JP2001348256A - Thickener for mortar - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem that thickeners for mortar consisting of cellulose ethers retard setting. SOLUTION: This new thickener for mortar is manufactured from polyalkylene glycol, novel comb-shaped hydrophobic diol and polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mortar thickener which can be used in a wide range of mortars such as repair mortar, tile bonding mortar, masonry mortar, spray mortar, base mortar and finishing mortar. is there.

[0002]

2. Description of the Related Art Conventionally, various mortars have improved workability.
Mortars added with a cellulose ether thickener to increase the viscosity for the purpose of preventing breathing and the like have been used.

[0003]

SUMMARY OF THE INVENTION Cellulose ether-based mortar thickeners (more specifically, methylcellulose, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, hydroxyethylcellulose, hydroxyethylethylcellulose, etc.) have a thixotropic property suitable for mortar. And by giving water retention,
Although it is useful for improving the workability of the mortar (for example, making it easier to apply with a trowel) and preventing breathing, there is a problem that the hydration reaction of the mortar is inhibited and the curing time is delayed.
This has caused problems such as prolonged curing time under low temperature conditions (outdoors in winter, etc.) and insufficient strength of the mortar.

[0004]

Means for Solving the Problems The present inventors have worked diligently to develop a new thickener which can replace the thickener for mortar of the cellulose ether type, and have reached the present invention. Specifically, the present invention provides a compound represented by the general formula (1):

[0005]

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A repeating unit (U-1) represented by the general formula (2)

[0007]

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Wherein the molar ratio of the repeating unit (U-1) is 0.5 or more.
99 or less, the molar ratio of the repeating unit (U-2) is 0.01 or more and 0.5 or less, and the viscosity of the 2% aqueous solution at 20 ° C. is 10 mPa · s to 300,000 mPa · s.
Is a novel thickening agent for mortar comprising a polymer in the range of (1).

However, A is HO-A-OH having a hydroxyl group at least at both terminals and having a number average molecular weight of 400 to 10
A divalent group which is a 000 water-soluble polyalkylene polyol (compound A), and B is a polyisocyanate in which OCN-B-NCO is selected from the group consisting of polyisocyanates having 3 to 18 carbon atoms in total. A divalent group which is a naart compound (compound B), and D is HO-D-OH represented by the general formula (3)

[0010]

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(Where R ¹ is a hydrocarbon group having 1 to 20 carbon atoms. R ² and R ³ are a hydrocarbon group having 4 to 21 carbon atoms. The hydrocarbon groups R ¹ , R ² and R
Part or all of hydrogen in ³ may be substituted with fluorine, chlorine, bromine or iodine, and R ² and R ³ may be the same or different. Y and Y ′ are hydrogen, a methyl group or a CH ₂ Cl group, and Y and Y ′ may be the same or different. Z and Z ′ are oxygen, sulfur or CH ₂
Z and Z ′ may be the same or different. N is an integer of 0 to 15 when Z is oxygen, and 0 when Z is sulfur or a CH ₂ group. N ′ is an integer of 0 to 15 when Z ′ is oxygen, and Z ′ is sulfur or C
In the case of an H ₂ group, it is 0, and n and n ′ may be the same or different.)

[0012]

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(Wherein R ⁴ has 1 to 20 carbon atoms)
Is a hydrocarbon group. R ⁵ and R ^{6 each} have 4 to 4 carbon atoms.
21 hydrocarbon groups. Part or all of the hydrogen in the hydrocarbon groups R ⁴ , R ⁵ and R ⁶ may be substituted with fluorine, chlorine, bromine or iodine, and R ⁵ and R ⁶ may be the same or different. . X, X 'and X "are alkylene groups having 2 to 10 carbon atoms, and X, X' and X" may be the same or different. Part of the hydrogen of the alkylene group may be substituted with an alkyl group, chlorine or an alkyl chloride group. Z and Z ′ are oxygen, sulfur or CH ₂ groups, and Z and Z ′ may be the same or different. R ⁷ has a total carbon number of 2 to 2
10 alkylene groups, and k is an integer of 0 to 15. N is an integer of 0 to 15 when Z is oxygen;
It is 0 when Z is a sulfur or CH ₂ group. N ′ is an integer of 0 to 15 when Z ′ is oxygen, and 0 when Z ′ is a sulfur or CH ₂ group, and n and n ′ may be the same or different. ) Or general formula (5)

[0014]

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(However, R⁸And R⁹Is R⁸And R⁹Carbon
The sum of the numbers is 2 to 20 hydrocarbon groups. Also R^TenAnd
And R¹¹Is a hydrocarbon group having 4 to 21 carbon atoms. Also
Hydrocarbon group R⁸, R⁹, R^TenAnd R¹¹No part of the hydrogen
All are substituted with fluorine, chlorine, bromine or iodine.
You may. R⁸And R⁹May be the same or different. R
^TenAnd R¹¹May be the same or different. Also R¹²Is charcoal
It is an alkylene group having a prime number of 2 to 7. Y and Y '
Is hydrogen, methyl or CH_TwoCl and Y and Y ′ are
They may be the same or different. Z and Z 'are acids
Elemental, sulfur or CH_TwoZ and Z 'are the same but different
It may be. N is 0 to 15 when Z is oxygen.
Z is sulfur or CH_Two0 for a group
You. N ′ is an integer of 0 to 15 when Z ′ is oxygen.
And Z ′ is sulfur or CH_Two0 for a group, n and
n 'may be the same or different)
It is a divalent group that is a hydrophobic diol (Compound D).

In the mortar thickener of the present invention, the compound A is preferably a polyethylene glycol having a number average molecular weight of 1,000 to 20,000. In the mortar thickener of the present invention, it is preferable that the compound B is a chain aliphatic diisocyanate or a cycloaliphatic diisocyanate. Further, the compound B is preferably hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate or norbornane diisocyanate methyl.

In the thickener for mortar of the present invention, the compound represented by the general formula (4) is replaced by the following general formula (4a)

[0018]

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(However, R^FourIs carbonized with 1 to 20 carbon atoms
It is a hydrogen group. Also R^FiveAnd R⁶Has 4 to 21 carbon atoms
It is a hydrocarbon group. The hydrocarbon group R^Four, R^FiveAnd R
⁶Some or all of the hydrogen in it is fluorine, chlorine, bromine or
May be substituted with iodine;^FiveAnd R⁶Are the same but different
It may be. Y, Y 'and Y "are hydrogen, methyl
Or CH_TwoCl and Y and Y 'are the same or different
It may be. Z and Z ′ are oxygen, sulfur or
CH_TwoAnd Z and Z ′ may be the same or different
No. Also R⁷Is an alkylene group having 2 to 4 carbon atoms,
k is an integer of 0 to 15. And n is when Z is oxygen
An integer from 0 to 15, wherein Z is sulfur or CH _TwoGroup
Is 0. N ′ is an integer of 0 to 15 when Z ′ is oxygen.
Z ′ is sulfur or CH_Two0 for a group,
n and n 'may be the same or different)
preferable.

The thickener for mortar of the present invention includes
Compound D has the general formula (6)

[0021]

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[0022] (wherein, R ¹³ represents a linear or branched alkyl group having a carbon number of 4 to 18. The R ¹⁴ and R
¹⁵ is a linear or branched alkyl group having 4 to 18 carbon atoms. And the alkyl groups R ¹⁴ and R ¹⁵ may be the same or different). Alternatively, as the mortar thickener of the present invention, compound D is represented by the general formula (9)

[0023]

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(Wherein, R¹⁶Has 1 to 18 carbon atoms
Is an alkyl group. Also R¹⁷And R¹⁸Has 4 carbon atoms
~ 21 hydrocarbon groups;¹⁷And R¹⁸Is the same.
Also R ¹⁹Is 1,2-ethylene group, 1,3-propylene group
Or a 1,4-butylene group. Comb shaped sparse represented by)
It is preferably an aqueous diol. Solving the above problems
The present invention also provides at least a hydraulic inorganic powder as described above.
Dry mol characterized by containing a mortar thickener
It is a tall composition.

The present invention for solving the above-mentioned problems is also a mortar composition comprising at least hydraulic inorganic powder, water and the above-mentioned mortar thickener.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail based on its embodiments. The polymer used in the present invention is a polyurethane having a comb-shaped hydrophobic group, which is obtained by linking a water-soluble polyalkylene polyol and a comb-shaped hydrophobic diol with a polyisocyanate.

The water-soluble polyalkylene polyol (compound A) used in the present invention is an alkylene oxide polymer having hydroxyl groups at least at both ends of a polymer chain. However, when a polyalkylene polyol having three or more hydroxyl groups is used, the solubility of the product in water tends to decrease. Therefore, it is more preferable to use a polyalkylene glycol having hydroxyl groups at both ends of the polymer chain.

Examples of the monomer alkylene oxide include ethylene oxide, propylene oxide, butylene oxide and epichlorohydrin. In order to increase the solubility in water, the content of ethylene oxide is preferably 4%.
It is more preferably 0% by weight or more, further preferably 60% by weight or more, and particularly preferably 70 to 100% by weight. More preferably, a polymer of ethylene oxide (polyethylene glycol; hereinafter abbreviated as PEG) is used.

The compound A has a number average molecular weight of 40.
Those having 0 to 100,000 are preferred. More preferably, it is 1,000 to 20,000. Molecular weight 400-1
This is because if it is in the range of 00000, it is easy to obtain a product having both appropriate thickening and solubility. If the molecular weight is 1,
In the range of 000 to 20,000, a product exhibiting sufficient viscosity and solubility is most easily obtained.

