JP2001150417A - Concrete curing retarding resin composition and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a concrete curing retarding resin composition having high concrete curing retarding capability and capable of accurately forming a pattern. SOLUTION: The concrete curing retarding resin composition solid at ambient temperature is formed of a polymer (1) having the concrete curing retarding capability, and a polymer component (2) of (i) polymer 2a having a functional group reactable with the polymer (1) or (ii) a polymer composition constituted of a polymerizable polymer 2b and a polymerizable diluent, in such a manner that at least one of them has a functional group reactable with the polymer (1). In the case, the polymer (1) may have a carboxyl group, an acid anhydride group, a hydrolyzable ester group, and the functional group of the polymer component (2) may be reactable with the active group of the polymer (1).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a solid concrete hardening retarding resin composition, the above-mentioned retarding resin composition or a method for producing a solid resin constituting the above-mentioned retarding resin composition.
The present invention relates to a method for treating the surface of concrete using the setting retardant resin composition, and a concrete setting retarder.

[0002]

2. Description of the Related Art It is often practiced to decorate the surfaces of concrete moldings and various buildings using a so-called washing method, which is one of plastering techniques. This washing-out method is a method in which a part of the aggregate is exposed by washing with water immediately before the cement hardens, and by washing away the mortar of the concrete surface layer. In this method, the timing of the washing is closely related to the setting speed of the cement,
It is necessary to perform the washing operation in a narrow range that is extremely limited in time. Therefore, if it is possible to delay only the hardening of the concrete surface layer while hardening the concrete, it is advantageous that the timing of washing is not limited by the hardening speed of the concrete. Further, when the sheet coated with the curing retardant is cut into a predetermined shape and applied to the concrete surface, a pattern of the predetermined shape can be formed on the concrete surface.

[0003] As a concrete hardening retarder capable of delaying the hardening of concrete, for example, JP-A-1-17225
No. 0 discloses inorganic hardening retardants such as lead oxide, boron oxide, borax, zinc chloride, zinc oxide, magnesium fluorosilicate, sugar, oxycarboxylate, lignin sulfonate, gluconate, pyruvate. And organic curing retarders such as keto acids such as α-ketoglutaric acid. However, these cure retarders are water-soluble. Therefore, even if a sheet coated with these hardening retardants is applied to a predetermined portion in order to form a pattern on the concrete surface, the retarding agent dissolves in the moisture in the concrete due to contact with the concrete, and furthermore, Since a lateral flow occurs to an unintended site together with water (bleed water) released from the water, a pattern cannot be formed with high accuracy.
Further, the curing retarder does not always have sufficient curing retardation, and has a shallow curing delay depth. In addition, the hardening of the concrete cannot be delayed for a long time.

[0004] US Pat. No. 4,946,904 discloses a concrete admixture having anti-slump loss properties.
A copolymer of an allyl ether having an oxyalkylene unit and maleic anhydride is disclosed. However, this admixture has a very strong concrete setting ability, but is liquid and water-soluble. For this reason, even if this copolymer is applied to the concrete surface and used as a concrete hardening retarder, the retarder flows out depending on the application site (vertical surface or the like), and the pattern cannot be formed accurately. Also, due to water solubility, bleed water causes cross flow.

[0005] Japanese Patent Application Laid-Open No. 9-18363 discloses a
Polyvalent C_{2- 6}Carboxylic acid and polyvalent
C_2-4Various polyesters composed of alcohol and
It is shown. Of these, unsaturated polyester
Bridge-hardened concrete setting retarder is insoluble in water at room temperature
Solid, so that when casting concrete,
A retarder that is difficult to cause and is extremely effective in solving the above problems
It is. However, this type of retarder is
In some cases, the curing delay ability is low, and the curing delay depth is shallow.

JP-A-10-53445 discloses that as a curing retarder, a maleic acid unit having (anhydride), a vinyl ether-based monomer unit having a (poly) oxyalkylene segment, and a copolymer having a vinyl monomer unit are provided. Coalescing is disclosed. This type of polymer also has a strong ability to retard concrete hardening, but is generally water-soluble and liquid at room temperature. Further, it is disclosed that the copolymer can be used by mixing or complexing with another resin (unsaturated polyester, (meth) acrylic acid (ester) copolymer, etc.). JP-A-10-53444 discloses a polymer of a dicarboxylic acid such as maleic acid or fumaric acid and a methacrylate such as polyoxyethylene glycol mono (meth) acrylate or hydroxyethyl (meth) acrylate or other polymer. Using a copolymer with a copolymerizable monomer as a concrete hardening delay component, the delay component,
A concrete setting retarder encapsulated (dispersed, coated, etc.) in an alkali-soluble or alkali-hydrolysable polymer is disclosed. However, with these curing retardants, the curing retardation depth of concrete is often too shallow or too deep to cause cross-flow, so that the curing retardation depth cannot be controlled.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a concrete setting retarding resin composition having a high concrete setting delay ability and capable of forming a pattern with high accuracy.
A method for producing the above-mentioned retarding resin composition or a solid resin constituting the above-mentioned retarding resin composition, a method for treating the surface of concrete using the above-mentioned retarding resin composition, and using the above-mentioned retarding resin composition. To provide a hardened concrete hardening retarder.

Another object of the present invention is to provide a concrete setting delaying resin composition capable of controlling the concrete setting delay depth, a method for producing the above-mentioned delaying resin composition or a solid resin constituting the above-mentioned delaying resin composition, It is an object of the present invention to provide a method for treating the surface of concrete using the setting delay resin composition, and a concrete setting delay material using the setting delay resin composition.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a polymer (1) having a concrete curing retarding ability and a functional group capable of reacting with the polymer (1) are provided. When the concrete setting retarding resin composition which is solid at room temperature with the specific polymer component (2) having the polymer (1), even if the polymer (1) is liquid or water-soluble, the solidification can highly prevent lateral flow, Moreover,
The present inventors have found that the polymer (1) has a high curing retardation ability without impairing the curing retardation property, and completed the present invention.

