by weight of the organic or inorganic powder.
More preferably, it may be selected from the range of about 5 to 100 parts by weight. The shape of the granular material (1) is not particularly limited, and may be, for example, any of an amorphous shape, a spherical shape, an elliptical shape, a rod shape, and the like. The particle diameter of the powder (1) can be selected, for example, from the range of about 1 μm to 10 mm, preferably 5 μm to 30 mm, particularly about 10 μm to 10 mm.

(2) The curing retardation sheet may be (2a) a film or sheet composed of the polymer,
(2b) A film or sheet holding the polymer on a substrate may be used. Furthermore, the film or sheet (2b) holding the polymer may be (2b-1) a film or sheet formed on a base sheet that may be subjected to a mold release treatment, wherein the curing retardation layer containing the polymer may be (2b-2) A film or sheet in which the polymer is impregnated into a porous substrate may be used.

(2a) The film or sheet composed of the above-mentioned polymer can be prepared by a conventional molding method using a resin composition composed of a polymer into which a curing retarding component has been introduced and, if necessary, another polymer. For example, it can be prepared by forming a film or a sheet by an extrusion method, a casting method, a calendar method, or the like. (2b-1) a film or sheet having a curing retardation layer formed on a substrate sheet, and (2b-2) the weight The film or sheet in which the coalesced material is impregnated into the porous base material is formed by applying or impregnating the base sheet with a polymer containing a curing delay component and, if necessary, a binder resin to form a curing delay layer. Can be prepared. In this method, for application, impregnation or coating, a composition which is heated and melted may be used, or a composition containing water or an organic solvent may be used. Examples of the organic solvent include alcohols such as ethanol and isopropanol; aliphatic hydrocarbons such as hexane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; and halogens such as dichloromethane and dichloroethane. Examples include fluorinated hydrocarbons, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, ethers such as diethyl ether and tetrahydrofuran, and mixed solvents thereof. The composition containing the polymer into which the curing retarding component has been introduced may be applied to at least one surface of the substrate sheet, and the coating layer may be formed on the entire surface of the substrate sheet, and may be partially (eg, regular) (As a static pattern or an irregular pattern).

The base sheet includes, for example, non-porous sheets such as plastic sheets and metal foils, and porous sheets such as paper, woven fabric and non-woven fabric. Of the base sheets, preferred non-porous sheets include plastic sheets, and porous sheets include nonwoven fabrics. Polymer constituting the base sheet is not particularly limited, for example,
Polyolefins such as polyethylene terephthalate and polybutylene terephthalate (especially polyalkylene terephthalate); ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer; acrylic resin; polystyrene; polyvinyl chloride; Polyamide; polycarbonate;
Examples include polyvinyl alcohol and ethylene-vinyl alcohol copolymer. One or more of these polymers can be used. Preferred substrate sheets include plastic sheets and nonwoven fabrics. The base sheet is
It may be a single-layer sheet or a composite sheet in which a plurality of layers are laminated, such as a laminated sheet in which a sheet made of polyethylene or the like is laminated on one or both sides of a cloth woven with fibers such as polyethylene fibers. You may. The base sheet such as a plastic sheet may be an unstretched sheet or a uniaxially or biaxially stretched sheet. Further, in order to enhance the adhesion, the surface of the base sheet may be surface-treated by a flame treatment, a corona discharge treatment, a plasma treatment or the like. The surface tension of the surface-treated substrate sheet is often about 40 dyn / cm or more. The thickness of the base sheet can be selected within a range that does not impair workability, mechanical strength, and the like.
μm, preferably about 20 to 400 μm, more preferably about 30 to 300 μm, and often about 50 to 300 μm.

The curing retardation sheet may be appropriately cut and used as a surface decoration sheet. For example, on the inner wall or the bottom wall of the formwork corresponding to the washing out part of the concrete product, fix the cut hardening delay sheet by attaching it, cast concrete, and after the concrete has hardened, remove the mold, By washing off the uncured mortar on the surface of the concrete product corresponding to the application site, a decorative finish concrete product can be obtained. In addition, since the setting retardant component is held on the base sheet in a coated form, even when the concrete is cast, the movement of the setting delay component can be suppressed, and the component does not flow due to bleed water. Therefore, of concrete moldings or buildings,
A decorative pattern such as a character or a pattern can be accurately and clearly applied to a desired surface portion.