The polyisocyanate compound (compound B) used in the present invention has a total number of carbon atoms selected from the group consisting of linear aliphatic polyisocyanates, cycloaliphatic polyisocyanates and aromatic polyisocyanates. Is (N
3-18 polyisocyanate compounds (including the carbon of the CO group). When the total number of carbon atoms of the polyisocyanates is in this range, the solubility of the polymer becomes good.

However, when polyisocyanates having three or more NCO groups in the molecule are used, the solubility of the product in water tends to decrease. Therefore, it is more preferable to use diisocyanates having two NCO groups in the molecule. As the diisocyanates, there are aromatic diisocyanates, chain aliphatic diisocyanates, cycloaliphatic diisocyanates, etc., and chain aliphatic diisocyanates and cycloaliphatic diisocyanates. The polymer used is more excellent in alkali resistance than the one using aromatic diisocyanate.

Therefore, it is more preferable to use chain and cyclic aliphatic diisocyanates having 3 to 18 carbon atoms in total. More preferably, hexamethylene diisocyanate (commonly referred to as HDI), isophorone diisocyanate (commonly known as I)
PDI), hydrogenated tolylene diisocyanate (commonly known as HT
DI), hydrogenated xylylene diisocyanate (commonly known as HX
DI) or norbornane diisocyanatomethyl (commonly called NBDI). Particularly preferably HD
I.

The chain aliphatic diisocyanates are NCO
A diisocyanate compound having a structure in which groups are connected by a linear or branched alkylene group, and specific examples include methylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, and 1-methylethylene. Diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 2-methylbutane-1,4-diisocyanate, hexamethylene diisocyanate (HDI), heptamethylene diisocyanate, 2,2′-dimethylpentane -1,5-diisocyanate, lysine diisocyanate methyl ester (LD
I), octamethylene diisocyanate, 2,5-dimethylhexane-1,6-diisocyanate, 2,2,4
-Trimethylpentane-1,5-diisocyanate, nonamethyldiisocyanate, 2,4,4-trimethylhexane-1,6-diisocyanate, decamethylenediisocyanate, undecamethylenediisocyanate, dodecamethylenedi Isocyanate, tridecamethylene diisocyanate, tetradecamethylene diisocyanate,
Pentadecamethylene diisocyanate, hexadecamethylene diisocyanate, trimethylhexamethylene diisocyanate and the like can be mentioned.

Cycloaliphatic diisocyanates are NCO
A diisocyanate compound in which an alkylene group connecting the groups has a cyclic structure, and specific examples thereof include cyclohexane-1,2-diisocyanate and cyclohexane-1,3.
-Diisocyanate, cyclohexane-1,4-diisocyanate, 1-methylcyclohexane-2,4-diisocyanate, 1-methylcyclohexane-2,6-diisocyanate, 1-ethylcyclohexane-2,4-
Diisocyanate, 4,5-dimethylcyclohexane-
1,3-diisocyanate, 1,2-dimethylcyclohexane-ω, ω′-diisocyanate, 1,4-dimethylcyclohexane-ω, ω′-diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane -4,4'-diisocyanate, dicyclohexylmethylmethane-4,4'-diisocyanate, dicyclohexyldimethylmethane-4,4'-diisocyanate, 2,2'-dimethyldicyclohexylmethane
4,4′-diisocyanate, 3,3′-dimethyldicyclohexylmethane-4,4′-diisocyanate, 4,
4'-methylene-bis (isocyanatocyclohexane), isopropylidenebis (4-cyclohexyl isocyanate) (IPCI), 1,3-bis (isocyanatomethyl) cyclohexane, hydrogenated tolylene diisocyanate (HTDI), hydrogenation 4,4'-diphenylmethane diisocyanate (HMDI), hydrogenated xylylene diisocyanate (HXDI), norbornane diisocyanate methyl (NBDI) and the like.

The aromatic diisocyanate is a diisocyanate compound in which NCO groups are linked by an aromatic group such as a phenylene group, an alkyl-substituted phenylene group and an aralkylene group or a hydrocarbon group containing an aromatic group. Specific examples thereof include 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate (2,4-TDI), and 1-methyl-2,6-
Phenylene isocyanate (2,6-TDI), 1-
Methyl-2,5-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1,3
-Dimethyl-2,4-phenylene diisocyanate,
1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, m-xylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate, 1- Methyl-3,5-diethylbenzene-
2,4-diisocyanate, 3-methyl-1,5-diethylbenzene-2,4-diisocyanate, 1,3,5
-Triethylbenzene-2,4-diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-
1,5-diisocyanate, 1-methylnaphthalene-
1,5-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 1,1-dinaphthyl-2,2'-diisocyanate, biphenyl-2,4'- Diisocyanate, biphenyl-4,4'-diisocyanate, 1,3-bis (1
-Isocyanato-1-methylethyl) benzene, 3,
3'-dimethylbiphenyl-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate (MDI), diphenylmethane-2,2'-diisocyanate, diphenylmethane-2,4'-diisocyanate And xylylene diisocyanate (XDI).

Other polyisocyanates include 1,
6,11-undecatriisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane,
1,3,6-hexamethylene triisocyanate and the like. The comb-shaped hydrophobic diol (compound D) used in the present invention has two secondary hydroxyl groups in the molecule represented by the following general formula (3), (4) or (5) and has a hydrophobic chain in the molecule. These are hydrophobic diols having at least three of them.

That is, the compound D used in the present invention includes a comb-shaped diol having a structure represented by the following general formula (3).

[0038]

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However, in the general formula (3), R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 4 to 18 alkyl groups, alkenyl groups, aralkyl groups or aryl groups. is there. R ² and R ³ are a hydrocarbon group having 4 to 21 carbon atoms, more preferably 4 to 1 carbon atoms.
8 is a hydrocarbon group such as an alkyl group, an alkenyl group, an aralkyl group or an aryl group.

Some or all of the hydrogen atoms in the hydrocarbon groups R ¹ , R ² and R ³ may be substituted with halogen atoms such as fluorine, chlorine, bromine or iodine, and R ² and R ³ are the same. But they may be different. Y and Y ′ are hydrogen, a methyl group or a CH ₂ Cl group, and Y and Y ′ may be the same or different, but are more preferably the same.

Z and Z ′ are oxygen, sulfur or CH ₂
Z and Z ′ may be the same or different,
More preferably, they are the same. More preferably, both Z and Z 'are oxygen. N is an integer of 0 to 15, more preferably 0 to 5 when Z is oxygen, and 0 when Z is a sulfur or CH ₂ group.
N ′ is an integer of 0 to 15 when Z ′ is oxygen, and more preferably an integer of 0 to 5 when Z ′ is sulfur or a CH ₂ group. Although they may be different, they are more preferably the same.

In the compound D represented by the general formula (3), a comb-shaped diol represented by the following general formula (6) is particularly preferable.

[0043]

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However, in the general formula (6), R ¹³ is a linear or branched alkyl group having 4 to 18 carbon atoms. R ¹⁴ and R ¹⁵ are a linear or branched alkyl group having 4 to 18 carbon atoms. The alkyl group R ¹⁴
And R ¹⁵ may be the same or different. The compound D used in the present invention includes a comb-shaped diol having a structure represented by the following general formula (4).

[0045]

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However, in the general formula (4), R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, more preferably 4 to 18 carbon atoms, such as an alkyl group, an alkenyl group, an aralkyl group or an aryl group. R ⁵ and R ^{6 each} have 4 to 4 carbon atoms.
21, and more preferably 4 to 18 hydrocarbon groups such as an alkyl group, an alkenyl group, an aralkyl group and an aryl group. A part or all of the hydrogen in the hydrocarbon groups R ⁴ , R ⁵ and R ⁶ may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine. R ⁴ and R ⁵ may be the same or different, but are more preferably the same.

X, X 'and X "each have 2 to 1 carbon atoms.
0, more preferably 2 to 4 alkylene groups, X,
X 'and X "may be of different even for the same. In addition some of the hydrogen of the alkylene group, an alkyl group, chlorine or optionally substituted with an alkyl chloride group .R ⁷ All It is an alkylene group having 2 to 10 carbon atoms.
More specifically, examples of the alkylene group R ⁷ include a 1,2-ethylene group, a 1,3-propylene group, a 1,2-propylene group, a 1,4-butylene group, and a 2,3-butylene group. .

K is an integer of 0 to 15, more preferably 0 to 5. Z and Z ′ are oxygen, sulfur or CH ₂ groups, and Z and Z ′ may be the same or different, but are preferably the same. More preferably, both Z and Z 'are oxygen. N is an integer of 0 to 15, more preferably 0 to 5 when Z is oxygen, and 0 when Z is sulfur or a CH ₂ group. Also n '
Is 0 to 15, more preferably 0 to 5 when Z ′ is oxygen.
And 0 when Z ′ is a sulfur or CH ₂ group, and n and n ′ may be the same or different, but are more preferably the same.

The compound D represented by the general formula (4) according to the present invention typically includes a comb-shaped diol represented by the following general formula (4a).

[0050]

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However, in the general formula (4a), R ⁴ is a hydrocarbon group having 1 to 20, more preferably 4 to 18 carbon atoms such as an alkyl group, an alkenyl group, an aralkyl group or an aryl group. In the general formula (4a), R ⁵
And R ⁶ have 4 to 21 carbon atoms, more preferably 4 to 1 carbon atoms.
8 is a hydrocarbon group such as an alkyl group, an alkenyl group, an aralkyl group or an aryl group. A hydrocarbon group R ⁴ ,
Part or all of hydrogen in R ⁵ and R ⁶ may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine. R ⁵ and R ⁶ may be the same or different,
More preferably, they are the same.

