KR102405279B1 - Functional Fluid Compositions - Google Patents

Abstract

The present invention is a functional fluid composition based on glycols, and relates to a functional fluid composition comprising a monoamine-based noise reducing agent.
According to the present invention as described above, the functional fluid composition comprising a monoamine-based noise reducing agent represented by Formula 1 and based on glycols has an excellent noise reduction effect.
In addition, the functional fluid composition of the present invention uses a monoamine-based compound as a noise reducing agent, so that even when a metal corrosion inhibitor composed of a triazole-based compound that does not contain an amine-based compound is used as a metal corrosion inhibitor, there is an excellent metal corrosion prevention effect. .

Description

Functional Fluid Compositions

The present invention relates to a functional fluid composition, and more particularly, to a functional fluid composition based on glycols, and to a functional fluid composition comprising a monoamine-based noise reducing agent.

The present invention relates to a functional fluid composition useful as a brake fluid. Common automotive brake fluids include three types (DOT-3) type brake fluid using only glycol ether compounds as solvents, and 4 types (DOT-4) type brake fluid containing about 30 to 60% by weight of boron ester compounds. It is mainly used. The DOT-3 type brake fluid uses only glycol ether compounds, which are low molecular weight substances, so that when used for a long time, it absorbs moisture from the atmosphere, lowers the wet boiling point, and causes a vapor lock phenomenon to prevent a braking failure accident. There is a risk of causing damage, and the long-term metal corrosion protection ability is weak. In addition, the DOT-4 type brake fluid has a higher level of safety than the DOT-3 type because of its high equilibrium reflux boiling point and wet boiling point by using a boron ester compound. However, the DOT-4 type brake fluid causes hydrolysis when the boron ester-based compound comes into contact with moisture, and as boric acid is precipitated, there is a problem in that the physical properties of the brake fluid are deteriorated and foreign substances are generated.

Accordingly, the DOT-4 type brake fluid is used by adding an amine or silane-based stabilizer to prevent boric acid precipitation (Korean Patent Application Laid-Open No. 10-2004-0023917). However, there is another problem in that noise is greatly increased when the master cylinder in the brake device is operated by further including such a stabilizer.

In addition, Japanese Patent Application Laid-Open No. 2013-227380 describes that brake fluid containing a fluorine compound is effective in preventing stick-slip by improving lubricity, but the fluorine compound having a lipophilic group is mixed with a glycol ether solvent having hydrophilicity There is a difficult problem.

Accordingly, as a result of intensive efforts for the development of a functional fluid composition, the present inventors have found that the functional fluid composition comprising a monoamine-based noise reducing agent represented by the following Chemical Formula 1 has excellent noise reduction effect as well as excellent metal corrosion prevention effect. The present invention was completed by confirming experimentally.

Accordingly, an object of the present invention is to provide a functional fluid composition comprising a monoamine-based noise reducing agent represented by the following Chemical Formula 1 as a functional fluid composition based on glycols.

[Formula 1]

In Formula 1, X and Y are integers of 1 or more, R is H or CH ₃ , and the weight average molecular weight of the compound represented by Formula 1 is 600 or more.

According to one aspect of the present invention, as a functional fluid composition based on glycols, there is provided a functional fluid composition comprising a monoamine-based noise reducing agent represented by the following formula (1).

[Formula 1]

In Formula 1, X and Y are integers of 1 or more, R is H or CH ₃ , and the weight average molecular weight of the compound represented by Formula 1 is 600 or more.

In the composition of the present invention, the glycol base includes a glycol compound and a boric acid ester compound.

As the glycol compound, any known in the art may be used, but preferably ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, polyalkylene glycol, glycol ether, and their is selected from the group consisting of mixtures. More preferably, the glycol compound suitable for the composition of the present invention is ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, polyalkylene glycol or glycol ether.