The curing retardation sheet is prepared by mixing a pressure-sensitive adhesive or an adhesive (hereinafter simply referred to as a pressure-sensitive adhesive) into the sheet, applying the pressure-sensitive adhesive, or coating a coating layer comprising a polymer having a curing retardation component introduced therein. The sheet may be provided with tackiness or adhesiveness by mixing an adhesive. Furthermore, the tackiness is
A polymerizable monomer having a cure retarding component, a copolymerizable monomer,
The selection may be made by selecting a copolymerizable polymer (especially, among copolymerizable monomers, selecting a C _2-8 alkyl acrylate such as ethyl acrylate, butyl acrylate, or 2-ethylhexyl acrylate). . When using a curing retardation sheet to which tackiness has been given by an adhesive, the pattern on the surface,
It is useful for manufacturing concrete products in which figures and washing surfaces are formed and are integrally fixed to the decorative material. That is, the sheet is laid in the mold with the adhesive surface facing upward, and the surface side of a plurality of decorative materials such as stones and tiles is arranged on the adhesive surface by adhesive, and the decorative material is positioned and fixed. Next, the inorganic curable composition is cast into a mold, cured by a conventional curing method such as curing, and the cured molded product is removed from the mold.
Then, the surface side of the cosmetic material (the side in contact with the sheet) is water,
By washing with pressurized water, jet flow, etc., the uncured composition adhering to the decorative material can be easily removed, and by removing the adhesive, the concrete product with the cleaned face decorative material bonded thereto ( Decorative blocks, precast concrete boards, etc.).
In the case where the decorative material is not adhered to the adhesive surface of the sheet, the aggregates are exposed by the washing, and a pattern or a washed surface can be formed.

Further, when a cured retardation sheet provided with tackiness is used, the decorative material is not disposed in the formwork,
A kit sheet in which decoration materials are arranged or arranged in advance on the adhesive surface may be arranged in the mold. For example, a unit tile can be formed by sticking a plurality of tiles as decorative materials continuously or scattered on the adhesive surface in the surface direction. A plurality of tiles are often arranged adjacent to each other (continuously) in the plane direction (for example, the vertical direction, the horizontal direction, and the vertical and horizontal directions) or at intervals. By using such a decorative material kit sheet, there is no need to separately arrange decorative materials in the formwork, and only the decorative material kit sheet produced in a separate process needs to be disposed in the formwork. Efficiency can be increased. As the decorative material, various materials, for example, natural stones such as cobble stone, black stone, iron flat stone, stone materials such as artificial stones, ceramic materials such as tiles, metal materials, glass materials, wood, woven fabrics and the like can be used. The decorative material may be flat, and the tile may be a mosaic tile or a split tile in addition to a normal tile. In the production of a concrete product, if necessary, a reinforcing material such as a reinforcing bar may be provided in the mold to cast the inorganic curable composition.

The decorative material kit film such as the unit tile is useful for producing a decorative finish concrete product such as a precast concrete plate. That is, the decorative material kit sheet is placed on a concrete casting formwork with the back surface of the decorative material such as the tiles facing upward, concrete is cast and cured, then the mold is removed, and the adhesive sheet is removed. By exposing the surface of the decorative material and washing the surface of the decorative material with water, the uncured inorganic curable composition (cement, etc.) that has wrapped around the surface of the decorative material is washed away, thereby integrating with the decorative material. Precast concrete boards can be manufactured. That is, even if the inorganic curable composition wraps around the surface side of a decorative material such as a tile, the curing retarder can suppress the curing of the inorganic curable composition, and becomes a non-cured (semi-cured or uncured) state, The surface finish for removing the inorganic curable composition from the surface of the decorative material can be efficiently and completely performed by a simple operation such as washing with water.