[0052] Also Y, Y 'and Y "is hydrogen, methyl group or CH ₂ Cl group, Y and Y' may be the same or different, but are preferably the same .R ⁷ All An alkylene group having 2 to 4 carbon atoms, and k is 0 to 1
5, and more preferably an integer of 0 to 5. Z and Z ′ are oxygen, sulfur or CH ₂ groups, and Z and Z ′ may be the same or different, but are preferably the same. More preferably, both Z and Z 'are oxygen.

N is an integer of 0 to 15, more preferably 0 to 5 when Z is oxygen, and Z is sulfur or CH _2.
In the case of a group, it is 0. N ′ is 0 when Z ′ is oxygen.
15, more preferably an integer of 0 to 5, and 0 when Z ′ is a sulfur or CH ₂ group, and n and n ′ may be the same or different, but are more preferably the same.

In a more preferred embodiment, the compound D represented by the general formula (4) according to the present invention is a comb-shaped diol represented by the following general formula (9).

[0055]

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However, in the general formula (9), R ¹⁶ is an alkyl group having 1 to 18 carbon atoms, more preferably 4 to 18 carbon atoms. R ¹⁷ and R ¹⁸ are a hydrocarbon group having 4 to 21 carbon atoms, more preferably 4 to ¹⁸ carbon atoms, and R ¹⁷ and R ¹⁸ are the same. R ¹⁹ is a 1,2-ethylene group, 1,3-propylene group, or 1,4-butylene group. further,
The compound D used in the present invention includes a comb-shaped diol having a structure represented by the following general formula (5).

[0057]

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In the general formula (5), R ⁸ and R ⁹ are R
The total number of carbon atoms in ⁸ and R ⁹ is a hydrocarbon group having 2 to 20 carbon atoms.
Preferably, R ⁸ and R ⁹ are a hydrocarbon group such as an alkyl group, an alkenyl group, an aralkyl group or an aryl group having 4 to 18 carbon atoms in total. R ¹⁰ and R ¹¹ are a hydrocarbon group having 4 to 21 carbon atoms. Further, the hydrocarbon group R ⁸ ,
A part or all of hydrogen of R ⁹ , R ¹⁰ and R ¹¹ may be substituted with a halogen atom such as fluorine, chlorine, bromine or iodine.

R ⁸ and R ⁹ may be the same or different, but are more preferably the same. R ¹⁰ and R ¹¹ may be the same or different, but are more preferably the same. R ¹² is an alkylene group having 2 to 7 carbon atoms. Y and Y ′ are hydrogen, a methyl group or CH ₂ Cl
And Y and Y ′ may be the same or different,
More preferably, they are the same.

Z and Z ′ are oxygen, sulfur or CH ₂
Z and Z ′ may be the same or different,
More preferably, they are the same. More preferably, both Z and Z 'are oxygen. N is an integer of 0 to 15, more preferably 0 to 5 when Z is oxygen, and 0 when Z is a sulfur or CH ₂ group.
N ′ is an integer of 0 to 15 when Z ′ is oxygen, and more preferably an integer of 0 to 5 when Z ′ is sulfur or a CH ₂ group. Although they may be different, they are more preferably the same.

As described above, the general formulas (3), (4),
The comb-shaped hydrophobic diols represented by and (5) can be obtained by adding various oxirane-containing compounds (compounds having an oxirane ring) to primary amines. The addition reaction between the amino group of the amines and the oxirane-containing compound has a high activity, and the reaction proceeds sufficiently without a catalyst.

More specifically, the primary amines include primary linear or cyclic alkylamines, primary linear or cyclic alkenylamines, primary aralkylamines, and primary dialkylamino. Alkylamines,
Primary N-benzylaminopyrrolidines, primary N-aminoalkylmorpholines, primary arylamines,
Primary aminopyridines, primary aminoalkylpyridines, primary alkyloxyalkylamines, primary alkenyloxyalkylamines, primary aryloxyalkylamines, primary aralkyloxyalkylamines And the like.

Examples of primary chain alkylamines include:
Methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, sec-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, 2-aminoheptane, n-octylamine, Isooctylamine, 2-aminooctane, 2-ethylhexylamine,
2-amino-6-methylheptane, nonylamine, isononylamine, 1,4-dimethylheptylamine, 3-
Aminononane, 2-amino-6-ethylheptane, n-
Decylamine, n-undecylamine, 2-aminoundecane, 6-aminoundecane, n-dodecylamine,
n-tridecylamine, 2-aminotridecane, n-tetradecylamine, 2-aminotetradecane, n-pentadecylamine, 8-aminopentadecane, n-hexadecylamine, n-heptadecylamine, n-octadecylamine And linear alkylamines such as n-nonadecylamine and 2-aminononadecane.

Examples of primary chain alkenylamines include allylamine and oleylamine. Examples of primary cyclic alkylamines include cyclohexylamine, cycloheptylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, aminomethylcyclohexane, cyclooctylamine, 2,3-dimethylcyclohexyl Amines, 3,3,5-trimethylcyclohexylamine, 4-tert-butylcyclohexylamine,
1-cyclopentyl-2-aminopropane, 1-aminoindan, cyclododecylamine, o-aminobicyclohexyl, 3-aminospiro [5,5] undecane, bornylamine, 1-adamantanamine, 2-aminonorbornane, 1-adamantanmethyl Amines and the like.

Examples of primary cyclic alkenylamines include dihydroabiethylamine, 2- (1-cyclohexenyl) ethylamine and the like. Examples of primary aralkylamines include benzylamine, phenethylamine, p-methoxyphenethylamine, α-phenylethylamine, 1-methoxy-3-phenylpropylamine, N-aminopropylaniline and the like.

Examples of primary dialkylaminoalkylamines include N, N-dimethylethylenediamine, N, N
N-diethylethylenediamine, N, N-diisopropylethylenediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, diethylaminopropylamine, dibutylaminopropylamine, 1-dimethyl amino-2-propylamine, N ^2, N ² - dimethyl-1,2-propanediamine, 4-dimethylamino-butyl amine, 1-dimethylamino-ethyl-2-aminopropane, N, N-dimethyl neopentanediamine, 1- Diethylamino-2-propylamine, 6-dimethylaminohexylamine, 2-di-n-propylaminoethylamine, N-ethyl-N-
Butyl ethylenediamine, 7-diethyl amino heptyl amine, N ^1, N ¹ - di -n- propyl-1,2-propanediamine, N ', N'-di -n- propanediamine, 5
-Diethylaminopentylamine, 2-amino-5-diethylaminopentane, N, N-di-n-butylethylenediamine, N, N-di-tert-butylethylenediamine, 2-diisobutylaminoethylamine, 4-diisopropylaminobutylamine, 7- Diethylaminoheptylamine, 3- (di-n-butylamino) propylamine, N, N-diisobutyl-1,6-hexanediamine, 3-dioctylaminopropylamine, 3-didecylaminopropylamine, 1- (2- Aminoethyl) piperidine, 3-piperidinopropylamine, 4-
Pyrrolidinobutylamine, N-aminoethyl-4-pipecholine, 3-aminotropane, 5-pyrrolidinoamylamine, N-aminopropyl-4-pipecholine, 1- (3
-Aminopropyl) -2-pipecholine, 1-aza-bicyclo [2.2.2] oct-3-ylamine, 1-benzyl-3-aminopyrrolidine, N ¹ -ethyl-N ¹ -phenylpropane-1,3 -Diamine and the like.

Examples of primary N-benzylaminopyrrolidines include N-benzyl-3-aminopyrrolidine and N-benzylaminopyrrolidine.
-Benzyl-2-methyl-3-aminopyrrolidine and the like. Examples of primary N-aminoalkylmorpholines include N-aminoethylmorpholine, N-aminopropylmorpholine and the like.

Examples of primary arylamines include aniline, 2-chloroaniline, 2,3-dichloroaniline, 2,4-dibromoaniline, 2,4,6-tribromoaniline, o-toluidine, -Chloro-4-methylaniline, 2,3-dimethylaniline, 2,4-dimethylaniline, 2,5-dimethylaniline, 2-ethylaniline, 2-isopropylaniline, 4-tert-butylaniline, p-decylaniline , P-dodecylaniline, p-tetradecylaniline, 4-cyclohexylaniline, 2-aminobiphenyl, 1-naphthylamine, 5-aminoindane, 1-aminonaphthacene, 6-
Aminochrysene, 1-aminopyrene and the like can be mentioned.

Examples of primary aminopyridines include 2
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propylpyridine, 2-amino-4, 6-dimethylpyridine, 2
-Amino-3-nitropyridine and the like. Examples of primary aminoalkylpyridines include 2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine, 3-aminomethyl-6-chloropyridine, and the like.

The primary alkyloxyalkylamines include 2-alkoxyethylamines, 3-alkoxypropylamines, 4-alkoxybutylamines, alkenyloxyalkylamines, aralkyloxyalkylamines, and aryloxyalkylamines. Phenols, aminoalkyl ethers of alcohol-alkylene oxide adducts, and aminoalkyl ethers of phenol / alkyl-substituted phenol-alkylene oxide adducts.

