JP6442666B2 - Anti-whitening agent for cement composition - Google Patents

Description

  The present invention relates to an anti-whitening agent for cement compositions.

  Whiteness of hardened body of cement composition (Calcium hydroxide contained in the composition or hardened body dissolves in water and migrates to the surface of the hardened body during or after hardening of the cement composition. To prevent poor appearance (color cement composition is more conspicuous than normal cement composition) due to reaction and the phenomenon that water-insoluble calcium carbonate precipitates) and problems such as peeling of finishing materials such as paint. Furthermore, “a cement admixture characterized by containing an alkali salt of a fatty acid, a water-soluble solvent, and water” is known (Patent Document 1).

Japanese Patent Laid-Open No. 11-60301

Conventional anti-whitening agents (fatty acid derivatives) for cement compositions have insufficient whiteness prevention properties.
That is, an object of the present invention is to provide a cement composition anti-wrinkle agent having excellent white-wax-proofing properties.

  The gist of the anti-whitening agent for cement composition of the present invention is that it contains the polyoxyalkylene compound (X) represented by the formula (1).

R ¹ —N {(— AO) n—H} ₂ (1)

R ¹ is an alkyl group having 10 to 18 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, N represents a nitrogen atom, H is a hydrogen atom, n is an integer of 2 to 15.

  Moreover, the characteristics of the powder white-fade inhibitor for cement composition of the present invention are selected from the group consisting of the polyoxyalkylene compound (X) represented by the formula (1), silicon oxide, aluminum oxide, calcium carbonate and magnesium carbonate. The gist of the present invention is that it comprises at least one kind of porous powder (Y).

  The whitening prevention agent for cement composition and the whitening prevention agent for cement composition of the present invention exhibit superior whitening prevention properties compared to conventional whitening prevention agents.

2 is a photograph of the surface of a hardened cement for evaluation cured using the anti-whitening agent (1) for a cement composition of the present invention obtained in Example 1. 2 is a photograph of the surface of a hardened cement for evaluation cured using the comparative whitening inhibitor for cement composition (C1) obtained in Comparative Example 1. FIG.

Among the alkyl group, alkenyl group, cycloalkyl group and aryl group (R ¹ ), the alkyl group includes an alkyl group having 4 to 18 carbon atoms, and includes n-butyl, n-pentyl, n-hexyl, n- Heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n- Examples include octadecyl and isooctadecyl.

  Examples of the alkenyl group include alkenyl groups having 4 to 18 carbon atoms, and include butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl and octadecenyl. .

  The cycloalkyl group includes a cycloalkylene group having 4 to 15 carbon atoms, and examples thereof include cyclobutyl, cyclopentyl, cyclohexyl, dicyclohexyl, methylcyclohexyl, trimethylcyclohexyl, and nonylcyclohexyl.

  The aryl group includes an aryl group having 6 to 15 carbon atoms, and examples thereof include phenyl, tolyl, benzyl, xylyl, nonylphenyl and naphthyl.

Of these R ¹ , an alkyl group and a cycloalkyl group are preferable, and an alkyl group is more preferable.

  Examples of the oxyalkylene group (AO) having 2 to 4 carbon atoms include oxyethylene, oxypropylene, and oxybutylene.

All of the oxyalkylene groups (AO) contained in (-AO) n may be the same or different. From the viewpoint of preventing white flower, when R ¹ is an alkyl group having 12 to 18 carbon atoms, oxyethylene alone is preferable, and R ¹ is an alkyl group, alkenyl group, cycloalkyl group or aryl group having 4 to 11 carbon atoms. In this case, a mixture of oxyethylene and oxypropylene and / or oxybutylene is preferred.

  When the mixture of oxypropylene and / or oxybutylene and oxyethylene is included, the content ratio (mol%) of oxyethylene is preferably 50 to 90, more preferably 60 to 90, based on the total number of moles of oxyalkylene. Especially preferably, it is 60-80. In this case, it is preferable that oxypropylene and / or oxybutylene is located on the nitrogen atom N. That is, it is preferable that oxyethylene is bonded to a terminal portion away from the nitrogen atom N. Further, when a plurality of types of oxyalkylene groups are included, the bonding mode may be any of a block shape, a random shape, and a mixture thereof, but preferably includes at least a block shape.

  n is preferably an integer of 2 to 15, more preferably an integer of 3 to 12, and particularly preferably an integer of 4 to 10. When it is in this range, the whitening prevention property is further improved.