In the curing retardation sheet, the curing retardation layer containing the polymer into which the curing retardation component has been introduced may be peelable from the base sheet. When the hardening delay layer can be peeled from the base sheet, the predetermined part or region is cut in accordance with a desired pattern or the like in the hardening delay layer and peeled off from the base sheet, and the sheet is placed in a mold. In order to cope with the non-cutting part of the surface of the concrete product by washing out the contact surface with the sheet in the cured and hardened concrete product by casting the inorganic curable composition (such as mortar composition) A washout surface where a pattern, a graphic pattern, an aggregate, and the like are exposed can be formed at a portion to be washed. The surface of the base sheet may be untreated, for example, may be treated with a release agent such as wax, higher fatty acid amide, silicone oil, etc., in order to make the hardening delay layer peelable. The surface tension of the substrate sheet can be relatively selected in a range that does not impair the releasability of the hardening delay layer, in association with the adhesive strength of the hardening delay layer. The surface tension of the substrate sheet is, for example, 38 dyn / cm or less, preferably 20 to 38 dy.
n / cm, more preferably about 25 to 36 dyn / cm in many cases.

The cement setting retarder of the present invention includes various cements, for example, air-hardened cement (lime such as gypsum, slaked lime and dolomite plaster); hydraulic cements (for example, Portland cement, early-strength Portland cement, alumina cement, Self-hardening cement such as rapid hardening high strength cement and calcined gypsum; lime slag cement,
It can be applied to the suppression of hardening of blast furnace cement and the like; mixed cement). Preferred cements include, for example, gypsum,
Dolomite plaster and hydraulic cement are included. The cement may be used as a paste composition with water (cement paste), or may be used as a mortar composition or a concrete composition containing fine aggregate, coarse aggregate such as sand, silica sand, or pearlite. Good. The paste composition and the mortar composition, if necessary, a coloring agent,
Hardening agents, hardening accelerators such as calcium chloride, water reducing agents such as sodium naphthalene sulfonate, coagulants, thickeners such as carboxymethylcellulose, methylcellulose and polyvinyl alcohol, foaming agents, waterproofing agents such as synthetic resin emulsions, plasticizers, etc. May be included.

The cement setting retarder of the present invention can be used for the production of various concrete products, for example, concrete panels such as curtain walls and wall materials, concrete blocks, etc., and especially for the production of decorative concrete products (for example, precast concrete boards). Useful.

[0046]

According to the present invention, since the curing retarding component is introduced into the polymer in a hydrolyzable bonding manner, elution by moisture can be suppressed and high curing retarding ability can be effectively exhibited. In addition, high curing retarding ability can be maintained for a long period of time. Therefore, the decorative pattern can be accurately formed on the surface of the concrete product by the washing out method.

[0047]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples. Example 1 130.1 g (1.0 mol) of 2-hydroxyethyl methacrylate and 67 g of DL-malic acid in an acetone solvent
(0.5 mol), molecular sieve 10 g and 96
% Sulfuric acid was added thereto, and the mixture was reacted under reflux for 24 hours to produce a malic acid-modified acrylic monomer (malic acid-modified acrylic monomer content: 46% by weight). After the reaction, the molecular sieve was filtered, acetone as a solvent was replaced with benzene, and azoisobutyronitrile (AIBN) was added as a polymerization initiator in an amount of 0.5% by weight based on the malic acid-modified acrylic monomer. And under a nitrogen stream, 50
C. for 15 hours to obtain a number average molecular weight of about 1
0000 polymer was obtained.

Then, a polymer solution containing a polymer is applied to a polyethylene terephthalate film with a thickness of about 60 μm after drying using a bar coater, and the obtained cured retardation sheet is attached to the bottom surface of a plastic tray to form a mortar. It was cast. After one day, the surface of the demolded and hardened concrete was washed out with water, and the washing-out depth of the recess was measured using a non-contact type laser displacement sensor. As a result, the washing-out depth was 6.0 mm.

Example 2 Maleic anhydride (159.7 g), propylene glycol (169.6 g) and tetra-n-butyl titanate (160 mg) were charged into a reaction vessel, and the temperature was gradually raised to 120 ° C. under a nitrogen stream. Then, the mixture was stirred for 7 hours while removing water generated by the reaction outside the reaction system to obtain an unsaturated polyester having a number average molecular weight of about 500. This polyester (50 g), the malic acid-modified acrylic monomer (35 g) obtained in Example 1, an organic peroxide (1.7 g) as a curing agent (Nippon Oil & Fats Co., Ltd., Perbutyl O), Cobalt naphthenate (1.7 g) as an accelerator was added,
The mixture was heated at 80 ° C. for 30 minutes to obtain a crosslinked polymer. The crosslinked polymer was cooled with liquid nitrogen and pulverized to obtain a powder (average particle size: 120 μm). The powder was sprayed on the bottom of a plastic tray and mortar was poured. 1
After the elapse of days, the surface of the demolded and hardened concrete was washed out with water, and the depth of the recesses was measured using a non-contact laser displacement sensor.
It was 8 mm.