The 2-alkoxyethylamines include
2-methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2-isopropoxyethylamine, 2-butoxyethylamine, 2- (isobutoxy) ethylamine, 2- (tert-butoxy)
Ethylamine, 2-pentyloxyethylamine, 2-
Hexyloxyethylamine, 2-heptyloxyethylamine, 2-octyloxyethylamine, 2- (2
-Ethylhexyloxy) ethylamine, 2- (α-butyloctyloxy) ethylamine, 2-decyloxyethylamine, 2-dodecyloxyethylamine, 2-
Examples thereof include tetradecyloxyethylamine, 2-pentadecyloxyethylamine, 2-hexadecyloxyethylamine, 2-heptadecyloxyethylamine, 2-octadecyloxyethylamine, 2-nonadecylethylamine, and 2-eicosylethylamine.

Examples of 3-alkoxypropylamines include 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, 3-butoxypropylamine, 3- (isobutoxy) Propylamine, 3- (te
rt-butoxy) propylamine, 3-pentyloxypropylamine, 3-hexyloxypropylamine,
3-heptyloxypropylamine, 3-octyloxypropylamine, 3- (2-ethylhexyloxy)
Propylamine, 3- (α-butyloctyloxy) propylamine, 3-decyloxypropylamine,
Dodecyloxypropylamine, 3-tetradecyloxypropylamine, 3-pentadecyloxypropylamine, 3-hexadecyloxypropylamine, 3-heptadecyloxypropylamine, 3-octadecyloxypropylamine, 3-nonadecylpropylamine ,
3-eicosylpropylamine and the like.

Examples of 4-alkoxybutylamines include 4-methoxybutylamine, 4-ethoxybutylamine, 4-propoxybutylamine, 4-isopropoxybutylamine, 4-butoxybutylamine, 4- (isobutoxy) butylamine, and 4- (tert) -Butoxy) butylamine, 4-pentyloxybutylamine,
4-hexyloxybutylamine, 4-heptyloxybutylamine, 4-octyloxybutylamine, 4-
(2-ethylhexyloxy) butylamine, 4- (α
-Butyloctyloxy) butylamine, 4-decyloxybutylamine, 4-dodecyloxybutylamine,
4-tetradecyloxybutylamine, 4-pentadecyloxybutylamine, 4-hexadecyloxybutylamine, 4-heptadecyloxybutylamine, 4-octadecyloxybutylamine, 4-nonadecylbutylamine, 4-eicosylbutylamine, 4- (2 , 4-
Di-tert-amylphenoxy) butylamine and the like.

Examples of the alkenyloxyalkylamines include 3-vinylpropylamine, 2-allyloxyethylamine, 3-oleyloxypropylamine and the like. Examples of aralkyloxyalkylamines include 2-benzyloxyethylamine,
Examples include 3-phenethyloxypropylamine.

Examples of the aryloxyalkylamines include 2-phenyloxyethylamine and 3- (p-nonylphenyloxy) propylamine. Other amines include aminoalkanol ethers of alkylene oxide adducts of alcohols and phenols (such as ethylene oxide adducts, propylene oxide adducts, and epichlorohydrin adducts).

Examples of aminoalkanol ethers of alcohol-ethylene oxide adducts include 2- [2-
(Dodecyloxy) ethoxy] ethylamine, 3,6
9-trioxapentadecylamine and the like.
Similarly, aminoalkanol ethers of propylene oxide adducts of alcohols and phenols, propylene oxide / ethylene oxide adducts, and epichlorohydrin adducts can also be used. From the viewpoint of the aqueous solution viscosity of the polymer, the addition number k is suitably about 1 to 15.

Examples of other primary amines include pyrazines such as 2-aminomethylpyrazine, 2-aminopyrazine and sulfalene. On the other hand, various glycidyl ethers and 1,2,
-Epoxy alkanes, 1,2-epoxy alkenes,
Glycidyl sulfides and the like can be used.

Examples of glycidyl ethers include alkyl glycidyl ethers, alkenyl glycidyl ethers, aralkyl glycidyl ethers, and aryl glycidyl ethers. Examples of alkyl glycidyl ethers include n-butyl glycidyl ether, sec-butyl glycidyl ether, tert-butyl glycidyl ether, glycidyl pentyl ether, glycidyl hexyl ether, glycidyl octyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether,
Glycidyl nonyl ether, decyl glycidyl ether, dodecyl glycidyl ether, glycidyl lauryl ether, glycidyl tridecyl ether, glycidyl tetradecyl ether, glycidyl pentadecyl ether, glycidyl hexadecyl ether, glycidyl stearyl ether, 3- (2- (perfluorohexyl)
Ethoxy) -1,2-epoxypropane, 3- (3-perfluorooctyl-2-iodopropoxy) -1,2
-Epoxypropane and the like.

Examples of alkenyl glycidyl ethers include allyl glycidyl ether and oleyl glycidyl ether. Examples of aralkyl glycidyl ethers include benzyl glycidyl ether and phenethyl glycidyl ether. Examples of aryl glycidyl ethers include phenyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, 2-ethylphenyl glycidyl ether,
4-ethylphenylglycidyl ether, 2-methylphenylglycidylether, glycidyl-4-nonylphenylether, glycidyl-3- (pentadecadienyl) phenylether, 2-bisphenylglycidylether, benzylglycidylether, α-naphthylglycidyl Ether and dibromophenyl glycidyl ether.

Other glycidyl ethers include glycidyl ethers of alkylene oxide adducts of alcohols and phenols (ethylene oxide adduct, propylene oxide adduct, epichlorohydrin adduct, etc.). Examples of glycidyl ethers of ethylene oxide adducts include glycidyl ether of 2-ethylhexyl alcohol-ethylene oxide adduct, glycidyl ether of lauryl alcohol-ethylene oxide adduct, glycidyl ether of 4-tert-butylphenol-ethylene oxide adduct and Glycidyl ethers of nonylphenol-ethylene oxide adduct and the like can be mentioned. Similarly, glycidyl ethers of propylene oxide adducts of alcohols and phenols, propylene oxide / ethylene oxide adducts, and epichlorohydrin adducts can also be used. The glycidyl ethers of industrial chemicals usually contain glycidyl ethers of epichlorohydrin adduct as by-products, but such low-purity raw materials can also be used. From the viewpoint of the aqueous solution viscosity of the polymer, the addition number n is suitably about 1 to 15.

Further, 1,2-epoxyalkanes and 1,2-epoxyalkanes
Examples of epoxy alkenes include 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, and 1,2-epoxidedodecane. , 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,
Examples thereof include 2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxy-7-octene, and 1,2-epoxy-9-decene.

Other oxirane-containing compounds include 2
Alkyl glycidyl thioethers (alkyl glycidyl sulfides) such as -ethylhexyl glycidyl sulfide and decyl glycidyl sulfide; and aryl glycidyl thioethers (aryl glycidyl sulfide) such as p-nonylphenyl glycidyl sulfide.

The compound D can be obtained by reacting the amines and the oxirane-containing compound at a ratio of one molecule of the amine to two molecules of the oxirane-containing compound.
Next, the reaction formula is shown.

[0084]

Embedded image

(However, R ^a , R ^b , and R ^c correspond to the respective substituents of the general formulas (3), (4), (4a), (5), (6) and (9).) In the reaction, the target compound D can be obtained almost quantitatively when the molar ratio of the amines and the oxirane-containing compounds as the raw materials is 1: 2. Even though compound D itself has a hydroxyl group capable of reacting with the oxirane-containing compound, one or more molecules of the oxirane-containing compound are added to compound D, and only a few by-products may actually occur. . This is probably because the reaction of the amines with the oxirane-containing compounds is much faster than the reaction of the diols with the oxirane-containing compounds.

The molar ratio of the raw materials is not limited to 1: 2, and the reaction is carried out using an oxirane-containing compound in excess with respect to the amines (for example, at a molar ratio of 1: 3). Compound D can also be produced by removing the oxirane-containing compound in the reaction by distillation or the like. Also in this case, by-products are slight. The reaction was carried out using 1,2-epoxyalkanes,
It is easier to use glycidyl ethers than to use 2-epoxyalkenes and glycidyl sulfides. This is probably because the reactivity of glycidyl ethers with amines is higher.

Compound D has 3 to 4 hydrophobic chains (R ¹ , R ² and R ^{3 in} the general formula (3) or R ⁴ and R ^{5 in the} general formulas (4) and (4a)) in the molecule. And R ⁶ , or R ⁸ , R ⁹ , R ¹⁰ and R ^{11 in} the general formula (5), R ¹³ , R ¹⁴ and R ^{15 in} the general formula (6), or R ^{16 in the} general formula (9) , R ¹⁷ and R ¹⁸ ), but having these hydrophobic chains close to each other has an effect of imparting appropriate hydrophobicity to the polymer. It is presumed that it is this moderate hydrophobicity that gives the mortar an appropriate viscosity. The number of carbon atoms in each hydrophobic chain needs to be long enough to impart appropriate hydrophobicity to the polymer.

The hydrophobic chains of the amines have 1 to 20 carbon atoms.
Below is preferred. Substituent R¹, R^Four, R ¹³Or R¹⁶Carbon
Polymers obtained by using amines with numbers in this range
Does not decrease in water solubility. Similarly, the substituent R⁸And R⁹of
If amines with total carbon number within 20 are used, high
The solubility of the child in water does not decrease. More preferably a hydrophobic chain
Having 1 to 18, more preferably 4 to 18 carbon atoms
Having a branched or branched alkyl group as a hydrophobic group
Using ruamines or alkyloxyalkylamines
It is that you are.