As the glycol ether, any known in the art may be used, but preferably ethylene glycol ethyl ether, diethylene glycol ethyl ether, triethylene glycol ethyl ether, ethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, polyethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether, polyethylene glycol butyl ether, dipropylene glycol methyl ether, polypropylene glycol methyl ether, and mixtures thereof. . More preferably, glycol ethers suitable for the composition of the present invention are ethylene glycol methyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, polyethylene glycol methyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, triethylene glycol butyl ether or polyethylene glycol butyl ether, and most preferably triethylene glycol monomethyl ether, polyethylene glycol monomethyl ether or polyethylene glycol monobutyl ether.

The boric acid ester compound is used to prevent a boiling point drop due to moisture absorption, and the boric acid ester compound is included in a content range of 30 to 60% by weight based on 100% of the total weight of the functional fluid composition. At this time, if the amount of the boric acid ester compound used is less than the above range, the desired effect cannot be achieved, and when it exceeds the above range, there is a risk of increased manufacturing cost and precipitation of boric acid.

According to the most preferred embodiment of the present invention, the glycol base used in the present invention is a mixture of polyalkylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, triethylene glycol monomethyl ether and boric acid ester compound. .

In the composition of the present invention, the content of the glycol base including the glycol compound and the boric acid ester compound is preferably 20-99% by weight, more preferably 40-99% by weight, based on the total weight of the functional fluid composition, Even more preferably 60-99% by weight, still more preferably 70-99% by weight, most preferably 85-99% by weight.

In the composition of the present invention, the monoamine-based noise reducing agent may be represented by the following formula (1).

[Formula 1]

In Formula 1, X and Y are integers of 1 or more, R is H or CH ₃ ,

The weight average molecular weight of the compound represented by Formula 1 is 600 or more.

Preferably, the weight average molecular weight of the compound represented by Formula 1 is 600 or more and 2000 or less, and more preferably 1000 or more and 2000 or less.

)은 R이 H인 경우 다음의 계산식 1에 의해 계산될 수 있고, R이 CH₃인 경우 다음의 계산식 2에 의해 계산될 수 있다.The molecular weight of one compound arbitrarily selected from different molecular weights (M) that the compound represented by Formula 1 may have in the present specification (

) can be calculated by Equation 1 below when R is H, and can be calculated by Equation 2 below when R is CH ₃ .

[Formula 1]

[Formula 2]

In Equations 1 and 2, X and Y are integers of 1 or more.

Meanwhile, the weight averaged molecular weight (Mw) of the compound represented by Formula 1 may be calculated by the following Formula 3.

[Formula 3]

는 임의의 분자량 M_i를 갖는 화합물들의 총 개수를 의미한다. In Equation 2 above

means the total number of compounds having any molecular weight M _i .

In the composition of the present invention, the monoamine compound represented by Formula 1 as a noise reducing agent is 0.05-5.0 wt%, more preferably 0.1-5.0 wt%, most preferably based on the total weight of the functional fluid composition It may be included in 0.2-5.0 wt%.

According to one embodiment of the present invention, the composition of the present invention may include one or more additives of a metal corrosion inhibitor and an antioxidant.

The metal corrosion inhibitor may be any known in the art, but the corrosion inhibitor used in the present invention is a triazole-based compound, an amine-based compound, or a mixture thereof.

