JPH0720616B2 - Mold release agent composition for concrete - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an improved mold release agent for concrete. More specifically, concrete is not adhered to the surface of metal plates such as iron plates and plywood used for formwork, imparts smoothness to the concrete surface, and further cement is dispersed by the components in the mold release agent. The present invention relates to a novel mold-releasing agent for concrete, characterized in that the cement on the surface is finely dispersed to give a fine and beautiful appearance to the concrete surface, and the concrete surface is not colored.

[Prior Art and its Problems] Various concrete molds currently used in concrete pouring and the surface of the material used for the molds can be easily demolded after concrete pouring, and To improve the finish of the concrete surface, a mold release agent is applied.

Conventionally, these releasing agents include an oily type and a water-emulsifying aqueous type. The basic composition of oil type is kerosene; light oil; lubricating oil such as machine oil, spindle oil, turbine oil; synthetic hydrocarbon oil such as polybutene, etc. as a base (base oil), and paraffin, low molecular weight polyethylene,
Waxes such as atactic polypropylene, petroleum resin, petrolatum, montan wax; animal and vegetable oils such as soybean oil, olive oil, rapeseed oil, pearl oil, lard; caproic acid, iso-caproic acid, enanthic acid, caprylic acid, i
so-caprylic acid, pelargonic acid, capric acid, octylic acid, palmitic acid, stearic acid, and other linear or branched higher fatty acids; fatty acid amines derived from these fatty acids; also aliphatic amides; rosin amine; rosin amide; Metallic salt of fatty acid such as lithium metal soap, zirconium metal soap, and other metal soaps; compounded with an oil film enhancer such as aromatic sulfonic acid formalin high-condensate and melamine sulfonic acid formalin high-condensate formalin condensate . Similarly, the aqueous type is obtained by emulsifying these oily types in water with an appropriate emulsifier.

The technology relating to a mold release agent for concrete using a petroleum fraction such as a lubricant as a base oil includes JP-B-60-32565, JP-A-49-18768, and JP-A-49-76919. 53
No. 146718, No. 55-66506, No. 55-65507, No. 55-65508.

However, the release agents using these petroleum fractions are desired to be improved one step further. For example, a volatile base oil such as kerosene or light oil may have a bad odor when it is volatilized into the atmosphere, which may adversely affect the working environment. Kerosene oil contains aromatic hydrocarbons at a considerably high concentration, and from this point also concern about environmental pollution and safety to the human body.
Environmental pollution caused by aromatic hydrocarbons is the same even in a base oil having a relatively high boiling point, such as a lubricating oil fraction. Further, since this aromatic hydrocarbon has a good solubility in fat, when it is brought into contact with a hydrocarbon containing them, it is easy to cause a hand rash.

Therefore, it has been desired to develop a mold release agent for concrete which has little odor, is safe and has no fear of environmental pollution due to aromatic hydrocarbons, and is of course excellent in performance.

[Structure of the Invention] That is, the present invention was developed in view of the above-mentioned circumstances, and the gist of the invention is to use a kerosene fraction having a boiling point of 150 to 300 ° C as a nuclear hydrogen of an aromatic nucleus. Nuclear hydrogenation treatment is carried out under the conditions of a pressure of 10 to 100 Kg / cm ² and a temperature of 100 to 300 ° C. with a metal catalyst for addition, and at least one of n-paraffins in the kerosene fraction is then treated using a molecular sieve made of synthetic zeolite. The residual oil obtained by separating and removing the parts is fractionated by a precision distillation apparatus to obtain a hydrocarbon mixture fraction substantially free of naphthalene and biphenyl and having a boiling point of 150 to 300 ° C as base oil. The present invention relates to a mold release agent composition for concrete.

The second invention of the present invention is a kerosene fraction having a boiling point in the range of 150 to 300 ° C under the conditions of a pressure of 10 to 100 kg / cm ² and a temperature of 100 to 300 ° C by a metal catalyst for nuclear hydrogenation of aromatic nuclei. The residual oil obtained by separating and removing at least a part of the n-paraffins in the kerosene fraction using a molecular sieve made of synthetic zeolite after the first stage nuclear hydrogenation treatment is refined as necessary. Fractional distillation by a distillation apparatus, further hydrogenation treatment of the second stage under the conditions substantially the same as or milder than the first stage, which is subjected to precision distillation, the boiling point of substantially aromatic hydrocarbon-free 150 ~ 300 It relates to a mold release agent composition for concrete, which comprises a hydrocarbon mixture fraction in the range of ° C as a base oil.

The present invention will be further described below.