  As the polyoxyalkylene compound (X) represented by the formula (1), an amine having any one of an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group (primary amine; a1 to a4) 1 mol And a polyoxyalkylene compound having a structure produced by a chemical reaction of 4 to 30 mol of alkylene oxide (a5) having 2 to 4 carbon atoms.

  Examples of amines having an alkyl group include alkylamines (a1) having 4 to 18 carbon atoms, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and 2-ethylhexyl. Amines, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, isotridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine and n-octadecylamine etc. are mentioned.

  Examples of the amine having an alkenyl group include alkenylamines having 4 to 18 carbon atoms (a2), butenylamine, pentenylamine, hexenylamine, heptenylamine, octenylamine, nonenylamine, decenylamine, undecenylamine, dodecenylamine, tridecenylamine, tetra Examples include decenylamine, pentadecenylamine, hexadecenylamine, heptadecenylamine, and octadecenylamine.

  Examples of amines having a cycloalkyl group include cycloalkylamines (a3) having 4 to 15 carbon atoms, such as cyclobutylamine, cyclopentylamine, cyclohexylamine, dicyclohexylamine, methylcyclohexylamine, trimethylcyclohexylamine, and nonylcyclohexylamine. Can be mentioned.

  Examples of the amine having an aryl group include arylamine (a4) having 6 to 15 carbon atoms, and examples include phenylamine (aniline), toluidine, benzylamine, xylidine, nonylphenylamine, and naphthylamine.

  Among these, alkylamine (a1) and cycloalkylamine (a3) are preferable, more preferably alkylamine (a1), particularly preferably n-decylamine, n-undecylamine, n-dodecylamine, n-tridecyl. An amine is n-tetradecylamine.

  Examples of the alkylene oxide (a5) having 2 to 4 carbon atoms include ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and mixtures thereof. Among these, from the viewpoint of whitening prevention, when the primary amine is an amine having an alkyl group and the alkyl group has 12 to 18 carbon atoms, EO is preferably used alone. When the secondary amine is an amine having an alkyl group (4 to 11 carbon atoms), an alkenyl group, a cycloalkyl group or an aryl group, it is preferable to use EO with PO and / or BO.

  When a mixture of PO and / or BO and EO is included, the content ratio (mol%) of EO is preferably 50 to 90, more preferably 60 to 90, particularly preferably based on the total number of moles of alkylene oxide. 60-80. In this case, it is preferable that PO and / or BO react with the nitrogen atom N. That is, it is preferable that EO is bonded to the terminal portion away from the nitrogen atom N. Further, when a plurality of types of oxyalkylene groups are included, the bonding mode may be any of a block shape, a random shape, and a mixture thereof, but preferably includes at least a block shape.

  The chemical reaction of the primary amine {(a1) to (a4)} and the alkylene oxide (a5) may be carried out in any form such as anionic polymerization, cationic polymerization or coordination anionic polymerization. These polymerization forms may be used alone or in combination according to the degree of polymerization.

  The chemical reaction between the primary amine and the alkylene oxide (a5) does not necessarily require a reaction catalyst, but a reaction catalyst may be used. In particular, when an amide described below is used as a reaction solvent, it is not necessary to use a reaction catalyst. As the reaction catalyst, a conventionally used alkylene oxide addition reaction catalyst or the like can be used. Alkali metal or alkaline earth metal hydroxides (potassium hydroxide, rubidium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates (Potassium methylate and cesium ethylate), alkali metal or alkaline earth metal carbonates (potassium carbonate, cesium carbonate, barium carbonate, etc.), tertiary amines having 3 to 24 carbon atoms (trimethylamine, trioctylamine, Triethylenediamine and tetramethylethylenediamine) and Lewis acids (such as stannic chloride and boron trifluoride) are used. Of these, alkali metal hydroxides and tertiary amines are preferable, and potassium hydroxide, cesium hydroxide, and trimethylamine are more preferable.