The hydrophobic chains of glycidyl ethers (R ² and R ^{3 in} the general formula (3), R ⁵ and R ^{6 in} the general formulas (4) and (4a), or R ⁵ and R ^{6 in} the general formula (5) The carbon number of ¹⁰ and R ¹¹ , R ¹⁴ and R ¹⁵ in the general formula (6), or R ¹⁷ and R ^{18 in} the general formula (9) is preferably 4 or more and 21 or less. When a glycidyl ether having a carbon number within this range is used, the hydrophobicity of the polymer is sufficiently high and the solubility of the polymer is also good. More preferably, alkyl glycidyl ethers having a linear or branched alkyl group having 4 to 18 carbon atoms as a hydrophobic group, or an aromatic group having 6 to 18 carbon atoms or an alkyl-substituted aromatic group as a hydrophobic group. Aryl glycidyl ethers.

For the same reason, the hydrophobic group of 1,2-epoxyalkane, 1,2-epoxyalkene, alkyl glycidyl thioether and aryl glycidyl thioether preferably has 4 to 21 carbon atoms. The method for producing the comb-shaped hydrophobic diol (compound D) is described below, but the method for synthesizing the comb-shaped hydrophobic diol used in the present invention is not limited to this example.

Raw materials, such as amines and oxirane-containing compounds, are charged into a reaction vessel having a stirring device, a raw material introduction mechanism, and a temperature control mechanism, and reacted at a predetermined reaction temperature while stirring. The reaction can be performed without a solvent, but a general solvent such as dimethylformamide (DMF) may be used.

For the introduction of the raw materials, the amines and the oxirane-containing compounds may be charged at once, or one of them may be charged into a reaction vessel, and the other may be introduced continuously or stepwise. The reaction temperature is suitably room temperature to about 160 ° C, more preferably about 60 ° C to 120 ° C.

The reaction time depends on the reaction temperature and the like.
It is about 5 to 10 hours. The unreacted raw materials slightly remaining in the diol after the reaction can be purified by a conventional method such as evaporating low boiling components under reduced pressure. The OH value of the obtained diol can be determined by an ordinary method. The polymer used in the present invention has the general formula (8)

[0094]

Embedded image

As shown in the above formula, the compound is synthesized by a reaction between two hydroxyl groups of a polyalkylene glycol (compound A) and a comb-shaped hydrophobic diol (compound D) and two NCO groups of a diisocyanate compound (compound B). . In a polymer in which the molar ratio of the repeating unit (U-1) is (1-x) and the molar ratio of the repeating unit (U-2) is x, the molar ratio of the compound A to the compound D is (1-x). : X.

The method for producing the mortar thickener will be described below with reference to examples, but the present invention is, of course, not limited to the following method. The inside of a reaction vessel having a stirring device, a raw material introduction mechanism, and a temperature control mechanism is replaced with an inert gas. A polyalkylene glycol is charged into a reaction vessel. In some cases, a solvent is charged.

The catalyst is added while controlling the reaction vessel at the set reaction temperature. While stirring the inside of the vessel, the polyisocyanate compound and the comb-shaped hydrophobic diol are introduced into the reaction vessel.
The method of introduction is not particularly limited. It may be introduced continuously or intermittently. Also, the polyisocyanate compound and the comb-shaped hydrophobic diol may be introduced simultaneously, or the comb-shaped hydrophobic diol may be introduced after the introduction of the polyisocyanate compound, or the polyisocyanate compound may be introduced after the introduction of the comb-shaped hydrophobic diol. Is also good.

It is not necessary to add the catalyst to the polyalkylene glycol before the reaction, and the reaction can be started by adding the catalyst after adding the polyisocyanate compound or the comb-shaped hydrophobic diol to the polyalkylene glycol. Alternatively, it is also possible to add a catalyst in advance to the polyisocyanate compound or the comb-shaped hydrophobic diol, and to add them to the polyalkylene glycol to cause a reaction.

The catalyst used for the reaction is not particularly limited, and is generally used for the reaction of polyisocyanates and polyols such as organometallic compounds, metal salts, tertiary amines, other base catalysts and acid catalysts. Known catalysts can be used. Examples include dibutyltin dilaurate (hereinafter abbreviated as DBTDL), dibutyltin di (dodecylthiolate), stannous octanoate, phenylmercuric acetate, zinc octoate, lead octoate, zinc naphthenate, lead naphthenate, triethylamine (T
EA), tetramethylbutanediamine (TMBDA),
N-ethylmorpholine (NEM), 1,4-diaza [2.2.2] bicyclooctane (DABCO),
8-diazabicyclo [5.4.0] -7-undecene (DBU) and N, N'-dimethyl-1,4-diazacyclohexane (DMP).

The amount of the catalyst used in the reaction varies depending on the reaction temperature and the type of the catalyst, and is not particularly limited.
0.0001 per mole of polyalkylene glycol
0.1 mol, more preferably about 0.001 to 0.1 mol is sufficient. The reaction can be carried out without a solvent, but the reaction can also be carried out using a solvent in order to reduce the melt viscosity of the product. Solvents include halogenated solvents such as carbon tetrachloride, dichloromethane, chloroform and trichlene; aromatic solvents such as xylene, toluene and benzene; and saturated hydrocarbons such as decane, octane, heptane, hexane, cyclohexane and pentane. Solvent or
Dioxane, tetrahydrofuran, diethyl ether,
Solvents without active hydrogen, such as ether solvents such as dimethyl ether and ethylene glycol dimethyl ether, ketone solvents such as diethyl ketone, methyl ethyl ketone and dimethyl ketone, and ester solvents such as ethyl acetate and methyl acetate are effectively used. .

However, the production without using a solvent is advantageous in terms of production cost since the step of removing the solvent is unnecessary, and is more preferable because there is little risk of environmental pollution. The amount of the polyisocyanate compound used in the reaction is such that the ratio (NCO / OH) of the number of moles of NCO groups of the polyisocyanate compound to the total number of moles of OH groups of the polyalkylene glycol and the comb-shaped hydrophobic diol is 0. .7
To 1.3 mol / mol, more preferably 0.8 to 1.05
Mol / mol, more preferably 0.95 to 0.995 mol / mol. When the value of NCO / OH is in the range of 0.7 to 1.3 mol, the average molecular weight of the product is sufficiently large,
The ability as a thickener is sufficient, and the solubility of the product is not reduced by a crosslinking reaction or the like.

However, when water is contained in the polyalkylene glycol or the comb-shaped hydrophobic diol, the amount of the above-mentioned polyisocyanate compound needs to be used in excess of the amount by which the polyisocyanate is decomposed by the water. Therefore, it is more preferable to use a sufficiently dried raw material.
If possible, the water content of the raw material is preferably 5,000 ppm or less. It is more preferably at most 1,000 ppm, still more preferably at most 200 ppm.

The amount of the comb-shaped hydrophobic diol used in the reaction is as follows:
Depending on the molecular weight of the polyalkylene glycol and the number of carbon atoms in the hydrophobic group of the comb-shaped hydrophobic diol, the number of moles of the comb-shaped hydrophobic diol is 0.01 to 1 mole per mole of the polyalkylene glycol (x is 0.01 to 0). .5) is appropriate. When the number of moles of the comb-shaped hydrophobic diol is in this range, a sufficient thickening effect as a use of the mortar thickener and a sufficient hydrophobic effect are provided, and the solubility is not reduced. preferable. The numerical value in parentheses indicates the value of x in the general formula (8).

The reaction temperature varies depending on the type and amount of the catalyst used, but is preferably from 50 to 180 ° C. More preferably 60 to 150 ° C, further preferably 80 to 12 ° C.
It is in the range of 0 ° C. When the reaction temperature is in the range of 50 to 180 ° C., the reaction rate is high and economical, and the product is not thermally decomposed. The reaction time varies depending on the type and amount of the catalyst used, the reaction temperature and the like, and is not particularly limited, but about 1 minute to 10 hours is sufficient.

The reaction pressure is not particularly limited. The reaction can be carried out under normal pressure, reduced pressure or increased pressure. More preferably, the reaction is carried out under normal pressure or weak pressure. The product after the reaction is taken out of the reaction vessel and pulverized to about 1 mm or less. As the pulverizing method, a device usually used for pulverizing a polymer having a relatively low melting point, such as a freezing pulverizer, an impact pulverizer or a grinder pulverizer, can be used.

It is preferable that most of the particle diameter of the powder is 1 mm or less. More preferably, the particles having a particle diameter of 1 mm or less are 95% by weight or more and the particle diameter is 600% or less.
The particles having a particle size of μm or less account for 50% by weight or more. More preferably, the particles having a particle diameter of 1 mm or less are 99% by weight or more, and the particles having a particle diameter of 400 μm or less are 50% by weight or more. When the number of particles having a particle diameter exceeding 1 mm is small, the solubility is improved.

The mortar thickener includes antioxidants,
Additives such as a stabilizer, an anti-blocking agent and a grinding aid may be added. Hereinafter, the aqueous solution viscosity of the polymer will be described. The polymer used in the present invention has a viscosity of 2% aqueous solution at 20 ° C. of 10 mPa · s to 300,000.
mPa · s. When the 2% aqueous solution viscosity is within this range, the viscosifying effect on the mortar is sufficient and appropriate, and the workability of the mortar is enhanced. More preferably, a 2% aqueous solution of 2%
A polymer having a viscosity at 0 ° C. of 50 to 100,000 mPa · s is used. The 2% aqueous solution of the polymer is obtained by dissolving 2 g of the polymer in 98 g of distilled water.

For measuring the viscosity of the aqueous solution, a rotary cylindrical viscometer, which is generally widely used, is used. 20 ° C for viscosity measurement
The temperature is controlled using a 2% aqueous solution, and the measurement is performed under the condition that the rotational speed of the cylinder of the viscometer is 6 rpm. However, for a sample whose aqueous solution viscosity exceeds 100,000 mPa · s, the number of rotations is 4 r.
Measure under pm conditions. Hereinafter, a method of using the thickener comprising the polymer as a thickener for mortar will be described.