In the present invention, a kerosene fraction having a boiling point of 150 to 300 ° C. is hydrogenated by a metal catalyst for nuclear hydrogenation of aromatic nuclei. Any conventionally known metal catalyst for hydrogenation of aromatic nuclei can be preferably used as this catalyst. For example,
Nickel, nickel oxide, nickel / diatomaceous earth, Raney nickel, nickel / copper, platinum, platinum oxide, platinum / activated carbon, platinum / rhodium, platinum / lithium / alumina, rhodium / activated carbon, palladium, cobalt, Raney cobalt, ruthenium, nickel / tungsten. , Tungsten sulfide / nickel sulfide / alumina, cobalt / molybdenum, etc. can be preferably used. Hydrogen pressure is 10 ~ 100Kg / c
m ² and temperature are 100 to 300 ° C. The hydrogenation reaction does not proceed sufficiently at a pressure lower than 10 kg / cm ² or a temperature lower than 100 ° C, and a side reaction such as decomposition takes precedence at a pressure higher than 100 kg / cm ² or a temperature higher than 300 ° C, which is not preferable. . The reaction system may be a batch system or a continuous / flow system.

Here, the aromatic hydrocarbons in the kerosene fraction are nuclear hydrogenated into naphthenes by the above hydrogenation, but usually 100% of the aromatic hydrocarbons contained are not nuclear hydrogenated and the above catalyst is used. Depending on the type, reaction conditions, etc., some amount of aromatic hydrocarbon remains without being hydrogenated. In addition, hydrogenation treatment often involves decomposition and isomerization as a side reaction, and thus products related to these reactions are inevitably included in the hydrogenated kerosene fraction.

Following the above hydrogenation treatment, at least a part of n-paraffins in the kerosene fraction is separated and removed using a molecular sieve made of synthetic zeolite to obtain a residual oil.

A method of separating and obtaining n-paraffins from a hydrocarbon mixture by repeating adsorption / desorption in a gas phase or a liquid phase using a molecular sieve has hitherto been an industrial method for producing n-paraffins as follows. Has been widely implemented.

That is, for example, using a molecular sieve made of synthetic Zealite having a large number of pores adjusted to 5A as a fixed bed, adsorption and desorption of n-paraffins are alternately performed in the liquid phase, and the molecular sieve adsorbing n-paraffins is desorbed. Washed with low molecular weight paraffin
The paraffins are desorbed, and the mixed desorption low-molecular weight paraffin is separated by distillation and recirculated. The Molex method is used, and the adsorption and desorption by a molecular sieve made of synthetic zeolite also having 5A pores is used for n-paraffin in the gas phase. TS that adsorbs compounds and desorbs them with low molecular weight paraffin
F method (Texaco selective finishing method),
Similarly, using a molecular sieve made of 5A synthetic zeolite,
Adsorption / desorption of n-paraffins to the molecular sieve is carried out by alternately repeating pressurization and depressurization, and is a method combining the vapor phase and liquid bed methods, and has 5A pores of n-paraffins. Adsorption to a molecular sieve made of synthetic zeolite is continuously carried out in a liquid bed in the adsorption device, and its desorption is operated at a temperature higher than the adsorption in the regenerator, and the regenerated molecular sieve is returned from the regenerator to the adsorption device. There is an esso method to recycle.

The n-paraffins can be separated by any method using a molecular sieve made of synthetic zeolite having pores of 5A.

Generally, in the separation of n-paraffins, theoretically only n-paraffins should be separated. However, depending on the method, hydrocarbons other than n-paraffins may be n-paraffins.
-The content of components other than n-paraffins in the residual oil obtained as a result of separation accompanying the paraffins may change. Considering these points, there is a method of industrially separating n-paraffins by using urea crystals, but as the method of the present invention, a molecular sieve made of synthetic zeolite having pores of 5A is used. The method as described above is suitable.

The n-paraffins are separated from the hydrogenated kerosene fraction as described above to obtain a residual oil. Next, this residual oil is subjected to precision distillation. For example, a precision distillation apparatus comprising two or more distillation columns is used to remove light hydrocarbons from the top of the first column, and the target fraction is removed from the top of the second or subsequent columns. Manufactured. Of course, if the separation efficiency such as the number of distillation stages is appropriate, light hydrocarbons and heavy hydrocarbons are removed from the top and top of a precision distillation apparatus consisting of one distillation column, respectively, and the objective is taken from the center of the column. Fractions can also be produced. The precision distillation may be performed after the second-stage nuclear hydrogenation described below.

With the above precision distillation apparatus, the boiling point is 150 to 300 ° C, preferably 20
A hydrocarbon mixture fraction in the range 0-280 ° C is obtained.