  When using a reaction catalyst, the amount used (% by weight) is preferably 0.05 to 2, based on the total weight of the primary amine {(a1) to (a4)} and the alkylene oxide (a5), More preferably, it is 0.1-1 and Most preferably, it is 0.2-0.6.

  When using a reaction catalyst, it is preferable to remove the reaction catalyst from the reaction product. As the method, an alkali adsorbent such as a synthetic aluminosilicate {for example, trade name: Kyoward 700, Kyowa Chemical Industry Co., Ltd., “ "KYOWARD" is a registered trademark of the company. } (JP-A-53-123499, etc.), a method of dissolving in a solvent such as xylene or toluene and washing with water (JP-B-49-14359, etc.), a method using an ion exchange resin (JP-A-51 No. 23211, etc.) and a method of filtering a carbonate formed by neutralizing an alkaline catalyst with carbon dioxide (Japanese Patent Publication No. 52-33000).

  The end point of removal of the reaction catalyst is preferably a CPR (Controlled Polymerization Rate) value of 20 or less, more preferably 10 or less, particularly preferably 5 or less, and most preferably 2 or less. CPR is measured in accordance with JIS K1557-4: 2007.

  As the reaction vessel, it is preferable to use a pressure-resistant reaction vessel capable of heating, cooling and stirring. As the reaction atmosphere, the inside of the reaction apparatus is preferably evacuated before introducing the alkylene oxide (a5) into the reaction system, or an atmosphere of a dry inert gas (such as argon, nitrogen and carbon dioxide). Moreover, as reaction temperature (degreeC), 80-150 are preferable, More preferably, it is 90-130. The reaction pressure (gauge pressure: MPa) is preferably 0.8 or less, more preferably 0.5 or less.

  The end point of the reaction can be confirmed by the following method. That is, when the reaction temperature is kept constant for 15 minutes, the reaction end point is set when the decrease in the reaction pressure (gauge pressure) is 0.001 MPa or less. The required reaction time is usually 4 to 12 hours.

  The porous powder (Y) is not limited as long as it is at least one selected from the group consisting of silicon oxide, aluminum oxide, calcium carbonate and magnesium carbonate, but silicon oxide and calcium carbonate are preferable, and silicon oxide is more preferable. It is.

The BET specific surface area (m ² / g) of the porous powder (Y) is preferably 0.5 to 1000, more preferably 50 to 800, and particularly preferably 100 to 500. When it is in this range, the whitening prevention property is further improved.

  The porous powder (Y) has a di-n-butyl phthalate (DBP) oil absorption (ml / 100 g) of preferably 10 to 500, more preferably 50 to 400, and particularly preferably 100 to 300. When it is in this range, the whitening prevention property is further improved.

  The content (% by weight) of the polyoxyalkylene compound (X) contained in the powder whitening inhibitor is 1 to 70 based on the total weight of the polyoxyalkylene compound (X) and the porous powder (Y). More preferably, it is 10-65, Most preferably, it is 20-60. When it is in this range, the whitening prevention property is further improved.

  The content (% by weight) of the porous powder (Y) contained in the powder whitening inhibitor is 30 to 99 based on the total weight of the polyoxyalkylene compound (X) and the porous powder (Y). More preferably, it is 35-90, Most preferably, it is 40-80. When it is in this range, the whitening prevention property is further improved.

  Although there is no restriction | limiting in particular as a manufacturing method of the powder white-fade inhibitor of this invention, The method of charging polyether compound (X) and porous powder (Y) to a stirring mixing apparatus and stirring and mixing is preferable. As a method of charging (X) and (Y) into the stirring and mixing apparatus, a method in which all the amounts of (X) and (Y) are added all at once (1), and (Y) is continuously added to the total amount of (X) little by little. Alternatively, the method (2) in which the charging is performed in a divided manner, the method (3) in which the total amount of (Y) is continuously or dividedly added in a small amount (3), and (X) and (Y) are continuously or divided in small portions at the same time. (4) or the like can be applied. Among these, from the viewpoint of production efficiency and the like, the method (4) in which (X) is continuously or dividedly added to the total amount of (Y) little by little is preferable.