The dry mortar composition includes (1) hydraulic inorganic powders such as portland cement, alumina cement and calcium silicate, (2) sand, fly ash, silica fume, perlite, pumice, crushed foamed concrete,
A dry mortar can be obtained by mixing and thoroughly mixing a crushed foam plastic, fine aggregate such as hollow polystyrene particles, and (3) the thickener according to the present invention. However, the fine aggregate of (2) is not always essential.

In addition to the above-mentioned components, other components conventionally used in mortar preparation can be added, if necessary. For example, various water reducing agents, re-emulsifiable resin powders, antifoaming agents, fibers, and the like. When these are powders (solids), they can be mixed with the above components (1), (2) and (3) to obtain dry mortar. It is appropriate that the amount of the thickener is about 0.01 to 5% by weight / wt. More preferably, the content is 0.1 to 1% by weight.

When the amount of the thickener is in the range of 0.01 to 5% by weight, the effect of the thickener is sufficiently exhibited, and the necessary and sufficient amount for obtaining the desired effect is obtained. However, it is preferable from an economic viewpoint. The amount of the hydraulic inorganic powder also depends on the use of the mortar, the amount of fine aggregate used, and the like. For example, 99.99 relative to the total dry mortar.
About 10 to 10% by weight, more preferably about 80 to
20% w / w.

The amount of the fine aggregate depends on the use of the mortar and the type of the fine aggregate, but is, for example, about 89.99 to 0% by weight / wt% based on the total dry mortar. Preferably it is 80 to 20% w / w. Water is added to the dry mortar so as to have a necessary water / cement ratio (weight ratio of water to hydraulic inorganic powder), and the mortar can be kneaded well.

An appropriate water / cement ratio is about 0.2-1. More preferably, it is 0.3 to 0.7. When the water / cement ratio is in the range of 0.2 to 1, the amount of water necessary for the hydration reaction of the cement is secured, and the strength after hardening is sufficient. A feature of the thickener of the present invention is that it has the same thickening action as a thickener composed of cellulose ethers, though it has less settling delay than a thickener composed of cellulose ethers.

The reason why the thickener of the present invention exhibits such excellent properties is not fully understood at the present time, but can be inferred as follows. The mechanism by which the cellulose ethers thicken in the mortar is a hydrophobic group such as a methyl group substituting a part of the hydroxyl group of the cellulose unit,
It is presumed that the polymer interacts hydrophobically in water to form an association between the polymer chains via the hydrophobic group.

On the other hand, the polymer used in the present invention has a comb-like hydrophobic group (a kind of hydrophobic group aggregate) derived from the comb-like hydrophobic diol as a raw material in the polymer chain, and a small amount of the hydrophobic group. Can effectively form an aggregate. It is notable that a polymer having a hydrophobic group aggregate formed by gathering several hydrophobic groups forms a network structure in an aqueous solution by the association of the hydrophobic group aggregate, and as a result, the viscosity of the aqueous polymer solution is improved. It is also described in detail in JP-A-59-78226.

The mechanism by which cellulose ethers delay the setting of mortar has not been fully elucidated at present, but (a) the hydroxyl groups of the cellulose unit bind to calcium in the mortar and the hydration reaction of cement (B) It is estimated that cellulose ethers are adsorbed on cement particles by a hydrophobic group such as a methyl group to delay the hydration reaction.

On the other hand, it is considered that the polymer used in the present invention does not have a hydroxyl group in the repeating unit of the polymer and does not bind to calcium. Also, since the amount of the hydrophobic group is small, the amount adsorbed on the cement surface is also small, and as a result, the setting delay of the mortar is considered to be shorter than that of cellulose ethers. Here, the difference between the polymer having a hydrophobic group aggregate disclosed in JP-A-59-78226 (hereinafter referred to as a polymer in the literature) and the polymer used in the present invention is described. Is described.

In the literature, a hydrophobic group is formed by adding a few molecules of an oxirane-containing compound such as 1,2-epoxyalkane to a low molecular weight diol such as diethylene glycol (hereinafter referred to as a spacer) using an acid catalyst or an alkali catalyst. It has been shown to obtain diols having aggregates. As another method, it is also disclosed that a diol obtained by adding two molecules of glycidyl ether to methylamine is reacted with diisocyanate to obtain a diisocyanate or a diol having a hydrophobic group aggregate.

However, according to these methods, it is not possible to obtain a hydrophobic group aggregate in which a specific number of hydrophobic groups are aggregated, but in practice, it is only possible to obtain a mixture of several types of hydrophobic group aggregates having different numbers of hydrophobic groups. Did not. This is because the hydroxyl groups generated by the reaction of the spacer glycols with the oxirane-containing compound further react with the oxirane-containing compound, so that various diols having different numbers of added oxirane-containing compounds to the spacer are simultaneously formed. is there. Similarly, when a diol is bonded with a diisocyanate, a mixture of several types of diisocyanates and diols having different numbers of hydrophobic groups is generated.

For this reason, the polymer in the literature is considered to be a polymer having a plurality of hydrophobic group aggregates having different numbers of hydrophobic groups in the molecule. A thickener using a polymer having a plurality of hydrophobic group aggregates having different numbers of hydrophobic groups in the molecule tends to cause a decrease in the solubility of the thickener in the mortar and a delay in setting of the mortar. Because the number of hydrophobic groups in the hydrophobic group aggregate has a distribution, it is inevitable that the hydrophobic group aggregate with a higher number of hydrophobic groups than necessary is included in the polymer at a certain ratio. It is presumed that the hydrophobic group aggregate having too high hydrophobicity causes a decrease in solubility and a delay in setting of mortar.

On the other hand, the polymer of the present invention is characterized in that it contains only hydrophobic group aggregates having substantially the same number of hydrophobic groups, and it is possible to avoid the adverse effects of a hydrophobic group aggregate having too high a hydrophobicity. As has been shown, the mortar thickener according to the present invention reduces the setting retardation, which is a drawback of the existing thickeners, and provides the same thickening effect.
It can be used for a wide range of mortars, such as tile bonding mortar, masonry mortar, spray mortar, repair mortar, base mortar, finishing mortar, etc., which improves the efficiency of construction and civil engineering processes, improves reliability, and reduces costs. Can greatly contribute to

[0122]

EXAMPLES Hereinafter, the present invention will be further described with reference to Examples, but it should be understood that the present invention is not limited to these Examples. (Example of synthesis of comb-shaped hydrophobic diol)

[0123]

Example 1 A magnetic stirrer, a thermometer and a dropping funnel were placed in a 500 ml round bottom flask, and 64.6 g of 2-ethylhexylamine (Kanto Chemical) was charged.
The atmosphere in the flask was replaced with nitrogen. The flask was heated to 60 ° C. in an oil bath, and 2-ethylhexyl glycidyl ether (manufactured by Asahi Denka Co., Ltd.,
Adekaglycylol ED518, epoxy value 220) 2
20.0 g was added dropwise over 40 minutes. After the addition, the temperature of the oil bath was raised to 80 ° C., and the flask was heated for 10 hours. Subsequently, the temperature of the oil bath was raised to 120 ° C., and a small amount of unreacted substances was distilled off under reduced pressure using a vacuum pump at a degree of vacuum of 3 mmHg. 2-ethylhexylamine 1
A comb-shaped hydrophobic diol 1 (average molecular weight from OH number: 532) to which 2-ethylhexyl glycidyl ether was added at a ratio of 2 mol per mol was obtained in a yield of 90%.

[0124]

Example 2 A magnetic stirrer, a thermometer and a dropping funnel were set in a 500 ml round bottom flask, and
93.7 g of (dodecyloxy) -1-propylamine (manufactured by Koei Chemical Industry Co., Ltd.) was charged, and the atmosphere in the flask was replaced with nitrogen. Heat the flask to 60 ° C in an oil bath,
With stirring, 188.0 g of 2-ethylhexyl glycidyl ether (Denacol EX-121, epoxy value 188) manufactured by Nagase Kasei Kogyo Co., Ltd.
It was added dropwise over 0 minutes. After the addition, the temperature of the oil bath was raised to 80 ° C., and the flask was heated for 10 hours. Subsequently, the temperature of the oil bath was raised to 120 ° C., and a small amount of unreacted substances was distilled off under reduced pressure using a vacuum pump at a degree of vacuum of 3 mmHg. Comb-shaped hydrophobic diol 2 (O) in which 2-ethylhexyl glycidyl ether is added at a ratio of 2 mol per mol of 3- (dodecyloxy) -1-propylamine
The average molecular weight from H value 620) was obtained in a yield of 85%. (Synthesis example of polymer) Hereinafter, synthesis examples of the polymer using the hydrophobic diols of Examples 1 and 2 will be described, but the present invention is not limited to the following examples.

[0125]

Example 3 Commercially available polyethylene glycol (PEG # 600) was placed in a 1000 ml SUS separable flask.
0, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 8,63
0) was charged and melted at 150 ° C. under a nitrogen seal. This was stirred under reduced pressure (3 mmHg) for 3 hours.
Dried for hours. The residual moisture was 200 ppm.
The temperature was lowered to 70 ° C., and the inside of the flask was filled with 1 atm of nitrogen. 300 ppm of BHT (di-tert-butylhydroxytoluene) was added as an antioxidant. While stirring the inside of the flask, 1.70 g of the comb-shaped hydrophobic diol 1 obtained in Example 1 and 4.35 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged (N
(CO / OH = 0.98 mol / mol). D as catalyst
When 0.05 g of BTDL was added, the viscosity rapidly increased in about 10 minutes. The stirring was stopped and the reaction was carried out at 70 ° C. for 2 hours. 1
The temperature was raised to 20 ° C. and kept constant for 30 minutes, after which the product was removed from the flask. The melting point of the product is about 6
It was 0 ° C.