Example 3 A mixture of glycerin (92 g) and 96% sulfuric acid (0.5 g) was heated to 65 ° C., and pyruvate methyl ester (3
4 g) was slowly added dropwise. By reacting the methanol produced by the reaction while driving it out of the system, glyceryl pyruvate (glycerin monoester,
A mixture of diesters) was obtained. 30 g of the above-mentioned glycerin pyruvate ester was added to 110 g of an ethyl acetate solution (solid content: 45% by weight) of a copolymer of 70 g of butyl acrylate and 30 g of acrylic acid (polymer having a carboxyl group, weight average molecular weight: 20,000), and tetratitanate as a catalyst. 30 mg of -n-butyl was added, and the mixture was stirred at 130 ° C while flowing out ethyl acetate as a solvent to obtain a gelled product. The gel was cooled with liquid nitrogen and pulverized to obtain a powder (average particle size: 150 μm).
When the washing depth was measured using this powder and granular material in the same manner as in Example 2, the washing depth was 4.5 mm.

Example 4 20 g of DL-glyceric acid (65% aqueous solution) and 12.1 g of maleic anhydride were charged into a reactor, and the resulting water was driven out of the system under a nitrogen stream at 120 ° C. for 1 hour. By heating at 150 ° C. for 2 hours and further at 200 ° C. for 3 hours, a gel was obtained. The produced gel was cooled with liquid nitrogen and pulverized to obtain a powder (average particle size: 180 μm).

When the washing depth was measured using this powder and granular material in the same manner as in Example 2, the washing depth was 5.1 m.
m.

Example 5 A compound in which glucose and 2-hydroxyethyl methacrylate were ether-bonded [Nippon Seika Co., Ltd., trade name "SU"
CRAPH-GEMA, 50% by weight aqueous solution] was charged with 0.1 g of ammonium peroxodisulfate as a redox initiator and stirred at 40 ° C. for 3 hours. The polymerization solution was placed in an aluminum foil (radius: 2 cm) and left at room temperature for 24 hours to gel. The resulting gel was adhered to the bottom of a plastic tray, mortar was poured, and the mixture was left in a high-temperature and high-humidity tank for 24 hours. Thereafter, the hardened mortar was removed from the tray, washed with water, and dried. The washing depth of the concave portion was measured using a non-contact laser displacement sensor, and was found to be 15 mm.

Comparative Example 1 To a benzene solution of 30 g of 2-hydroxyethyl acrylate, azobisisobutyronitrile (AIBN) was added as a polymerization initiator in an amount of 0.5% by weight based on 2-hydroxyethyl acrylate. By performing polymerization in the same manner as in Example 1, the number average molecular weight was about 1200.
0 acrylic resin was obtained. The washing depth was measured in the same manner as in Example 1 using a polymer solution containing an acrylic resin. As a result, the washing depth was 0.2 mm.

COMPARATIVE EXAMPLE 2 Maleic anhydride (159.7 g), propylene glycol (169.6 g) and tetra-n-butyl titanate (160 mg) were charged into a reaction vessel, and slowly added under a nitrogen stream.
The temperature was raised to 00 ° C, and the generated water was removed outside the reaction system.
By stirring for an hour, an unsaturated polyester having a number average molecular weight of about 500 was obtained. The polyester (50 g), 2-hydroxyethyl acrylate (35 g), and an organic peroxide (1.7 g) as a curing agent (manufactured by NOF Corporation)
Perbutyl O) and cobalt naphthenate (1.7 g) as an accelerator were added and heated at 80 ° C. for 30 minutes to obtain a crosslinked polymer. The crosslinked polymer was cooled with liquid nitrogen and pulverized to obtain a powder (average particle size: 150 μm). When the washing depth was measured using this powder and granular material in the same manner as in Example 2, the washing depth was 2.9 mm.