The boiling point of the hydrocarbon mixture fraction of the present invention is required to be in the above range, and if it is out of this range, the presence of each component and the balance of the content thereof are disturbed and the intended purpose cannot be achieved, which is preferable. Absent. That is, in a range lower than the boiling point range, a large amount of harmful aromatic hydrocarbons such as benzene and toluene is contained, which is not preferable. Further 300
When the boiling point temperature is higher than 0 ° C, the boiling point becomes too high, the drying property at the time of drying becomes poor, and the residual odor becomes strong, which is not preferable.

The above hydrocarbon fraction is substantially free of benzene, toluene, etc., and has a low content of other aromatic hydrocarbons, and is particularly substantially free of naphthalene and biphenyl. However, in the present invention, for the purpose of higher safety, for example, in order not to contain substantially all kinds of aromatic hydrocarbons, the residual oil is subjected to a second stage hydrogenation treatment. It is also possible to obtain a fraction containing substantially no aromatic hydrocarbon.

Here, the hydrogenation performed in the second stage on the above residual oil is
It can be carried out in the same manner as the above-mentioned first stage nuclear hydrogenation. Alternatively, the nuclear hydrogenation may be performed under milder conditions, that is, lower temperature or lower pressure. The nuclear hydrogenation metal catalyst used in the second stage does not necessarily have to be the same as in the first stage. That is, the catalyst may be the same or different. In any case, it may be appropriately selected from the above-mentioned hydrogenation conditions.

Next, after the second-stage nuclear hydrogenation, fine distillation is carried out as necessary as described above.

A hydrocarbon mixture fraction having a boiling point in the range of 150 to 300 ° C. is obtained by the above precision distillation apparatus.

The base oil of the mold release agent for concrete of the present invention is composed of the fraction obtained as described above, and the fraction has a low aromatic hydrocarbon content or substantially no hydrocarbon content. It is a fraction.

To produce a mold release agent for concrete using the base oil of the present invention, the oil film strengthening agent as described above is blended. These can be blended with one kind or a mixture of two or more kinds, and the blending amount is 0.001 to 3 in total with respect to the base oil of the present invention.
It is in the range of 0% by weight. If the blending amount is less than this range, the oil film will not be sufficiently retained, and the effect of the base oil of the present invention will be insufficient. Further, even if the blending amount exceeds this range, there is no corresponding effect, which is not preferable from the economical viewpoint.

The oil film enhancer of the present invention is not limited to the oil film enhancer described above, and conventionally known ones can be used. To give a concrete example again, paraffin, low molecular weight polyethylene, atactic polypropylene; aromatic, alicyclic or aliphatic petroleum resin; waxes such as petrolatum and montan wax; soybean oil, olive oil, Rapeseed oil, pearl oil,
Flaxseed oil, animal and vegetable oils and fats such as lard, these distillation residue pitches; caproic acid, iso-caproic acid, enanthate,
Straight-chain or branched higher fatty acids such as caprylic acid, iso-caprylic acid, pelargonic acid, capric acid, octylic acid, lauric acid, palmitic acid, stearic acid, oleic acid; distillation residue pitch of these fatty acids; Derived fatty acid amines; also aliphatic amides; rosin amines; rosin amides; metal soaps of the fatty acid metal salts such as lithium metal soaps and zirconium metal soaps; aromatic sulfonic acid formalin high-condensates, meminsulfonic acid formalin high-condensates The formalin condensate and the like are exemplified. Any of these oil film enhancers can be used as long as it dissolves in the hydrocarbon fraction of the present invention.

The release agent of the present invention can be used as an oily type or an emulsion type, but is preferably used as an oily type. When used as an oily type, it can be used as a liquid as it is or as a semi-kneaded (paste) form.

The mold release agent of the present invention preferably contains a lubricating oil fraction such as machine oil, spindle oil or turbine oil or a polymer as a thickener. These amounts can be appropriately determined depending on the viscosity of the obtained release agent. Of course, on the contrary, kerosene may be mixed to reduce the viscosity before use. Further, a rust preventive or the like which is conventionally blended with a release agent for metal frames can be included.
Furthermore, the effect of the present invention is not particularly affected even if a concrete admixture usually used in concrete, that is, an air entraining agent, a water-reducing agent, a hardening accelerator, a setting retarder, etc. is mixed.

In applying the release agent of the present invention, it can be used in any of metal molds such as iron, wood molds such as plywood, and can be applied by any of conventional brush coating, sponge coating and spraying methods. be able to.

[Effects of the Invention] By using the release agent of the present invention, the work environment is not polluted because it has less odor and less aromatic hydrocarbons.