That is, the concrete setting retarding resin composition of the present invention comprises a polymer (1) having a concrete setting delaying ability and a specific polymer component (2) having a functional group reactive with the polymer (1). And is solid at room temperature. The polymer component (2) comprises (i) a polymer (2a) having a functional group capable of reacting with the polymer (1),
Or (ii) a polymer composition comprising a polymerizable polymer (2b) and a polymerizable diluent, at least one of which has a functional group capable of reacting with the polymer (1). The polymer (1) may have at least one active group selected from an acidic group (such as a carboxyl group), an acid anhydride group, and a hydrolysable ester group, and the polymer component (2)
May be capable of reacting with the active group of the polymer (1). When the polymer (1) has a plurality of active groups, at least one pair of the active groups may be in a positional relationship capable of forming a chelate with calcium ions. The polymer (1) has, for example, structural units represented by the following formulas (IIa) to (IIc).

[0011]

Embedded image

(Wherein, Z represents a C _1-6 alkylene group, a carbonyl group or a C _2-7 alkylenecarbonyl group. The alkylene unit in the group Z may be branched.
^1a represents a C _2-6 alkylene group which may be branched. R
^1b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group (however, when Z is a carbonyl group, R ^1b is not a hydrogen atom). R ^1c
Represents a hydrogen atom or a methyl group. R ^2a and R ^2b represent a hydroxyl group or an alkoxyl group, or form an acid anhydride group together with an adjacent carbonyl group. R ³ represents a residue of a vinyl monomer. m is 0 or 1, n is 0 to 10
Indicates an integer of 0. p + q + r = 1, and p is 0.1 to
0.9 and q represent 0.1 to 0.9, and r represents 0 to 0.5. The polymer (1) may be liquid at room temperature. Also,
The functional group capable of reacting with the polymer (1) of the polymer component (2) may be a hydroxyl group, an epoxy group, a carboxyl group, a hydrolyzable acyloxyl group, or the like.
The polymer (2a) may be a condensate of a polyhydric alcohol, a homo- or copolymer of a monomer having a hydroxyl group, a hydroxyl-terminated polyester, or a reactive derivative thereof. The polymer (2b) may be an unsaturated polyester, and the polymerizable diluent is, for example, a styrene monomer or a compound represented by the following formula (III).

[0013]

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(Wherein X represents an optionally branched C _1-6 alkylene group or a carbonyl group. R ^1d represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an acyl group, or an epoxy group .R ^1a, R
^1c , m and n are the same as described above) The present invention includes a method for producing a concrete setting retarding resin composition in which a polymer (1) and a polymer component (2) are mixed, and a method for producing a solid resin. . Further, the present invention includes a concrete hardening delay material in which a concrete hardening delay layer formed of the concrete hardening delay resin composition is formed on a surface of a support. further,
In the present invention, a concrete setting retardation resin composition or a concrete setting delay layer formed with this resin composition,
A concrete surface treatment method in which unhardened concrete is brought into contact with the concrete and the concrete surface is washed out after the concrete is hardened is also included.

[0015] In the present specification, delaying the hardening of cement and a cement-based composition is collectively referred to as "concrete hardening delay".

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION [Polymer (1)] The polymer (1) constituting the concrete setting retarding resin composition of the present invention may be a metal ion (for example, sodium ion, calcium ion, magnesium ion or the like). It may have a group capable of forming a salt with a divalent metal ion (particularly a divalent metal ion such as a calcium ion), for example, an active group such as a carboxyl group, an acid anhydride group or an ester group. The ester group is a hydrolyzable ester group such as a carboxyl group and a lower alcohol (C _1-10
And an ester group between a carboxyl group and (poly) glycol or (poly) glycol monoallyl ether.

In many cases, a plurality of such active groups are formed on the same polymer, and among the plurality of curing retarding groups, at least one pair of curing retarding groups is capable of reacting with a divalent metal ion. It is preferable that they have a positional relationship capable of forming a chelate salt. For example, when the active group is a carboxyl group, the pair of active groups may form a succinic acid unit or a succinic anhydride unit.

Specific examples of the polymer (1) include, for example, a homopolymer of a polymerizable monomer having an active group, and a copolymer of the polymerizable monomer and a vinyl derivative represented by the following formula (I). And copolymers. In addition, these polymers may be copolymers with other copolymerizable monomers.

[0019]

Embedded image

(Wherein Y represents a C _1-6 alkylene group which may be branched; R ^1a represents a C _2-6 alkylene group which may be branched; R ^1b represents a hydrogen atom, an alkyl group; A cycloalkyl group, an aryl group, an aralkyl group or an acyl group,
R ^1c represents a hydrogen atom or a methyl group. m is 0 or 1,
n shows the integer of 0-100. The polymerizable monomer having an active group includes, for example, a polymerizable unsaturated monomer having a carboxyl group (for example, (meth)
Acrylic acid, ethylenically unsaturated monocarboxylic acids such as crotonic acid, unsaturated polyvalent carboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid), or derivatives thereof [acid anhydrides, esters ( Preferably C
_1-10 alkyl alcohol, (poly) oxyalkylene glycol, ester with (poly) oxyalkylene glycol monoalkyl ether, etc.). These monomers can be used alone or in combination of two or more. Preferred examples of the polymerizable monomer having a curing retarding group include unsaturated polycarboxylic acids such as maleic acid, maleic anhydride and fumaric acid, and acid anhydrides thereof.

In the vinyl derivative (I), preferred R
^1aIs C_2-4Alkylene group, especially C_{Two -3}An alkylene group
You.

The preferred number n of repeating oxyalkylene units is 2 to 100, especially about 2 to 75, and 3 to 5
It may be about 0. The greater the number of repetitions n, the greater the concrete curing retardation of the polymer (1).

Among the vinyl derivatives (I), examples of the vinyl ether monomer (compound with m = 0) include (poly) oxyalkylene glycol monovinyl ether [eg, ethylene glycol monovinyl ether, dioxyethylene glycol monovinyl ether, (Poly) oxyethylene glycol monovinyl ether such as trioxyethylene glycol monovinyl ether; (poly) oxypropylene glycol monovinyl ether such as propylene glycol monovinyl ether, dioxypropylene glycol monovinyl ether, and trioxypropylene glycol monovinyl ether; tetramethylene glycol; (Poly) oxytetramethyle such as dioxytetramethylene glycol and trioxytetramethylene glycol Glycol, etc.], these terminal hydroxyl groups of the monovinyl ether is C _1-20 alkyl, C _3-10 cycloalkyl, C _1-10 optionally having an alkyl group C _6-10 aryl group, C _{7 Monovinyl} ether blocked with an _-11 aralkyl group [eg, C _1-4 alkyl-polyoxyethylene monovinyl ether, etc.]
And the like.