  As the stirring and mixing device, a known stirring and mixing device can be used, and examples thereof include a propeller type stirrer, a dissolver, a homomixer, a ball mill, a sand mill, a kneader, a line mixer, a ribbon mixer, a tilt barrel mixer, an omni mixer, and a Henschel mixer. .

The anti-whitening agent and anti-powder whitening agent of the present invention are suitable as an anti-whitening agent for cement compositions (concrete, mortar, plaster, etc.), and are suitable as an anti-whitening agent for mortar.
These mortars are mainly composed of water curable substances such as dolomite or cement (silicic acid calcareous cement and aluminate calcareous cement) and gypsum (alpha gypsum and beta gypsum etc.), water, water-soluble polymer, silica sand Fine aggregates such as blast furnace slag, admixture materials such as fly ash and silica fume, and fiber reinforcing materials such as nylon, polypropylene, glass, steel and carbon, and materials containing pigments such as carbon black, iron oxide and phthalocyanine as appropriate Is mentioned.

  The amount (% by weight) of the white-white inhibitor or the white-white anti-whitening agent of the present invention is preferably 0.01 to 10, more preferably, based on the weight of the cement as the amount of the polyoxyalkylene compound (X). Is 0.03 to 5, particularly preferably 0.05 to 3. When it is in this range, the whitening prevention property is further improved.

Hereinafter, unless otherwise specified, parts means parts by weight and% means% by weight.
<Example 1>
In a pressure-resistant reaction vessel capable of stirring, heating, cooling, dropping, pressurizing with nitrogen, and depressurization with a vacuum pump, 185 parts (1 mole part) of n-dodecylamine {Tokyo Chemical Industry Co., Ltd.) and N, N-dimethylformamide {DMF, Mitsubishi Gas Chemical Co., Ltd., and so on. } After 200 parts were added, the operation of pressurizing to 0.2 MPa with nitrogen gas and discharging until 0.05 MPa was repeated three times (hereinafter, the operation using this nitrogen gas is referred to as “ Abbreviated “nitrogen gas replacement”). Thereafter, the temperature was raised to 100 ° C. while stirring, and then, at the same temperature, 440 parts (10 mole parts) of ethylene oxide (EO) was added dropwise over 2 hours, and the stirring was continued at the same temperature for 2 hours to remain. EO was reacted. Next, DMF was distilled off under reduced pressure (120 ° C., 1.3 to 13 kPa, the same applies hereinafter) to obtain a white-waxing inhibitor for cement composition of the present invention (1: dodecylamine EO 10 mol adduct).

<Example 2>
Example 1 except that “n-dodecylamine {Tokyo Chemical Industry Co., Ltd.} 185 parts (1 mole part)” was changed to “n-octadecylamine {Tokyo Chemical Industry Co., Ltd.} 270 parts (1 mole part)”. In the same manner as above, an anti-whitening agent for cement composition of the present invention (2: octadecylamine EO 10 mol adduct) was obtained.

<Example 3>
A white flower for a cement composition of the present invention was obtained in the same manner as in Example 1 except that “ethylene oxide (EO) 440 parts (10 mole parts)” was changed to “ethylene oxide (EO) 176 parts (4 mole parts)”. An inhibitor (3: dodecylamine EO 4 mol adduct) was obtained.

<Example 4>
Into the same reaction vessel as in Production Example 1, 73 parts (1 mole part) of n-butylamine {Tokyo Kasei Kogyo Co., Ltd.) and 200 parts of DMF were added, followed by replacement with nitrogen gas, and the temperature was raised to 100 ° C. while stirring. At the same temperature, 116 parts (2 mol parts) of propylene oxide (PO) was added dropwise over 1 hour, and further stirring was continued at the same temperature for 2 hours, followed by dropwise addition of 352 parts (8 mol parts) of EO over 2 hours. Further, stirring was continued for 2 hours at the same temperature. Next, DMF was distilled off under reduced pressure to obtain an anti-whitening agent for cement composition of the present invention (4: butylamine / PO2 mol / EO8 mol block adduct).