The triazole-based compound includes various triazoles known in the art, and may be selected from the group consisting of triazole derivatives, benzotriazole derivatives and tolutriazole derivatives. Specifically as benzotriazole derivatives, N,N-bis(2-ethylhexyl)-4-methyl-1 H-benzotriazole-1-methylamine, N,N-bis(2-ethylhexyl)-5- Methyl-1 H-benzotriazole-1-methylamine, octyl 1 H benzotriazole, ditertiary butylated 1 H benzotriazole, 1H-1,2,3-triazole, 2H-1,2,3- Triazole, 1H-1,2,4-triazole, 4H-1,2,4-triazole, 1-(1', 2'-di-carboxyethyl) benzotriazole, 2-(2'-hydride Roxy-5'-methyl phenyl) benzotriazole, 1H-1,2,3-triazole, 2H-1,2,3-triazole, 1H-1,2,4-triazole, 4H-1,2 ,4-triazole, benzotriazole, tolyltriazole, carboxybenzotriazole, 3-amino-1,2,4-triazole, chlorobenzotriazole, nitrobenzotriazole, aminobenzotriazole, cycloheki sano [1,2-d] triazole, 4,5,6,7-tetrahydroxytolyltriazole, 1-hydroxybenzotriazole, ethyl benzotriazole, naphthotriazole, 1-[N,N -Bis(2-ethylhexyl)aminomethyl]benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]tolyltriazole, 1-[N,N-bis(2-ethylhexyl) Aminomethyl]carboxybenzotriazole, 1-[N,N-bis(di-(ethanol)-aminomethyl]benzotriazole, 1-[N,N-bis(di-(ethanol)-aminomethyl]tolyltriazole) Sol, 1-[N,N-bis(di-(ethanol)-aminomethyl]carboxybenzotriazole, 1-[N,N-bis(2-hydroxypropyl)aminomethyl]carboxybenzotriazole, 1- [N,N-bis(1-butyl)aminomethyl]carboxybenzotriazole, 1-[N,N-bis(1-octyl)aminomethyl]carboxybenzotriazole, 1-(2', 3'-di -Hydroxypropyl) benzotriazole, 1-(2', 3'-di-carboxyethyl) benzotriazole, 2-(2'-hydroxy-3', 5'-di-tert-butyl phenyl) benzo triazole, 2-(2'-hydroxyl-3',5'-di-tert-amylphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2- (2'-hydroxyl-5'-tert-butyl phenyl) benzotriazole, 1-hydroxybenzotriazole-6-car Acid, 1-Na oil Benzotriazole, 1,2,4-triazol-3-ol, 3-amino-5-phenyl-1,2,4-triazole, 3-amino-5-heptyl-1 , 2,4-triazole, 3-amino-5- (4-isopropyl-phenyl) -1,2,4-triazole, 5-amino-3-mercapto-1,2,4-triazole, 3-Amino-5-(p.tert-butyl phenyl)-1,2,4-triazole, 5-amino-1,2,4-triazole-3-carboxylic acid, 1,2,4-triazole sol-3-carboxamide, 4-aminourasol, 1,2,4-triazol-5-one, and the like.

Preferably, it contains at least one selected from benzotriazole, mercaptobenzotriazole, tolytriazole, octyltriazole, decyltriazole, dodecyltriazole, and the like. More preferably, it is a mixture of benzotriazole and mercaptobenotriazole.

In the composition of the present invention, the content of the triazole compound as a metal corrosion inhibitor is 0.1-10 wt%, more preferably 0.5-5.0 wt%, most preferably 0.5-3.0 wt%, based on the total weight of the functional fluid composition to be.