Since conventional petroleum solvents contain a considerable amount of xylene and other aromatic hydrocarbons in their components, they are highly toxic to the human body and their adverse effects on the human body are regarded as important and pose a problem. In particular, in the Ordinance of the Ministry of Labor's Ordinance for Prevention of Disorders of Specific Chemical Substances, the benzene content exceeds 1% by volume, and in the Ordinance for Prevention of Organic Solvent Poisoning in the same Ordinance, the total of toluene and xylene exceeds 5% by weight. The handling of each is severely limited. Regarding naphthalene and biphenyls, OSHA (Occupational Safety and Health A
dministration) enacted "regulation of hazards of chemical substances etc." and subject to regulations, and products containing these compounds are required to label these compounds.

However, the solvent according to the present invention is a safe solvent which satisfies all the above-mentioned criteria and does not cause problems such as hand rash because it has a small amount of aromatic hydrocarbons. Furthermore, the concrete surface obtained by using this has a smooth surface with less surface unevenness caused by air bubbles, and does not show a yellow color on the surface as compared with the case of using kerosene, but rather becomes a white surface.

The present invention will be described in detail below with reference to examples.

[Example] Base oil production example-1 A kerosene fraction (65% by weight of paraffins, 25% by weight of naphthenes, 10% by weight of aromatics) obtained by distillation of crude oil in the boiling range of 150 to 300 ° C was added to 280 ° C. Using a Ni-W catalyst for nuclear hydrogenation of aromatic hydrocarbons as a catalyst under the condition of 90 Kg / cm ² , nuclear hydrogenation was performed, and the obtained product was composed of synthetic zeolite by the Molex method. The n-paraffins were separated by feeding to a separation column packed with a molecular sieve having angstrom holes. The resulting residual oil fraction depleted in n-paraffins was then precision distilled using a two-column precision distillation apparatus to obtain a hydrocarbon mixture fraction having a boiling point of 205 ° C to 235 ° C. The composition and properties of this base oil are shown in Table 1.

Base oil production example-2 The residual oil fraction obtained in the step of the above base oil production example-1 in which n-paraffins were reduced was treated with a nickel-based catalyst as a catalyst under the conditions of 200 ° C. and 50 kg / cm ^2. The product obtained by the second stage hydrogenation treatment was subjected to precision distillation using a two-column precision distillation apparatus to obtain a hydrocarbon mixture fraction having a boiling point of 203 to 233 ° C. The composition and properties of this base oil are also shown in Table 1.

Example A mold release agent was prepared by using each of the above base oil production examples 1 and 2 and kerosene (boiling range 200 to 280 ° C.) as a base oil according to the following formulation. The release performance was tested.

Base oil 50% by weight Machine oil 40% by weight Aromatic petroleum resin (hardening point 120) 10% by weight Lithium metal soap 0.5% by weight Test method: 50 × 50 × 5 cm mold made of 5 mm thick mild steel plate After applying a fixed amount of mold release agent to a dry film thickness of about 10μ and leaving it for about 2 hours, concrete (cement: sand: gravel = 1: 4: 8) was poured into it and cured for 5 days After demolding, the condition of the mold and the concrete surface was visually observed. The results are shown in Table-2. The results are shown as the average value of 10 samples.

Claims (2)

[Claims] 1. A kerosene fraction having a boiling point in the range of 150 to 300 ° C.,
Pressure 10〜100Kg / by metal catalyst for nuclear hydrogenation of aromatic nucleus
It is obtained by nuclear hydrogenation treatment under the conditions of cm ² and temperature of 100 to 300 ° C., and then separating and removing at least a part of n-paraffins in the kerosene fraction using a molecular sieve made of synthetic zeolite. Mold release for concrete, characterized in that the base oil is a hydrocarbon mixture fraction having a boiling point of 150 to 300 ° C., which is substantially free of naphthalene and biphenyl obtained by fractionating the residual oil with a precision distillation apparatus. Agent composition. 2. A kerosene fraction having a boiling point of 150 to 300 ° C.,
Pressure 10〜100Kg / by metal catalyst for nuclear hydrogenation of aromatic nucleus
cm ^{2 at} a temperature of 100 to 300 ° C., a first stage nuclear hydrogenation treatment is performed, and then at least a part of n-paraffins in the kerosene fraction is separated using a molecular sieve made of synthetic zeolite.
If necessary, the residual oil obtained by removal is fractionally distilled by a precision distillation apparatus, and then the second stage is subjected to hydrogenation treatment under conditions that are substantially the same as or milder than those of the first stage, and then precision distilled. A mold release agent composition for concrete, which comprises a hydrocarbon mixture fraction having a boiling point of 150 to 300 ° C. substantially free of aromatic hydrocarbons as a base oil.