The product taken out was cut into small pieces and allowed to cool. This was cooled with liquid nitrogen and pulverized with a small impact-type electric mill. The pulverized product was sieved to obtain a powder having a particle diameter of 600 μm or less as a mortar thickener. The average particle size of the powder was 400 μm. The viscosity of a 2% aqueous solution of this polymer was 15,000 mPa · s (15,000 centipoise).

Here, a method of measuring the viscosity of a 2% aqueous solution will be described. 2 g of the polymer was dissolved in 98 g of distilled water to obtain a 2% aqueous solution. This aqueous solution was placed in a beaker, immersed in a constant temperature water bath maintained at 20 ° C., and a rotary cylindrical viscometer (TOKIME) was used.
Using a C type BL viscometer) and the rotor rotation speed is 6r
The viscosity was measured in pm. However, the viscosity of the aqueous solution is 100,000 mP
For samples exceeding a · s, use TOKIMEC B
Using an H-type viscometer, the viscosity was measured at a rotor rotation speed of 4 rpm.

[0128]

Example 4 200 g of commercially available PEG # 6000 (manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight: 8,630) was charged into a 1000 ml SUS separable flask and melted at 150 ° C. under a nitrogen seal. This was dried under reduced pressure (3 mmHg) for 3 hours while stirring. The residual moisture was 200 ppm. The temperature was lowered to 70 ° C., and the inside of the flask was filled with 1 atm of nitrogen. B as antioxidant
HT (di-tert-butylhydroxytoluene)
00 ppm was added. While stirring the inside of the flask, 1.90 g of the comb-shaped hydrophobic diol 1 obtained in Example 1 and 4.41 g of hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.) were charged (NCO / OH = 0.98 mol). /
mol). When 0.05 g of DBTDL was added as a catalyst, the viscosity rapidly increased in about 10 minutes. Stop stirring, 70 ° C
For 2 hours. The temperature was raised to 120 ° C. and kept constant for 30 minutes, after which the product was removed from the flask. The melting point of the product was about 60 ° C.

The product taken out was cut into small pieces and allowed to cool. This was cooled with liquid nitrogen and pulverized with a small impact-type electric mill. The pulverized product was sieved to obtain a powder having a particle diameter of 600 μm or less as a mortar thickener. The average particle size of the powder was 400 μm. The viscosity of a 2% aqueous solution of this polymer measured by the same method as in Example 3 was 48,000.
mPa · s (48,000 centipoise).

[0130]

Example 5 200 g of commercially available PEG # 6000 (manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 8,630) was charged into a 1000 ml SUS separable flask and melted at 150 ° C. under a nitrogen seal. This was dried under reduced pressure (3 mmHg) for 3 hours while stirring. The residual moisture was 200 ppm. The temperature was lowered to 70 ° C., and the inside of the flask was filled with 1 atm of nitrogen. B as antioxidant
HT (di-tert-butylhydroxytoluene)
00 ppm was added. While stirring the inside of the flask, 1.208 g of the comb-shaped hydrophobic diol 2 obtained in Example 2 and hexamethylene diisocyanate (manufactured by Tokyo Chemical Industry Co., Ltd.)
Was charged (NCO / OH = 0.995 m
ol / mol). When 0.05 g of DBTDL was added as a catalyst, the viscosity rapidly increased in about 10 minutes. Stop stirring,
The reaction was performed at 70 ° C. for 2 hours. Raise the temperature to 120 ° C and 3
The temperature was kept constant for 0 minutes, after which the product was removed from the flask. The melting point of the obtained product was about 60 ° C.

The product taken out was cut into small pieces and allowed to cool. This was cooled with liquid nitrogen and pulverized with a small impact-type electric mill. The pulverized product was sieved to obtain a powder having a particle diameter of 600 μm or less as a mortar thickener. The average particle size of the powder was 400 μm. The 2% aqueous solution viscosity measured by the same method as in Example 3 was 67,000 mPa · s.

[0132]

Examples 6 to 14 Polymers were synthesized in the same manner as in Example 5 except that the amounts of the comb-shaped hydrophobic diol 2 and hexamethylene diisocyanate were different. The viscosity of a 2% aqueous solution of the obtained polymer was measured in the same manner as in Example 3. Table 1 summarizes the blending ratio and the viscosity of the obtained polymer in a 2% aqueous solution in each example.

[0133]

[Table 1]

(Production example of mortar using mortar thickener) Examples of production of mortar using mortar thickeners of Examples 3, 4 and 11 to 14 are shown below. It is not limited to the following example.

[0135]

Example 15 In a mortar mixer, 400 g of portland cement, 400 g of standard sand, and the thickener 1.6 of Example 3 were used.
g was added and stirred and mixed for 10 minutes to obtain a dry mortar. 180 g of water (water / cement ratio 0.45) was added to the dry mortar, and the mixture was stirred and mixed for 5 minutes to obtain a thickened mortar.

The viscosity of the mortar at room temperature (21 to 22 ° C.) was measured using a rotary cylindrical viscometer (B8M manufactured by TOKIMEC).
), The rotation speed of the rotor is 0.6 to 60 rpm
It measured in the range of. The composition of the mortar is shown in Table 2, and the relationship between the viscosity of the mortar and the rotation speed of the rotor used for the measurement is shown in FIG.

[0137]

Example 16 The same as Example 15 except that the thickener prepared in Example 4 was used as the thickener. The composition of the mortar is shown in Table 2, and the relationship between the viscosity of the mortar and the rotation speed of the rotor used for the measurement is shown in FIG.

[0138]

Examples 17 to 20 The same as Example 15 except that the thickeners prepared in Examples 11 to 14 were used as the thickener. The composition of the mortar is shown in Table 2, and the relationship between the viscosity of the mortar and the rotation speed of the rotor used for the measurement is shown in FIG.

[0139]

Comparative Example 1 Same as Example 15 except that the thickener was omitted from Example 15. Table 2 shows the composition of the mortar, and FIGS. 1 and 2 show the relationship between the viscosity of the mortar and the rotation speed of the rotor used for the measurement.

[0140]

Comparative Example 2 A mortar using the same amount of methylcellulose in place of the thickener used in Example 15 was produced.
The same viscosity measurement as in Example 5 was performed. As methylcellulose, Hi-Metroze 90SH-15 manufactured by Shin-Etsu Chemical Co., Ltd., having a viscosity of a 2% aqueous solution substantially equal to that of the thickener prepared in Example 3.
000 (2% aqueous solution having a viscosity of 15,000 mPa · s) was used.

Table 2 shows the composition of the mortar, and FIGS. 1 and 2 show the relationship between the viscosity of the mortar and the rotation speed of the rotor used for the measurement.

[0142]

[Table 2]

As shown in FIGS. 1 and 2, the viscosity decreased as the number of rotations increased in all the examples, which reflects the thixotropy of the mortar.
It can be seen that the use of the thickener increased the mortar viscosity. A high viscosity at a low rotation speed (low shear force) has an effect of suppressing the flow of the mortar after construction and preventing dripping. Further, the fact that the viscosity decreases at a high rotation speed (high shearing force) is a necessary property for good mortar removal of the mortar.

As shown in FIG. 1, the thickener prepared in Example 3 and the thickener used in Comparative Example 2 exhibited almost the same thickening effect in mortar. This is thought to be due to the fact that the 2% aqueous viscosities of the two are almost equal. The mortar using the thickener prepared in Example 4 showed higher viscosity. This is thought to be because the viscosity of the 2% aqueous solution of the thickener was higher than the former two thickeners.

Further, as shown in FIG. 2, the thickener produced in Example 11 and the thickener used in Comparative Example 2 also exhibited almost the same thickening effect in the mortar. Surprisingly, the mortars using the thickeners prepared in Examples 12 and 13 also showed high mortar viscosities comparable to Comparative Example 2. This indicates that the thickener of the present invention effectively exhibits a thickening effect in mortar.

By increasing or decreasing the amount of addition, the mortar viscosity also increases or decreases. When a thickener having a higher aqueous solution viscosity of 2% is used, the same amount of thickening effect as in the above embodiment can be obtained by reducing the amount of addition. be able to. As the mortar thickener, various cellulose ethers having different aqueous solution viscosities depending on the application are used. According to the present invention, a 2% aqueous solution having a viscosity of 10 to 300,000 mPa · s is obtained. In almost all applications,
The thickener of the present invention can replace an existing thickener such as methylcellulose. (Delay in setting of mortar) As a problem when cellulose ethers are used as a thickener, setting of mortar is delayed,
It is widely known that the development of the initial strength of the mortar is delayed.

[0147]

Examples 21 to 22 and Comparative Examples 3 to 4 Example 15,
The setting start time of the mortar of Example 17, Comparative Example 1 and Comparative Example 2 was measured. The measurement was carried out using a Vicat needle device manufactured by Maruto Co., Ltd. in accordance with JIS R5201. The mortar was filled in a container having a depth of 40 mm, a predetermined starting needle was dropped on the mortar by a predetermined method, and the position where the needle stopped was read using a scale attached to the needle. The measurement is performed at intervals of 30 minutes from the time when water is added to the mortar. If the position where the needle stops is 1 mm or more from the bottom of the container, it is considered that the setting has started,
The time from the time when the water was added to the mortar was defined as the initial setting time. The difference from the starting time of Comparative Example 1 was defined as the delay time. Also, three hours after the water was added to the mortar, the presence or absence of water seeping (breathing) on the mortar surface was visually checked. Table 3 shows the results.