Among the polymerizable ethers represented by the vinyl derivative (I), examples of vinyl alkyl ethers such as allyl ether derivatives (compounds with m = 1) include (poly) oxyalkylene glycol monovinyl alkyl ether [(Poly) oxyethylene glycol monovinyl alkyl ether, (poly) oxypropylene glycol monovinyl alkyl ether, etc.], the terminal hydroxyl group of these monovinyl alkyl ethers is a C _1-20 alkyl group, a C _3-10 cycloalkyl group, a C _{1 A} C _6-10 aryl group _optionally having a _-10 alkyl group, C _7-11
Monovinyl ethers blocked with an aralkyl group [for example, C _1-4 alkyl-polyoxyethylene glycol monovinyl alkyl ether and the like] can be exemplified.

The ratio of the vinyl derivative (I) is, for example, 5 parts by weight per 100 parts by weight of the polymerizable monomer having an active group.
About 0 to 2,000 parts by weight, preferably 100 to 1.0
It can be selected from a range of about 00 parts by weight.

Examples of other copolymerizable monomers include olefins (eg, ethylene, propylene, butene, etc.), diene monomers (eg, butadiene, isoprene, etc.), glycidyl (meth) acrylate, (meth)
Examples include acrylonitrile, vinyl esters (eg, vinyl acetate, vinyl propionate, etc.), and aromatic vinyl compounds (eg, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, etc.). Preferred other copolymerizable monomers include a monomer having high copolymerizability with maleic acid or a derivative thereof or maleic anhydride, particularly an aromatic vinyl compound such as styrene.

The ratio of the other copolymerizable monomer is such that the total amount of the polymerizable monomer having an active group and the vinyl derivative [I] is 100%.
About 0 to 500 parts by weight, preferably 0 to 500 parts by weight,
It may be about 200 parts by weight.

The preferred polymer (1) has, for example, structural units represented by the following formulas (IIa) to (IIc).

[0029]

Embedded image

(Where Z is C_1-6Alkylene group, carbo
Nyl group or C_2-7Shows an alkylenecarbonyl group. What
The alkylene unit in the group Z may be branched. R
^2aAnd R^2bRepresents a hydroxyl group or an alkoxyl group
Or form an anhydride group with an adjacent carbonyl group.
To achieve. R^ThreeRepresents a residue of a vinyl monomer. p + q + r
= 1, p is 0.1-0.9, and q is 0.1-0.
9, r represents 0 to 0.5. R ^1a~ R^1c, M and n are before
The same is true. However, when Z is a carbonyl group, R
^1bIs not a hydrogen atom. ) Preferred R^2aAnd R^2bIs an acid anhydride group, and is preferable.
Z is C_1-3An alkylene group (particularly, a methylene group).
R^2aAnd R^2bForms an anhydride group, the polymer
The reactivity between (1) and polymer (2) can be further improved
You.

Preferred coefficients p and q are 0.2 to 0.5.
8, particularly about 0.3 to 0.7, and a preferable coefficient r is about 0 to 0.4.

By selecting R ^1b in the above formula (IIb), the concrete setting retardation of the polymer (1) can be adjusted. For example, when the terminal hydroxyl group is not blocked (when R ^1b is a hydrogen atom) or blocked with a lower alkyl group (for example, when R ^1b is a C _1-4 alkyl group), the polymer (1) Can impart high hydrophilicity to the concrete, and can deeply form a concrete retardation layer. On the other hand, when the terminal hydroxyl group is blocked with a higher alkyl group (for example, when R ^1b is a C _10-20 alkyl group), it is possible to impart hydrophobicity to the polymer (1) and to form a concrete retardation layer with high precision. Can be formed.

The molecular weight of the polymer (1) is not particularly limited, and is, for example, 150 to 1,000 as a number average molecular weight determined by gel permeation chromatography (GPC).
About 0000 (for example, 300 to 1,000,000
Degree), preferably about 1,000 to 100,000 (for example, about 2,000 to 100,000), and more preferably about 5,000 to 50,000.

In the present invention, room temperature (about 20 to 30 ° C.)
Liquid) (liquid, viscous or non-viscous fluid, etc.)
Polymer (1) can be advantageously used. In general, when a liquid polymer is used as a curing retarder, since a lateral flow occurs, a curing retardation layer cannot be formed uniformly, but in the present invention,
Even when the polymer (1) is in a liquid state, a solid resin (solid resin) can be formed at room temperature in combination with the polymer component (2) described below, and lateral flow can be prevented.

[Polymer Component (2)] In the present invention, the second component used in combination with the concrete setting retarding polymer (1) is used.
As the polymer (1), a specific polymer component (2) having a functional group (reactive group) capable of reacting with the polymer (1) is used. The polymer component (2) is, as a first embodiment, a polymer (2a) having a functional group (reactive group) capable of reacting with the polymer (1). In addition, the polymer component (2)
Is, as a second embodiment, a composition of a polymerizable polymer (2b) and a polymerizable diluent, at least one of which has a functional group (reactive group) capable of reacting with the polymer (1). It is. By combining such a polymer component (2) with the polymer (1), a solid resin can be formed. In the solid resin, for example, the polymer (1) and the polymer component (2) may form a bond, and the polymer (1) is dispersed in a matrix composed of the polymer component (2). It may be.

The reactive groups of the polymer component (2) include the active groups (hydroxyl group, carboxyl group,
It may be a group capable of reacting with an acid anhydride group, particularly an acid anhydride group. As the reactive group capable of reacting with the active group, for example, a carboxyl group, a hydroxyl group, or a hydroxyl group-derived group (epoxy group, acyloxyl group, etc.)
And the like. The acyloxyl group may be a hydrolyzable acyloxyl group having about 2 to 10 carbon atoms, such as an acetoxy group, a propionyloxy group, and a butyryloxy group.

Among the polymer components (2), the polymer (2a) having a reactive group includes, for example, (i) a condensate of a polyhydric alcohol, (ii) a homo- or copolymer of a monomer having a hydroxyl group, (iii) Polyester (saturated or unsaturated polyester) or a reactive derivative thereof (epoxy derivative, acyloxy derivative, etc.).