The amine-based compound may be selected from the group consisting of alkanol amines, alkylamines, and cyclic amines. Looking specifically at the alkanol amine compounds, monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, nonethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, monoisopropanolamine, diisopropanol There are amines, triisopropanolamine, etc., and specifically looking at alkylamine compounds, dibutyl amine, tributyl amine, dicyclohexyl amine, cyclohexyl amine and its salts, piperazine, n-propylamine, isopropylamine, n -Butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n -decylamine, 2-propylheptylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, isotridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine , n-heptadecylamine, n-octadecylamine, n-nonadecylamine, n-eicosyl-amine, di-(n-hexyl)amine, di-(n-heptyl)amine, di-(n-octyl) )amine, di-(2-ethylhexyl)amine, di-(n-nonyl)amine, di-(n-decyl)amine, di-(2-propylheptyl)amine, di-(n-undecyl)amine , di-(n-dodecyl)amine, di-(n-tridecyl)amine, di-(isotridecyl)amine, di-(n-tetradecyl)amine, di-(n-pentadecyl)amine, Di-(n-hexadecyl)amine, di-(n-heptadecyl)amine, di-(n-octadecyl)-amine, di-(n-nonadecyl)amine, di-(n-eicosyl)amine , n-hexylmethylamine, n-heptyl-methylamine, n-octylmethylamine, (2-ethylhexyl)methylamine, n-nonylmethylamine, n-decylmethylamine, (2-propylheptyl)methylamine , n-undecylmethylamine, n-dodecyl-methylamine, n-tridecylmethylamine, isotridecylmethylamine, n-tetradecylmethylamine, n-pentadecylmethylamine, n-hexadecylmethylamine, n-heptadecylmethylamine, n-octa-decylmethylamine, n-nonadecylmethylamine, n-eicosylmethylamine, di-(n-nonyl)amine, di-(n-decyl)amine, di-( 2-propylheptyl)amine, di-(n-undecyl)amine, di-(n-dodecyl)amine, di-(n-tridecyl)amine, di-(isot Ridecyl)amine, di-(n-tetradecyl)amine, di-(n-pentadecyl)amine, di-(n-hexadecyl)amine, di-(n-heptadecyl)amine, di-(n- Octadecyl)-amine, di-(n-nonadecyl)amine, di-(n-eicosyl)amine, n-hexylmethylamine, n-heptyl-methylamine, n-octylmethylamine, (2-ethylhexyl) syl)methylamine, n-nonylmethylamine, n-decylmethylamine, (2-propylheptyl)methylamine, n-undecylmethylamine, n-dodecyl-methylamine, n-tridecylmethylamine, isotri Decylmethylamine, n-tetradecylmethylamine, n-pentadecylmethylamine, n-hexadecylmethylamine, n-heptadecylmethylamine, n-octa-decylmethylamine, n-nonadecylmethylamine, n-eico and silmethylamine, and examples of the cyclic amine compound include morpholine.

Preferably, one or more selected from methylamine, dibutylamine, triethylamine, triethanolamine, cyclohexylamine, and the like may be included, and more preferably a mixture of cyclohexylamine and dibutylamine.

In the composition of the present invention, the content of the amine-based compound as a metal corrosion inhibitor is 0.1-10 wt%, more preferably 0.5-5.0 wt%, most preferably 0.5-3.0 wt%, based on the total weight of the functional fluid composition to be.

On the other hand, if the content of the metal corrosion inhibitor is small, the effect of preventing corrosion cannot be obtained, and if the content is large, noise may be greatly generated when the master cylinder in the brake system is operated. The metal corrosion inhibitor may be used in a mixture of 0.1-1.5 wt% of a triazole-based compound and 0.5-2.5 wt% of an amine-based compound.

In addition, in the present invention, since the diamine-based noise reducing agent represented by Chemical Formula 1 described above not only exhibits an excellent noise reduction effect but also simultaneously exhibits a metal corrosion prevention effect, metal corrosion contained in the functional fluid composition of the present invention The inhibitor does not contain an amine compound and may consist of only a triazole compound, and when the metal corrosion inhibitor consists only of a triazole compound, the content of the triazole compound as a metal corrosion inhibitor is 0.1- based on the total weight of the functional fluid composition 10% by weight, more preferably 0.5-5.0% by weight, most preferably 0.5-3.0% by weight.

In the composition of the present invention, the antioxidant is used for the purpose of preventing oxidation, and any known in the art, such as phenolic, amine, sulfur, phosphorus, etc., can be used. Looking specifically at phenolic antioxidant 2, 6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tertiary-butyl-4-sec-butyl phenol, bisphenol A, dibutyl hydride hydroxyanisole, 4,4'-butylidenebis-(6-t-butyl-3-methylphenol), dibutyl hydroxy toluene, and the like, and trimethyl dihydroquinoline as an antioxidant that is a quinol.

Preferably, 3,5-di(tert-butyl)-4-hydroxytoluene (BHT) or the like can be used. The antioxidant is included in the range of 0.1-2.0% by weight based on the total weight of the functional fluid. If the content of the antioxidant is small, the antioxidant effect cannot be obtained. can occur greatly.