[0148]

[Table 3]

The mortars of Examples 15 and 17 had a shorter setting delay than those of Comparative Example 2, and the breathing as seen in Comparative Example 1 was sufficiently suppressed. Thickeners of the present invention, despite having less retardation of setting than commercially available thickeners, show the same thickening action as commercially available thickeners, the degree of thixotropy required for mortar work, It turns out that it gives water retention. (Solubility of mortar thickener)

[0150]

Example 23 The dissolution rate of the thickener obtained in Example 11 into mortar was examined. In this method, a mortar having the same composition as in Example 17 is kneaded with a mixer for 5 minutes, and the time until the mortar thickens and becomes almost constant is measured with a stopwatch.

As a result, the thickener was almost dissolved within one minute, the mortar was in a constant state, and it was shown that the polymer itself had very good solubility in the mortar.

[0152]

The thickener for mortar according to the present invention reduces the setting delay, which is a drawback of the existing thickener, and gives the mortar a thickening effect equivalent to that of the existing thickener. It can greatly contribute to efficiency of processes using mortar such as civil engineering, improvement of reliability, and cost reduction.

[Brief description of the drawings]

FIG. 1 is a diagram showing a thickening effect of a thickener according to the present invention on mortar.

FIG. 2 is a diagram showing a thickening effect of a thickener according to the present invention on mortar.

[Explanation of symbols]

 1 Viscosity of the mortar of Example 15 2 Viscosity of the mortar of Example 16 3 Viscosity of the mortar of Comparative Example 1 4 Viscosity of the mortar of Comparative Example 2 5 Viscosity of the mortar of Example 17 6 Viscosity of the mortar of Example 18 7 Viscosity of mortar of Example 19 8 Viscosity of mortar of Example 20

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor 580-32 32 Takuji, Nagaura-shi, Sodegaura-shi, Chiba Pref. Mitsui Chemicals, Inc. F-term (reference) 4G012 PB21 PB22 4J034 BA07 BA08 CA04 CB03 CC05 DA01 DB04 DC50 DG02 DG03 DG04 DG05 HA01 HA07 HA11 HC03 HC12 HC13 HC16 HC17 HC22 HC52 HC64 HC67 JA01 JA02 KA01 KC08 KC17 KC18 KD11 KD12 QC04 RA10

Claims (9)

[Claims] 1. A compound of the general formula (1)And a repeating unit (U-1) represented by the general formula (2):Consisting of a repeating unit (U-2) represented by
Molar ratio (U-1) is 0.5 or more and 0.99 or less
And the molar ratio of the repeating unit (U-2) is 0.01 or more
0.5 or less, and the viscosity of the 2% aqueous solution at 20 ° C. is 10
mPa · s to 300,000 mPa · s
Novel thickener for mortar made of polymer. Where A is
HO-A-OH has a hydroxyl group at least at both terminals and
Water-soluble polya having a number average molecular weight of 400 to 100,000
A divalent group that is a alkylene polyol (Compound A),
B is a polyisocyanate having a total carbon number of 3 to 18 in OCN-B-NCO.
Polyisocyanates selected from the group consisting of socyanates
Is a divalent group which is a salt compound (compound B), and D is HO
-D-OH is represented by the general formula (3):(However, R¹Is a hydrocarbon group having 1 to 20 carbon atoms.
You. Also R^TwoAnd R^ThreeIs a hydrocarbon group having 4 to 21 carbon atoms
It is. The hydrocarbon group R¹, R^TwoAnd R^ThreeHydrogen in
Part or all of it with fluorine, chlorine, bromine or iodine
May be replaced by R^TwoAnd R^ThreeAre the same but different
Is also good. Y and Y ′ are hydrogen, methyl or CH_Two
Cl and Y and Y ′ may be the same or different
No. Z and Z ′ are oxygen, sulfur or CH_TwoIn the base
Z and Z ′ may be the same or different. And n is
When Z is oxygen, it is an integer of 0 to 15, and Z is sulfur or
Is CH_TwoIn the case of a group, it is 0. Also, n 'is a place where Z' is oxygen.
Is an integer of 0 to 15, and Z ′ is sulfur or CH_Twobase
In this case, it is 0, and n and n 'may be the same or different
I), general formula (4)(However, in the formula, R^FourIs a hydrocarbon group having 1 to 20 carbon atoms
It is. Also R^FiveAnd R⁶Is a hydrocarbon having 4 to 21 carbon atoms
Elementary group. The hydrocarbon group R^Four, R^FiveAnd R⁶In
Part or all of hydrogen is fluorine, chlorine, bromine or iodine
May be substituted with^FiveAnd R⁶Are the same but different
May be. X, X ′ and X ″ have 2 to 1 carbon atoms.
X, X ′ and X ″ are the same
Or different. The alkylene
Some of the hydrogens of the group may be alkyl groups, chlorine or alkyl chlorides.
And may be substituted with a phenyl group. Z and Z 'are acids
Elemental, sulfur or CH_TwoZ and Z 'are the same but different
It may be. Also R⁷Is Al having 2 to 10 carbon atoms
A kylene group, and k is an integer of 0 to 15. And n is
When Z is oxygen, it is an integer of 0 to 15, and Z is sulfur or
Is CH_TwoIn the case of a group, it is 0. Also, n 'is a place where Z' is oxygen.
Is an integer of 0 to 15, and Z ′ is sulfur or CH_Twobase
In this case, it is 0, and n and n 'may be the same or different
No. ) Or general formula (5)(However, R⁸And R⁹Is R⁸And R⁹Has a total carbon number of 2
To 20 hydrocarbon groups. Also R^TenAnd R¹¹Is carbon
It is a hydrocarbon group having a number of 4 to 21. The hydrocarbon group R
⁸, R⁹, R^TenAnd R¹¹Some or all of the hydrogen
It may be substituted by nitrogen, chlorine, bromine or iodine. R
⁸And R⁹May be the same or different. R ^TenAnd R¹¹Is the same
It may be the same or different. Also R¹²Has 2 to 7 carbon atoms
Is an alkylene group. Y and Y ′ are hydrogen, methyl
Or CH_TwoCl and Y and Y 'are the same or different
It may be. Z and Z ′ are oxygen, sulfur or
CH_TwoAnd Z and Z ′ may be the same or different
No. N is an integer of 0 to 15 when Z is oxygen;
Z is sulfur or CH_TwoIt is 0 for a group. And n '
When Z 'is oxygen, it is an integer of 0 to 15, and Z' is sulfur or
Or CH_Two0 in the case of a group, and n and n 'are the same or different
Hydrophobic diol represented by the formula
Compound 2) is a divalent group. 2. The compound A has a number average molecular weight of 1,000-2.
The thickener for mortar made of the polymer according to claim 1, which is a polyethylene glycol of 000. 3. The mortar thickener comprising a polymer according to claim 1, wherein the compound B is a chain aliphatic diisocyanate or a cycloaliphatic diisocyanate. 4. The compound according to claim 1, wherein the compound B is hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate or norbornane diisocyanate methyl. Thickener for mortar consisting of high polymer. 5. A compound represented by the general formula (4)
Has the following general formula (4a):(However, R^FourIs a hydrocarbon group having 1 to 20 carbon atoms.
You. Also R^FiveAnd R⁶Is a hydrocarbon group having 4 to 21 carbon atoms
It is. The hydrocarbon group R^Four, R^FiveAnd R⁶Hydrogen in
Part or all of it with fluorine, chlorine, bromine or iodine
May be replaced by R^FiveAnd R⁶Are the same but different
Is also good. Y, Y ′ and Y ″ are hydrogen, methyl or
CH_TwoCl and Y and Y ′ may be the same or different
Good. Z and Z ′ are oxygen, sulfur or CH_TwoIn the base
Z and Z ′ may be the same or different. Also R⁷Is
An alkylene group having 2 to 4 carbon atoms, and k is 0 to 15
It is an integer. And n is an integer of 0 to 15 when Z is oxygen.
And Z is sulfur or CH _TwoIn the case of a group, it is 0. Ma
N ′ is an integer of 0 to 15 when Z ′ is oxygen;
Is sulfur or CH_Two0 in the case of a group, and n and n ′ are the same
Or may be different).
A thickener for mortar according to any of the above. 6. The compound D is represented by the general formula (6): (However, R ¹³ is a linear or branched alkyl group having 4 to 18 carbon atoms. R ¹⁴ and R ¹⁵ are a linear or branched alkyl group having 4 to 18 carbon atoms.) . the mortar thickening agent comprising a polymer according to any one of the alkyl groups R ¹⁴ and R ¹⁵ to the claims 1 a comb-shaped hydrophobic diol represented by may) be the same or different 4. 7. A compound D represented by the general formula (9):(However, in the formula, R¹⁶Is an alkyl group having 1 to 18 carbon atoms
It is. Also R¹⁷And R¹⁸Is carbonized with 4 to 21 carbon atoms
A hydrogen group,¹⁷And R¹⁸Is the same. Also R ¹⁹Is
1,2-ethylene group, 1,3-propylene group or 1,
4-butylene group. ) Comb-shaped hydrophobic dial
The polymer according to any one of claims 1 to 5, wherein the polymer is
A thickener for mortar. 8. A dry mortar composition comprising at least hydraulic inorganic powder and the mortar thickener according to any one of claims 1 to 7. 9. A mortar composition comprising at least hydraulic inorganic powder, water and the mortar thickener according to any one of claims 1 to 7.