Examples of the polyhydric alcohol condensate include (poly) oxyalkylene glycols, for example, polyethylene glycols such as ethylene glycol, dioxyethylene glycol, trioxyethylene glycol, and polyoxyethylene glycol; propylene glycol;
(Poly) oxy C ₂ such as polypropylene glycols such as dioxypropylene glycol, trioxypropylene glycol and polyoxypropylene glycol, and polytetramethylene glycols such as tetramethylene glycol, dioxytetramethylene glycol and polyoxytetramethylene glycol. _-6 alkylene glycol (preferably, (poly) oxy _C2-4 alkylene glycol). The degree of polymerization of the polyoxyalkylene glycol may be, for example, 20 or less, preferably about 10 or less. Further, the polyhydric alcohol condensate may be a condensate of a trivalent or higher polyol, for example, an aliphatic triol (glycerin, trimethylolethane, trimethylolpropane, etc.) or an aliphatic tetraol (pentaerythritol, etc.). Good. Preferred condensates of polyhydric alcohols are condensates of aliphatic diols or aliphatic triols. These condensates of polyhydric alcohols can be used alone or in combination of two or more.

Examples of the monomer having a hydroxyl group include (meth) acrylates having a hydroxyl group, for example, hydroxyethyl (meth) acrylate,
Hydroxy _C2-10 alkyl (meth) acrylates such as hydroxypropyl (meth) acrylate (preferably hydroxy _C2-4 alkyl (meth) acrylate); polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Polyoxy C _2-10 alkylene glycol mono (meth) acrylate such as polytetramethylene glycol mono (meth) acrylate (preferably polyoxy C
_2-4 alkylene glycol mono (meth) acrylate)
And the like. The hydroxyl group-containing (meth) acrylate may be an epoxy derivative, for example, glycidyl (meth) acrylate.

The homo- or copolymer of the monomer having a hydroxyl group may be polyvinyl alcohol or the like in addition to the polymer having the monomer having a hydroxyl group as a constitutional unit.

Examples of the saturated polyester include a condensate of a saturated polycarboxylic acid component and a polyol component.
As the saturated polycarboxylic acid component constituting the saturated polyester, oxalic acid, malonic acid, succinic acid, glutaric acid,
Aliphatic C such as adipic acid, azelaic acid and sebacic acid
Aromatic polycarboxylic acids such as _2-12 dicarboxylic acid (particularly, aliphatic C _2-6 dicarboxylic acid), phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, trimellitic acid, and pyromellitic acid (particularly, aromatic Group dicarboxylic acid) or a salt thereof.

As the polyol component, for example, a polyhydric alcohol constituting the polyhydric alcohol condensate can be used.

Preferred saturated polyesters are, for example, aliphatic saturated polyesters composed of an aliphatic C _2-6 dicarboxylic acid and a polyoxy C _2-4 alkylene glycol. When such a saturated polyester is used, the sustainability of the concrete curing retarding ability of the concrete curing retarding resin composition can be significantly improved.

The molecular weight of the saturated polyester is 500,000 or less (about 150 to 500,000), preferably about 1,000 to 100,000, more preferably about 5,000 to 50,000 in number average molecular weight. There may be. The number average molecular weight can be measured by gel permeation chromatography (in terms of polystyrene).

Examples of the unsaturated polyester include a condensate of a polyol component and a polyvalent carboxylic acid component containing at least an unsaturated polycarboxylic acid component. The polycarboxylic acid component may contain a saturated polycarboxylic acid component of the saturated polyester.

As the unsaturated polycarboxylic acid component constituting the unsaturated polyester, an unsaturated polycarboxylic acid of a polymerizable unsaturated monomer having an active group of the polymer (1) can be used. A preferred unsaturated polycarboxylic acid component is an unsaturated C _4-6 dicarboxylic acid (particularly, an unsaturated C ₄ dicarboxylic acid such as maleic acid) or an anhydride thereof. Also,
The polyol component is the same as the polyol component of the saturated polyester.

Preferred unsaturated polyesters are, for example,
Aliphatic unsaturated C _4-6 dicarboxylic acid and (polyoxy) C _2-4
It is an aliphatic unsaturated polyester composed of alkylene glycol. When such a saturated polyester is used, the sustainability of the concrete curing retarding ability of the concrete curing retarding resin composition can be significantly improved. Incidentally, the unsaturated polyester having a hydroxyl group, if necessary,
Part or all may be self-cured (cross-linked, graft-polymerized, etc.).

In the above-mentioned saturated and unsaturated polyesters, it is more advantageous that the terminal group is a hydroxyl group as the ratio of the component (IIa) in the components constituting the polymer (1) increases. In the reaction between the polyvalent carboxylic acid component and the polyol component, the hydroxyl group-terminated polyester is
It can be produced by using a polyol component in an amount larger than the polyvalent carboxylic acid (equivalent basis).

The unsaturated polyester has a number average molecular weight of 10,000 or less (for example, 150 to 10,000).
00), preferably about 300 to 8,000, and more preferably about 500 to 5,000.
In addition, the said number average molecular weight can be measured similarly to a saturated polyester. In addition, the molecular weight of the cured product of the unsaturated polyester cannot be usually measured.

As the polymer (2b), a polymer having a polymerizable group (such as an ethylenically unsaturated bond), for example,
Unsaturated polyesters. The polymer (2
The unsaturated polyester constituting b) may be at either a carboxyl group terminal or a hydroxyl group terminal.
Preferred unsaturated polyesters are aliphatic unsaturated C _4-6 dicarboxylic acid (polyoxy) C _2-4 aliphatic unsaturated polyester composed of an alkylene glycol.

Examples of the polymerizable diluent include vinyl monomers, unsaturated dicarboxylic acids, and monomers represented by the following formula (III).

[0052]

Embedded image

(Wherein X represents an optionally branched C _1-6 alkylene group or a carbonyl group. R ^1d represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an acyl group, or an epoxy group .R ^1a, R
^1c , m and n are the same as above. Examples of vinyl monomers include styrene-based monomers (styrene, α-methylstyrene, vinyltoluene, hydroxystyrene, etc.), vinyl halides (vinyl chloride, etc.), vinyl cyanide (acrylonitrile, etc.) ), Olefinic monomers (ethylene, propylene, etc.). The vinyl monomers also include vinyl alcohol derivatives, for example, vinyl esters (such as vinyl acetate).

Examples of the unsaturated dicarboxylic acids include unsaturated dicarboxylic esters (eg, C _1-10 alkyl esters of C _4-6 unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid). Is mentioned.