The features and advantages of the present invention are summarized as follows.

(a) The present invention provides a functional fluid composition comprising a monoamine-based noise reducing agent represented by the following Chemical Formula 1 as a functional fluid composition based on glycols.

[Formula 1]

In Formula 1, X and Y are integers of 1 or more, R is H or CH ₃ , and the weight average molecular weight of the compound represented by Formula 1 is 600 or more.

(b) The functional fluid composition of the present invention has an excellent noise reduction effect by using a monoamine-based compound as a noise reducing agent. In addition, even when a metal corrosion inhibitor composed of a triazole-based compound that does not contain an amine-based compound is used, there is an excellent effect of preventing metal corrosion.

1 is a photograph showing the configuration of a noise test device.
2 is an analysis showing the sound wave shape and sound pressure level (decibel) for noise in Examples and Experimental Example 1.
3 is a diagram showing the analysis of sound wave shape and sound pressure level (decibel) for noise in Examples and Experimental Example 2;
4 is a graph showing the analysis of sound wave shape and sound pressure level (decibel) for noise in Examples and Experimental Example 3;

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples according to the gist of the present invention. .

Examples and Experimental Example 1.

(1) Preparation of functional fluid composition

The functional fluid compositions of Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 were prepared with the components and composition ratios shown in Table 1-1 below.

[Table 1-1]

Meanwhile, as the monoamine-based noise reducing agent, a monoamine-based compound represented by the following Chemical Formula 1 having a molecular weight of 600 Mw was used.

[Formula 1]

The molar ratio of the compound in which R is H and the compound in which CH ₃ was 9:1.

(2) Noise test and metal corrosion test

For the noise test, a noise test device as shown in FIG. 1 was manufactured, and the noise level was evaluated while repeatedly operating/returning the brake pedal.

The noise test apparatus attached to the photograph of FIG. 1 includes a booster for generating braking force by operation of a brake pedal provided on one side of a driver's seat of a vehicle; a master cylinder receiving the force amplified from the booster and generating brake fluid pressure; wheel cylinders respectively installed on the front and rear wheels to achieve braking of the vehicle by the brake fluid pressure generated by the master cylinder; and an oil storage tank for supplying brake fluid to the master cylinder and storing brake fluid returned from the wheel cylinder. Meanwhile, the brake fluid refers to a functional fluid composition.

The noise level was measured using the noise test device, and the noise level was scored according to the evaluation criteria of Table 1-2 below, and the results are shown in Table 1-3. In addition. The sound wave shape and sound pressure level (decibel) for noise were analyzed (acoustic analysis program, WavwLab), and it is shown in FIG. 2 .

On the other hand, metal corrosion was evaluated according to the test method in Section 5.5 of KS M 2141, and the results are shown in Table 1-3.

[Table 1-2]

[Table 1-3]

Examples and Experimental Example 2.

(1) Preparation of functional fluid composition

The functional fluid compositions of Examples 2-1 to 2-5 and Comparative Examples 2-1 to 2-4 were prepared with components and composition ratios as shown in Table 2-1 below.

[Table 2-1]

Meanwhile, as the monoamine-based noise reducing agent, a monoamine-based compound represented by the following Chemical Formula 1 having a molecular weight of 1000 Mw was used.

[Formula 1]

The molar ratio of the compound in which R is H and the compound in which CH ₃ was 3:19.

(2) Noise test and metal corrosion test

The noise test and the metal corrosion test were performed according to the same methods and standards as in Examples and Experimental Example 1, and the results are shown in Table 2-2. Meanwhile, the sound wave shape and sound pressure level (decibel) for noise were analyzed (acoustic analysis program, WavwLab) and shown in FIG. 3 .

[Table 2-2]

Examples and Experimental Example 3.

(1) Preparation of functional fluid composition

The functional fluid compositions of Examples 3-1 to 3-5 and Comparative Examples 3-1 to 3-4 were prepared with components and composition ratios as shown in Table 3-1 below.