<Example 5>
Into the same reaction vessel as in Production Example 1, 171 parts (1 mole part) of n-undecylamine {Wako Pure Chemical Industries, Ltd.} and 200 parts of DMF were added, and then the temperature was raised to 100 ° C while stirring with nitrogen gas. Then, at the same temperature, 232 parts (4 mole parts) of propylene oxide (PO) was added dropwise over 2 hours, and stirring was further continued at the same temperature for 2 hours, and then 264 parts (6 mole parts) of EO was added for 2 hours. The mixture was added dropwise, and stirring was further continued at the same temperature for 2 hours. Next, DMF was distilled off under reduced pressure to obtain an anti-whitening agent for cement composition according to the present invention (5: undecylamine / PO4 mol / EO6 molblock adduct).

<Example 6>
Ribbon mixer (RMA-50, Alpha Co., Ltd.) with porous powder (Y1) {Nipsil NA, Tosoh Silica Co., Ltd., silicon oxide, BET specific surface area 160 m ² / g, DBP oil absorption 250 ml / 100 g, “Nipsil "Is a registered trademark of the company. } 3 kg of cement composition white anti-bacterial agent (1) obtained in Example 1 was added dropwise with stirring, and the mixture was further stirred and homogenized for 0.5 hours to obtain the powder for cement composition of the present invention. A white flower inhibitor (1) was obtained.

<Example 7>
“Porous powder (Y1) 2 kg” is changed to “Porous powder (Y2) {Nipsil ER, Tosoh Silica Co., Ltd., silicon oxide, BET specific surface area 100 m ² / g, DBP oil absorption 180 ml / 100 g} 4 kg” Similar to Example 6 except that the change was made and “white matter inhibiting agent for cement composition (1) 3 kg” was changed to “1 kg of cement composition white prevention agent (2) obtained in Example 2”. As a result, a powdery whitening inhibitor (2) for a cement composition of the present invention was obtained.

<Example 8>
“Porous powder (Y1) 2 kg” is replaced with “Porous powder (Y3) {SILYSIA 370, Fuji Silysia Chemical Co., Ltd., silicon oxide, BET specific surface area 300 m ² / g, DBP oil absorption 300 ml / 100 g,“ SILYSIA ”. Is a registered trademark of YKF Co., Ltd. } 2 kg ", and other than changing" 3 kg of whitening prevention agent for cement composition (1) 3 kg "to" 3 kg of whitening prevention agent for cement composition (3) obtained in Example 3 " In the same manner as in Example 6, a powdery whitening inhibitor (3) for a cement composition of the present invention was obtained.

<Example 9>
“Porous powder (Y1) 2 kg” is changed to “Porous powder (Y4) {SILYSIA 530, Fuji Silysia Chemical Co., Ltd., silicon oxide, BET specific surface area 500 m ² / g, DBP oil absorption 160 ml / 100 g} 2 kg” Similar to Example 6 except that the change was made and “white matter inhibiting agent for cement composition (1) 3 kg” was changed to “white matter preventing agent for cement composition (4) 3 kg obtained in Example 4”. As a result, a powder whiteness inhibitor (4) for a cement composition of the present invention was obtained.

<Example 10>
“Porous powder (Y1) 2 kg” is changed to “Porous powder (Y5) {SILYSIA 710, Fuji Silysia Chemical Ltd., silicon oxide, BET specific surface area 700 m ² / g, DBP oil absorption 100 ml / 100 g} 2 kg” In the same manner as in Example 6, except that the change was made and “white flower inhibitor (1) 3 kg” was changed to “white flower inhibitor (5) 3 kg for cement composition obtained in Example 5”. An anti-powder white powder agent (5) for a cement composition of the invention was obtained.