Examples of the vinyl ether monomer (m = 0) in the monomer (III) include, for example, the vinyl derivatives described above.
(I) (polyoxy) alkylene glycol monovinyl ether. Examples of the vinyl alkyl ethers (X = alkylene group, m = 1) of the monomer (III) include the (poly) oxyalkylene glycol monovinyl alkyl ether of the vinyl derivative (I).

In the above-mentioned vinyl ether monomer, vinyl alkyl ethers and (meth) acrylic monomer, a terminal hydroxyl group (or carboxyl group) is used.
_Represents a C _1-20 alkyl group, a C _3-10 cycloalkyl group,
_A C _6-10 aryl group _optionally having a _1-10 alkyl group,
The C _7-11 aralkyl group, C _2-6 acyl group, and C _1-4 alkyl group may be blocked with an optionally substituted epoxy group or the like.

When the polymer component (2) is composed of the polymerizable polymer (2b) and the polymerizable diluent, at least one of the polymerizable polymer (2b) and the polymerizable diluent contains a reactive group ( A compound having a hydroxyl group, an acyloxyl group, an epoxy group, a carboxyl group, or the like is used. Further, the polymerizable polymer (2b) may be partially cured (cross-linked, graft-polymerized, etc.) by a polymerizable diluent.

The ratio between the polymer (1) and the polymer component (2) is, for example, the former / the latter = 10/90 to 99/1.
(Weight ratio), preferably about 30/70 to 95/5 (weight ratio), more preferably 50/50 to 90/10.
(Weight ratio). The larger the proportion of the setting retarder polymer (1), the more the solid concrete setting retarder can be given tackiness. For this reason, for example, when a coating material of a retarder (for example, a concrete hardening delay material described later) is applied to the concrete surface, the coating material can be formed easily and conveniently.

[Concrete retarding resin composition] The concrete curing retarding resin composition of the present invention contains a solid resin formed of the polymer (1) and the polymer component (2). The solid resin is a resin that is solid at room temperature and formed of the polymer (1) and the polymer component (2), and is capable of releasing a concrete hardening delay component by hydrolysis. The resin that is solid at room temperature includes a resin that has a viscosity of 10,000 Pa · s or more at 20 ° C. in addition to a resin that is in a glassy state at room temperature.

The solid resin can be obtained, for example, by mixing the polymer (1) and the polymer component (2). Even if the polymer (1) is liquid, it can be solidified by mixing with the polymer component (2).

When mixing the polymer (1) and the polymer component (2), the mixture may be heated if necessary. The heating temperature is, for example, about 40 to 200 ° C., preferably 80 to 1
It is about 50 ° C.

In the case of mixing, if necessary, organic solvents such as aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol and ethanol, esters such as ethyl acetate and butyl acetate, acetone, etc. Ketones such as methyl ethyl ketone and cyclohexanone,
Halogenated hydrocarbons such as methylene chloride and ethers such as diethyl ether and methyl t-butyl ether may be used. The organic solvent can prevent the mixture from completely solidifying in the mixing vessel (mixer, mixing can, etc.).

When the mixture does not solidify, or when the mixture is dispersed (or dissolved) in an organic solvent or the like, the unsolidified mixture or the dispersion (solution) is heated (heat treated) to be solidified (heat treated). Or solidification by drying). The heat treatment temperature is, for example, about 40 to 200 ° C, preferably about 80 to 150 ° C.

Further, the concrete setting retarding resin composition may contain various additives (polymerization initiator, polymerization accelerator, active regulator, esterification catalyst, etc.) as required. In particular, when a polymerizable polymer (2b) and a polymerizable diluent are used as the polymer component (2), a polymerization initiator, a polymerization accelerator, an activity regulator and the like are often added.

Examples of the polymerization initiator include organic peroxides (ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; t-butyl peroxybenzoate, t-butyl peroxy-2-
Peroxyesters such as ethylhexanoate; acyl peroxides such as benzoyl peroxide and lauroyl peroxide; cumene hydroperoxide and dicumyl peroxide; and azo compounds (azobisisobutyronitrile and the like). it can. Preferably, organic peroxides, more preferably ketone peroxides, acyl peroxides, especially ketone peroxides can be mentioned. These polymerization initiators can be used alone or in combination of two or more. If necessary, a photopolymerization initiator (such as an aromatic ketone, a morpholine-based polymerization initiator, or a phosphine-based polymerization initiator) may be contained.

The amount of the polymerization initiator to be used is, for example, about 0 to 20 parts by weight, preferably about 0 to 10 parts by weight, more preferably about 100 parts by weight of the total amount of the polymer (1) and the polymer component (2). Is about 1 to 5 parts by weight.

Examples of the polymerization accelerator include transition metal complexes, salts of transition metals, and tertiary amines. Transition metals include 3A, 4A, 5A, 6A, 7
Elements belonging to Group A, 8, 1B or 2B are listed, and preferably elements belonging to Group 8 such as Fe and Co are listed. The ligand forms a complex, 1,3-diketone or acetylacetone include Lewis bases such as H ₂ O. Salts include salts with carboxylic acids such as naphthenic acid. The tertiary amines include aromatic tertiary amines such as dimethylaniline and dimethylparatoluidine. Preferred accelerators include Fe (aca
c) ₃ , Co (H ₂ O) ₂ (acac) ₂ , Co (acac) ₃ , cobalt naphthenate, iron naphthenate and the like (acac
Represents an acetylacetonato group). These polymerization accelerators can be used alone or in combination of two or more.

The amount of the polymerization accelerator to be used is as follows.
For example, about 0 to 5 parts by weight, preferably about 0 to 3 parts by weight, and more preferably 0.1 to
It is about 1 part by weight.

Examples of the activity modifier include carbonyl compounds such as 1,3-diketone (acetylacetone); amines such as pyridine and triethylamine; phosphorus compounds such as triphenylphosphine; sulfur compounds such as thiophene; Organic compounds having π electrons, such as cyclopentadiene, cyclooctadiene, and benzene, may be mentioned. Preferred are carbonyl compounds and amines (particularly, triethylamine).

The amount of the activity modifier used is, for example, about 0 to 20 parts by weight, preferably about 0 to 10 parts by weight, and more preferably about 100 parts by weight of the total of the polymer (1) and the polymer component (2). Is about 1 to 5 parts by weight.