Comparative Example 3 The washing depth was measured in the same manner as in Example 3 without using glycerin pyruvate, and it was 0.6 mm.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08G 73/00 NTB C08G 73/00 NTB C08L 51/08 LLU C08L 51/08 LLU 55/00 LMG 55 / 00 LMG 101/00 LTB 101/00 LTB E04F 13/02 0231-2E E04F 13/02 F // B28B 1/14 B28B 1/14 E C04B 41/72 C04B 41/72 C04B 103: 24

Claims (18)

[Claims] 1. A cement setting retarder comprising a polymer having a unit of a cement setting delay component which can be hydrolyzed by the action of an alkali. 2. The setting retarder according to claim 1, wherein the unit of the cement setting retarding component is bonded by an ester bond or an acid amide bond in a main chain or a side chain of the polymer. 3. The curing retarder according to claim 1, wherein the polymer is a homopolymer or a copolymer of a polymerizable monomer having a unit of a hydrolyzable cement setting retarding component. 4. A copolymer comprising a polymerizable monomer having a unit of a hydrolyzable cement setting delay component and at least one of a copolymerizable monomer and a copolymerizable polymer. The curing retarder according to claim 3, which is a coalescing. 5. The curing retarder according to claim 4, wherein the copolymerizable polymer is an unsaturated polyester. 6. The setting retarder according to claim 1, wherein the cement setting delay component has a hydroxyl group or a carboxyl group. 7. The cement setting retarding component having a hydroxyl group or a carboxyl group is at least one selected from oxycarboxylic acids, ketocarboxylic acids, polycarboxylic acids, sugars, glycosides, and polyhydric alcohols. 6. The curing retarder according to 6. 8. A polymerizable compound having at least one reactive group selected from at least one of a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group and an amino group; The setting retarder according to claim 3, which is an ester compound or an amide compound with a cement setting delay component having a group or a carboxyl group. 9. The polymerizable monomer is an ester of a polymerizable compound having a carboxyl group or an acid anhydride group and a hydroxyl group-containing cement setting retarding component.
The curing retarder as described. 10. A polymer having at least one reactive group selected from a hydroxyl group, a carboxyl group, an acid anhydride group and an amino group on a side chain, and an ester or amide bond to the polymer having the reactive group. The curing retarder according to claim 1, comprising a component having a cement curing retarding ability. 11. A polymer, wherein the polymer has at least two reactive groups selected from a hydroxyl group and a carboxyl group, and a cure delay selected from an oxycarboxylic acid having at least both a hydroxyl group and a carboxyl group. The curing retarder according to claim 2, which is a polyester formed by an esterification reaction with an active ingredient. 12. A component having a cement setting retarding ability,
The curing retarder according to claim 11, which is a dihydroxy compound. 13. The method according to claim 1, wherein the proportion of the unit of the cement setting retarding component is 5 to 60% by weight based on the whole polymer.
The curing retarder as described. 14. The form of the curing retarder is (1) a powder or granule,
Or (2) the curing retarder according to claim 1, which is a film or a sheet. 15. (1) The granules are (1a) a granules composed of the polymer according to claim 1, and (1b) a granules coated with the polymer according to claim 1. A curing retarder according to claim 14. (2) The film or sheet is (2a)
The curing retarder according to claim 14, which is a film or sheet comprising the polymer according to claim 1, and (2b) a film or sheet holding the polymer according to claim 1 on a substrate. 17. A film formed on a substrate sheet, wherein the film or sheet holding the polymer is (2b-1) a curing retardation layer containing the polymer according to claim 1, which may be subjected to a release treatment. The curing retarder according to claim 16, which is a film or sheet in which the polymer according to claim 1 is impregnated into a porous substrate or a sheet, or (2b-2). 18. (a) homopolymerization or copolymerization of a polymerizable monomer having a unit of a cement setting delay component which can be hydrolyzed by the action of an alkali, or (b) cement setting delay which can be hydrolyzed by an action of an alkali A method for producing a cement setting retarder, comprising introducing a unit of a cement setting delay component into a side chain or a main chain of a polymer by esterification or amidation reaction of the component.