<Example 11>
“Porous powder (Y1) 2 kg” is replaced with “Porous powder (Y6) {Kallite-KT, Shiroishi Kogyo Co., Ltd., calcium carbonate, BET specific surface area 40 m ² / g, DBP oil absorption 140 ml / 100 g,“ Kallite ”. Is a registered trademark of the company. } 4 kg ", and the same procedure as in Example 6 except that“ 3 kg of whitening prevention agent for cement composition (1) 3 kg ”was changed to“ 1 kg of whitening prevention agent for cement composition (1) ”. The powder white-fair prevention agent (6) for cement compositions of this invention was obtained.

<Comparative Example 1>
40 parts of potassium stearate {Kanto Chemical Co., Ltd.}, 24 parts of ethyl alcohol and 36 parts of water were uniformly mixed to obtain a whitening inhibitor (C1) for a cement composition for comparison.

<Evaluation of white flower prevention>
Mortar was prepared as follows, and the white-white prevention property was evaluated. The results are shown in the table below.
(1) Preparation of hardened cement 80 parts of cement {ordinary Portland cement, Taiheiyo Cement Co., Ltd.}, 20 parts of α-type hemihydrate gypsum {YGK, Yoshino Gypsum Co., Ltd.}, 100 parts of silica sand {dried silica sand of Aichi Yakusa district} 100 parts And 0.1 part of a thickener {methylcellulose, 90SH-30000, Shin-Etsu Chemical Co., Ltd.} with a mortar mixer {model: C138A-486, Maruto Seisakusho Co., Ltd.} for 10 seconds, and then a water reducing agent {Sanyo Reberon , SANYO KASEI KOGYO Co., Ltd.} 1 part, 50 parts of water and sample {0.1 part of white flower inhibitor or 0.2 part of powder white flower inhibitor} are added and kneaded for 2 minutes, 10 cm × 10 cm × 2 cm And then cured for 2 weeks (temperature 25 ° C., relative humidity 90%). Subsequently, it was demolded to obtain a hardened cement for evaluation.

(2) Whitening prevention evaluation The surface of the evaluation cement hardening body was visually observed, and whitening prevention was evaluated according to the following criteria.
Moreover, the surface of the hardened | cured material for evaluation hardened | cured using the white flower inhibiting agent (1) for cement compositions of this invention obtained in Example 1 was photographed, and it showed in FIG. Moreover, the surface of the hardened | cured material for evaluation hardened | cured using the anti-wrinkle agent for cement compositions for comparison (C1) obtained by the comparative example 1 was photographed, and it showed in FIG.
○ White flower was not recognized × White flower was recognized on the entire surface

As is clear from the results in Table 1, the anti-whitening agent and the powdery whiteness-inhibiting agent of the present invention exhibited excellent anti-whitening properties as compared with the comparative whitening-inhibiting agent.

Claims (5)

An anti-whitening agent for cement compositions comprising a polyoxyalkylene compound (X) represented by the formula (1).

R ¹ —N {(— AO) n—H} ₂ (1)

R ¹ is an alkyl group having 10 to 18 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, N represents a nitrogen atom, H is a hydrogen atom, n is an integer of 2 to 15. It comprises a polyoxyalkylene compound (X) represented by the formula (1) and at least one porous powder (Y) selected from the group consisting of silicon oxide, aluminum oxide, calcium carbonate and magnesium carbonate. An anti-powder white powder for cement compositions.

R ¹ —N {(— AO) n—H} ₂ (1)

R ¹ is an alkyl group having 10 to 18 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, N represents a nitrogen atom, H is a hydrogen atom, n is an integer of 2 to 15. The content of (X) is 1 to 70% by weight and the content of (Y) is 30 to 99% by weight based on the total weight of the polyoxyalkylene compound (X) and the porous powder (Y). Item 3. The powder whiteness inhibitor according to Item 2. 4. The powder whiteness inhibitor according to claim 2, wherein the porous powder (Y) is a powder having a BET specific surface area of 0.5 to 1000 m ² / g and a DBP oil absorption of 10 to 500 ml / 100 g. . Containing the cement and the whitening prevention agent according to any one of claims 2 to 4, or cement and the whitening prevention agent according to any one of claims 2 to 4,
A cement composition, wherein the content of the whitening inhibitor or the powdery whitening inhibitor relative to 100 parts by weight of cement is 0.01 to 10 parts by weight.