As the esterification catalyst, carboxylic acid salts such as sodium acetate and potassium acetate, aliphatic amines such as triethylamine, and aromatic amines such as pyridine and 4-dimethylaminopyridine can be used. These catalysts can be advantageously used particularly when the polymer (1) has an acid anhydride group. In addition, as the esterification catalyst,
If necessary, an acid catalyst such as an organic acid (sulfonic acids such as toluenesulfonic acid and methanesulfonic acid) can be used.

The amount of the esterification catalyst used is, for example, about 0 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of the polymer (1) and the polymer component (2).
It is about 5 parts by weight, more preferably about 0.1 to 3 parts by weight.

The concrete setting retarding resin composition may be used, if necessary, with coloring agents such as dyes and pigments, stabilizers, plasticizers, fillers such as inorganic powders and organic powders, and granular materials (eg, aggregates). Etc. may be added.

[Concrete retarder] The concrete retarder of the present invention may be used as a granular material, and may be a single-layer sheet or a support (substrate sheet, substrate) formed from the resin composition. It may be used as a concrete hardening retarder such as a composite in which a retarder layer (delay layer) is formed on the surface of a planar support such as a board. In addition, the said single-layer sheet uses a conventional method (for example, a sheet forming method using an extruder, a solution of the cement setting retarder is cast on release paper, and the release paper is peeled off after drying. And the like). Further, the composite (concrete curing delay sheet, concrete curing retardation board, etc.) may be a non-solidified mixture of the polymer (1) and the polymer component (2) or the polymer (1).
(A solidified mixture, a non-solidified mixture) of a mixture of a polymer and a polymer component (2) (a solidified mixture or an unsolidified mixture) is applied (or impregnated) to a support of an organic solvent, and then solidified or dried by heat treatment or the like. . Moreover, the concrete hardening retardant may be such that the concrete hardening retardant is adhered to the support with an adhesive or the like.

The thickness of the planar support is not particularly limited, but can be selected, for example, from a range of about 1 μm to 100 mm. For example, in the case of a substrate sheet, the thickness is 10 to 200
It is about μm, preferably about 15 to 150 μm, and more preferably about 20 to 100 μm. In the case of a substrate board, the thickness is about 1 to 100 mm, preferably 5 to 5 mm.
It is about 0 mm.

Amount of curing retarder (amount of application, amount of impregnation, etc.)
Is, in terms of non-volatile components, per m ² of the support, for example,
About 1 to 1,000 g / m ² , preferably 10 to 500 g / m ²
g / m ² approximately, more preferably about 50 to 250 g / m ^2. [Surface Treatment of Concrete] The concrete hardening retardant and concrete hardening retardant material of the present invention can be used for surface treatment of various types of concrete. For example, by contacting the upper surface of concrete cast on a formwork or the ground (such as a concrete pavement surface) with the surface of a concrete hardening retarder or a retarder layer of a concrete hardening retardant material, and after the concrete is hardened, the concrete surface is washed out. Can surface treat concrete.

[0077] Alternatively, the concrete can be surface-treated by casting unhardened concrete by using a mold on which a hardening delay layer is formed, curing the concrete, removing the concrete, and washing out the concrete surface. In addition, the said form should just have a hardening delay layer formed, For example, the formwork to which the concrete hardening delay sheet was stuck, the concrete hardening delay board, etc. may be sufficient.

In the concrete surface treatment method of the present invention, the concrete hardening retarding material (particularly, sheet) is used.
May be formed into a predetermined shape by cutting or the like to form a predetermined pattern on the concrete surface. For example, after arranging a setting delay sheet having a predetermined shape on a formwork, casting uncured concrete, and after hardening the concrete, removing the formwork and washing it out, corresponding to a predetermined pattern on the concrete surface. Decorations (for example, letters, designs,
Pattern, etc.). When the concrete hardening delay sheet of the present invention is used, since a solid resin is used, there is no lateral flow of the hardening delay component, and a pattern can be formed with high accuracy. Further, since the polymer (1) has a high concrete curing retarding ability, a deep pattern can be formed.

The concrete setting retarder or concrete setting delay material of the present invention has a high cement setting delay ability (accuracy, depth, etc.) and is useful for delaying the setting of a hardening composition containing cement. It is. Therefore, it can be advantageously used for surface treatment of concrete, particularly for surface decoration of concrete.

[0080]

The concrete hardening retardant of the present invention has a high concrete hardening delay ability even though it is solid, so that it can form a deep concrete hardening layer with high precision without lateral flow.

[0081]

The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

In the examples, the polymer component (2) shown in the following synthesis examples was used.

[Polymer component (2)] (Saturated polyester 1) 300.29 g (3.00 mol) of succinic anhydride, 253.72 g (3.33 mol) of propylene glycol, and Ti (OBu) as a catalyst were placed in a 1 L separable flask. ₄ ) 300 mg of a hexane solution (1 ml) was added, and the mixture was gradually added under a nitrogen stream.
The temperature was raised to 00 ° C, and the reaction was carried out for 7 hours while maintaining the temperature at 200 ° C. The acid value of the obtained polyester is 22 mgK.
OH / g. (Unsaturated Polyester 1) 266.19 g (2.71 mol) of maleic anhydride and 282.68 g (3.71 mol) of propylene glycol in a 1 L separable flask.
l) and a hexane solution (1 ml) of Ti (OBu) ₄ 260 mg as a catalyst were added, and the mixture was gradually heated to 200 ° C. under a nitrogen stream, and reacted for 7 hours while maintaining the temperature at 200 ° C. The acid value of the obtained polyester is 3
It was 0 mgKOH / g. (Unsaturated polyester 2) 266.19 g (2.71 mol) of maleic anhydride and 282.68 g (3.71 mol) of propylene glycol in a 1 L separable flask.
l) and a hexane solution (1 ml) of Ti (OBu) ₄ 260 mg as a catalyst were added, and the mixture was gradually heated to 200 ° C. under a nitrogen stream, and reacted for 7 hours while maintaining the temperature at 200 ° C. The acid value of the obtained polyester is 3
It was 0 mgKOH / g.