[Table 3-1]

Meanwhile, as the monoamine-based noise reducing agent, a monoamine-based compound represented by the following Chemical Formula 1 having a molecular weight of 2,000 Mw was used.

[Formula 1]

The molar ratio of the compound in which R is H and the compound in which CH ₃ was 10:31.

(2) Noise test and metal corrosion test

The noise test and the metal corrosion test were performed according to the same methods and standards as in Examples and Experimental Example 1, and the results are shown in Table 3-2. Meanwhile, the sound wave shape and sound pressure level (decibel) for noise were analyzed (acoustic analysis program, WavwLab) and shown in FIG. 4 .

[Table 3-2]

For reference, the method for evaluating metal corrosion according to the test method in Section 5.5 of KS M2141 is as follows.

(1) Corrosion test method

Prepare a metal test piece (tin alloy iron, steel, aluminum, cast iron, brass, copper) with a surface area of 25.5 cm2, polished with 320A silicon carbide so that there is no surface mark. Measure the weight of each metal piece up to 0.1 mg, and then assemble it with bolts to make electrical contact with each other.

Put each assembled metal piece and a standard SBR cup into a 475ml glass bottle and fill with 400ml of brake fluid mixed with 5vol% distilled water. Close the glass bottle tightly with a tin-plated iron lid with a ventilation hole of diameter (0.8±0.1) mm and place it in an oven at 100±2℃ for 120±2 hours.

Allow the bottle to cool at room temperature for 60 to 90 minutes, immediately remove the metal pieces, wash them with water, and wipe them with a cloth moistened with 95% ethanol one by one. Inspect the metal piece for corrosion or pan marks.

On the other hand, the metal test piece used for the corrosion test and the cup for the test of the brake solution are as shown in Tables 4 and 5 below.

[Table 4]

[Table 5]

(2) Corrosion evaluation method

When the brake fluid is tested according to the corrosion test method, the weight of the test piece is measured in units of 0.1 mg and the amount of change (mg/cm 2 ) is calculated according to Equation 4.

The change in weight should not show corrosion more than the reference value shown in Table 7 below. The outer contact surface of the metal piece shall not be so dented or roughened as to be discernible by the naked eye. However, staining or discoloration is permitted.

The brake fluid/water mixture should not harden at (23±5)℃ when the test is finished, and a crystal-like precipitate should not be formed and adhere to the wall of the glass bottle or the surface of the metal piece. This mixture should not contain more than 0.1% by volume of sediment, and the pH of this mixture should be not less than 7.0 and not more than 11.5.

[Formula 4]

[Table 6]

Claims (7)

As a functional fluid composition based on glycols, a brake fluid composition comprising 0.05 to 5.0 wt% of a monoamine-based noise reducing agent represented by the following formula (1) based on the total weight of the brake fluid composition:
[Formula 1]

In Formula 1, X and Y are integers of 1 or more, R is H or CH ₃ , and the weight average molecular weight of the compound represented by Formula 1 is 1000 or more and 2000 or less,
The content of the glycol base is 60 to 99% by weight based on the total weight of the brake fluid composition,
The glycol base includes a glycol compound and a boric acid ester compound,
The boric acid ester compound is included in a content range of 30 to 60% by weight based on the total weight of the brake fluid composition.
delete delete The method of claim 1,
A brake fluid composition comprising 0.1 to 5.0% by weight of the monoamine-based noise reducing agent of Formula 1 above.
The method of claim 1,
A brake fluid composition comprising 0.2 to 5.0% by weight of the monoamine-based noise reducing agent of Formula 1.
The method of claim 1,
A brake fluid composition comprising at least one additive of a metal corrosion inhibitor and an antioxidant.
7. The method of claim 6,
The metal corrosion inhibitor is a brake fluid composition which is a triazole-based metal corrosion inhibitor that does not contain an amine-based metal corrosion inhibitor.

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