To the reaction mixture was added 0.5 g of methoquinone (1,000 ppm (based on polyester)) as a polymerization inhibitor, and after cooling to 80 ° C., 450 g of 2-hydroxyethyl methacrylate and 50 g of styrene monomer were added. To this mixture was further added 0.3% of cobalt naphthenate.
% By weight. (Unsaturated polyester 3) 266.19 g (2.71 mol) of maleic anhydride and 282.68 g (3.71 mol) of propylene glycol in a 1 L separable flask.
l) and a hexane solution (1 ml) of Ti (OBu) ₄ 260 mg as a catalyst were added, and the mixture was gradually heated to 200 ° C. under a nitrogen stream, and reacted for 7 hours while maintaining the temperature at 200 ° C. The acid value of the obtained polyester is 3
It was 6 mgKOH / g.

To the reaction mixture was added 0.5 g (1,000 ppm (based on polyester)) of methoquinone as a polymerization inhibitor, and the mixture was cooled to 80 ° C., and then EO-modified 2-hydroxyethyl methacrylate (manufactured by NOF Corporation, PE -9
0) 450 g and 50 g of styrene monomer were added. To this mixture, cobalt naphthenate was further added so as to be 0.3% by weight. (Unsaturated polyester 4) 298.04 g (3.04 mol) of maleic anhydride and 256.67 g (3.37 mol) of propylene glycol in a 1 L separable flask.
l) and a hexane solution (1 ml) of 300 mg of Ti (OBu) ₄ as a catalyst were added, and the mixture was gradually heated to 200 ° C. under a nitrogen stream, and reacted for 7 hours while maintaining the temperature at 200 ° C. The acid value of the obtained polyester is 3
It was 6 mgKOH / g.

To the reaction mixture was added 0.5 g (1,000 ppm (based on polyester)) of methoquinone as a polymerization inhibitor, and after cooling to 80 ° C., EO-modified 2-hydroxyethyl methacrylate (manufactured by NOF Corporation, PE -9
0) 450 g and 50 g of styrene monomer were added. To this mixture, cobalt naphthenate was further added so as to be 0.3% by weight. (Unsaturated polyester 5) 163.40 g (1.67 mol) of maleic anhydride and 366.60 g (1.83 mol) of polyethylene glycol were placed in a 1 L separable flask.
1) and a hexane solution (1 ml) of 160 mg of Ti (OBu) ₄ were added as a catalyst, and the mixture was gradually heated to 200 ° C. under a nitrogen stream, and reacted for 7 hours while maintaining the temperature at 200 ° C. The obtained polyester has an acid value of 4
It was 0 mgKOH / g.

To the reaction mixture was added 0.5 g (1,000 ppm (based on polyester)) of methoquinone as a polymerization inhibitor, and after cooling to 80 ° C., 150 g of 2-hydroxyethyl methacrylate and 50 g of styrene monomer were added. To this mixture was further added 0.3% of cobalt naphthenate.
% By weight. (Polyglycerin) Daicel Chemical Industries, Ltd. (Polyethylene Glycol) Nippon Oil & Fats Co., Ltd., PEG # 200 Examples 1-10 Allyl ether of polyethylene glycol monomethyl ether and anhydrous maleic as concrete setting retarding polymer (1) A copolymer of acid and styrene [Mariarim AKM-0531 (manufactured by Nippon Oil & Fats Co., Ltd.)], a polymer component (2), and a polymerization initiator [Perbutyl O (Nippon Oil & Fats Co., Ltd.) in Examples 3 to 10] Or an esterification catalyst (triethylamine) at room temperature at a ratio shown in Table 1, and the mixture was applied to a polyethylene terephthalate film (thickness: 38 μm) using a # 40 bar coater. The coating was solidified by heating at 120 ° C. for 10 minutes in an oven to prepare a curing retardation sheet.

Comparative Examples 1 to 9 The same procedures as in Examples 1 to 4 and 6 to 10 were carried out except that no Marialim was used.

Comparative Examples 10 to 19 The same procedures as in Examples 1 to 10 were carried out except that the heat treatment (solidification of the coating film) in the oven was not carried out.

Comparative Example 20 A copolymer of allyl ether of polyethylene glycol monomethyl ether, maleic anhydride and styrene [Mariarim AKM-0531 (manufactured by NOF Corporation)] was used.
It was applied to a polyethylene terephthalate film (thickness: 38 μm) using a # 40 bar coater. The obtained coated sheet was heated in an oven at 120 ° C. for 10 minutes. Note that the coating film was solidified.

Comparative Example 21 The procedure of Comparative Example 20 was repeated except that the heat treatment in the oven was not performed.

The concrete hardening delay characteristics (delay strength (depth), delay accuracy) of the sheets obtained in Examples 1 to 10 and Comparative Examples 1 to 21 were evaluated according to the following methods.

A sheet of Examples 1 to 10 or Comparative Examples 1 to 21 cut to 7 cm in width and 10 cm in length was applied to the bottom surface of a tray (15 cm in width, 20 cm in length, 4 cm in depth) by applying a concrete hardening retardant. It was attached with the surface facing upward. Mortar (Portland cement: 28.2 parts by weight, standard sand (JIS-R5201): 56.3 parts by weight,
(Water: 15.5 parts by weight) to a thickness of 3 cm,
Cured at 50% RH for 24 hours. After curing, the mold was removed, and unhardened cement and sand on the concrete upper surface were removed using high-pressure water and scourers.

(Delay Accuracy) Measure the shape of the uncured part,
Was evaluated according to the following criteria.

◎: The uncured portion has a shape (rectangular shape) substantially the same as that of the delay sheet. ：: The uncured portion is slightly wider than the shape of the delay sheet. X: Lateral flow occurs. The uncured portion does not maintain the shape of the delay sheet and has a vibrating wavy rectangular shape or elliptical shape. XX: The uncured portion is not formed. The numerical values in parentheses in the table (for example, And (8.
4 × 12.5)) indicates the average width × average length of the uncured portion. That is, in the measurement of the delay accuracy, since a cured delay sheet having a width of 7 cm and a length of 10 cm is used, the difference between the sheet shape and the shape of the uncured portion (for example, in Example 1, about 1. The larger the 4 cm (about 0.7 cm on one side) and about 2.5 cm (about 1.25 cm on one side) in the length direction, the more the concrete hardening delay effect is likely to reach the non-contact portion with the sheet, and the delay accuracy Is low.

(Delayed Depth) The depth of the uncured portion (delayed depth) was measured using a laser displacement meter with the bottom surface (cured portion) not in contact with the retarder as a reference surface, and evaluated based on the following criteria. (The numerical values in parentheses in the table indicate measured values).

◎: Uniformly dug deeply Δ: Mixing of deeply dug and shallow dug ×: Uniformly shallow dug XX: No uncured portion is formed It is shown in Table 3.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

As is clear from Tables 1 to 3, the curing retardation sheets of the examples have good concrete curing retardation characteristics (delay strength (depth), delay accuracy).

Continued on the front page F term (reference) 4J002 BB03X BB12X BC02X BC03X BC09X BD00X BD03X BE04W BE04X BF01X BF02X BG01W BG02W BG04X BG05X BG10X BH00W BH00X BQ00W BQ00X CF03X CF04X CF0X CF0X CF0X CF04X CF04X CF04X CF04X CF04X CF04X

Claims (21)

[Claims] 1. A polymer (1) having a concrete curing retarding ability, and a polymer component (2) of the following (i) or (ii) having a functional group reactive with the polymer (1), and A concrete setting retardant resin composition which is solid at room temperature. (I) Polymer (2a) having a functional group capable of reacting with polymer (1) (ii) Consisting of polymerizable polymer (2b) and polymerizable diluent, at least one of which is capable of reacting with polymer (1) Polymer composition having functional group 2. The polymer (1) comprises at least one selected from an acid group, an acid anhydride group and a hydrolysable ester group.
The concrete retardation resin composition according to claim 1, which is a polymer having two active groups, wherein the functional group of the polymer component (2) can react with the active group of the polymer (1). 3. The concrete setting retarding resin composition according to claim 2, wherein the acidic group is a carboxyl group. 4. The polymer (1) has a plurality of active groups,
The concrete setting retarding resin composition according to claim 2 or 3, wherein at least one pair of the active groups has a positional relationship capable of forming a chelate with respect to calcium ions. 5. The polymer (1) wherein a pair of active groups form a succinic acid unit or a succinic anhydride unit.
The concrete hardening retarding composition according to the above. 6. The polymer (1) comprises at least one selected from an acid group, an acid anhydride group and a hydrolysable ester group.
The concrete setting retardation resin composition according to claim 1, which is a copolymer of a polymerizable monomer having two active groups and a vinyl derivative represented by the following formula (I). Embedded image (Wherein, Y represents a C _1-6 alkylene group which may be branched; R ^1a represents a C _2-6 alkylene group which may be branched; R ^1b represents a hydrogen atom, an alkyl group, or a cycloalkyl group; ,
An aryl group, an aralkyl group, or an acyl group, and R ^1c represents a hydrogen atom or a methyl group. m is 0 or 1, n is 0 to
Indicates an integer of 100. ) 7. The polymer (1) is represented by the following formulas (IIa) to (I)
The conch according to claim 1, which has a structural unit represented by Ic).
Riet curing retardation resin composition. Embedded image(Where Z is C_1-6Alkylene group, carbonyl group or C
_2-7Shows an alkylenecarbonyl group. In addition, a in group Z
The alkylene units may be branched. R^2aAnd R^2bIs
Shows or is adjacent to a hydroxyl group or an alkoxyl group
Form an anhydride group with the carbonyl group. R^ThreeIs
Shows the residue of the vinyl monomer. p + q + r = 1 and p
Is 0.1 to 0.9, q is 0.1 to 0.9, r is 0 to 0.
5 is shown. R ^1a~ R^1c, M and n are the same as above.
However, when Z is a carbonyl group, R ^1bIs a hydrogen atom
Absent. ) 8. The concrete setting retardant resin composition according to claim 1, wherein the polymer (1) is liquid at room temperature. 9. The polymer component (2) according to claim 1, wherein the functional group capable of reacting with the polymer (1) is at least one selected from a hydroxyl group, an epoxy group, and a hydrolyzable acyloxyl group. Concrete setting retardant resin composition. 10. The polymer according to claim 1, wherein the polymer (2a) is a condensate of a polyhydric alcohol, a homo- or copolymer of a monomer having a hydroxyl group, a polyester terminated with a hydroxyl group, or a reactive derivative thereof. Concrete setting retardant resin composition. 11. A polyester, wherein the polyester is a hydroxyl group composed of at least one dicarboxylic acid selected from aliphatic C _2-6 dicarboxylic acids and aliphatic unsaturated C _4-6 dicarboxylic acids and C _2-4 alkylene glycol. The concrete setting retarding resin composition according to claim 10, which is an aliphatic polyester at the terminal. 12. The polyester having a number average molecular weight of 50.
Saturated polyester having a molecular weight of not more than 000 or a number average molecular weight of 1
11. An unsaturated polyester having a molecular weight of not more than 000.
A concrete retarder according to the above. 13. The concrete curable resin composition according to claim 1, wherein the polymer (2b) is an unsaturated polyester. 14. The concrete setting retardant resin composition according to claim 1, wherein the polymerizable diluent is at least one selected from a styrene monomer and a compound represented by the following formula (III). Embedded image (In the formula, X represents an optionally branched C _1-6 alkylene group or a carbonyl group. R ^1d represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an acyl group, or an epoxy group. R ^1a , R ^1c , m and n
Is the same as above) 15. A polymer (1) and a polymer component (2)
The concrete setting retardation resin composition according to claim 1, wherein the ratio of the former to the latter is 10/90 to 99/1 (weight ratio). 16. The concrete setting retarding resin composition according to claim 1, further comprising a polymerization initiator. 17. The concrete setting retarding resin composition according to claim 1, which is solidified by a reaction between the polymer (1) and the polymer component (2). 18. A polymer (1) having the ability to retard concrete hardening, and a polymer component (2) of the following (i) or (ii):
To produce a solid concrete setting retarder at room temperature. (I) Polymer (2a) having a functional group capable of reacting with polymer (1) (ii) Consisting of polymerizable polymer (2b) and polymerizable diluent, at least one of which is capable of reacting with polymer (1) Polymer composition having functional group 19. A polymer (1) and a polymer component (2)
19. The method for producing a concrete setting retardant resin composition according to claim 18, wherein the mixture is heated and solidified. 20. A concrete setting delay layer formed from the concrete setting delaying resin composition according to claim 1,
Concrete setting retarder formed on the surface of the support. 21. A concrete for delaying the concrete setting resin composition according to claim 1 or a concrete setting delay layer formed of the resin composition and uncured concrete, and after hardening the concrete, washing the concrete surface. Surface treatment method.