JP6813499B2 - Cleaning agent composition, rinsing agent composition and cleaning method - Google Patents

Description

The present invention relates to a novel cleaning agent composition, a novel rinsing agent composition, and a novel cleaning method.

Various processing oils used when processing precision machine parts, optical machine parts, etc., such as cutting oil, pressing oil, drawing oil, heat treatment oil, rust preventive oil, lubricating oil, greases, waxes, etc. The dirt needs to be finally removed, which is commonly done with a solvent. In addition, fluxes used when soldering electrical and electronic parts, inks or pastes attached to screens used during substrate manufacturing, and resins attached to the mixing head of resin ejection devices can also be removed with a solvent. It is commonly done.

These cleaning and removal have many characteristics such as nonflammability, low toxicity, and excellent solubility. Therefore, 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as "trifluoroethane") It was washed with a solvent in which CFC113) or CFC113 and alcohol were mixed. However, the problem of global environmental pollution such as ozone layer depletion was pointed out for CFC113, and its production was completely abolished in Japan at the end of 1995. As an alternative to this CFC113, a mixture of 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (hereinafter). Hydrochlorofluorocarbons such as HCFC225) and 1,1-dichloro-1-fluoroethane (hereinafter referred to as HCFC141b) have been proposed, but since they also have a slight ozone depleting ability, they will be released in Japan in 2020. Its use will be banned.

In recent years, nonflammable fluorine-based solvents such as hydrofluorocarbons (hereinafter referred to as HFCs) and hydrofluoroethers (hereinafter referred to as HFEs) that do not contain chlorine atoms and have no ozone depleting ability have been proposed. Since it does not contain atoms, it has low dissolving ability and cannot be used alone as a cleaning agent. Patent Documents 1 to 3 describe HFC and HFE as a rinsing agent after cleaning with a cleaning agent in which a high boiling solvent is added to HFC and HFE. The technology used is disclosed.

Furthermore, since it has a double bond in the molecule, it generally has high reactivity with OH radicals in the atmosphere, so that the ozone depletion potential (ODP) and global warming potential (GWP) are small and it contains chlorine atoms. Patent Document 4 and Patent Document 5 disclose techniques using fluoropropens that are oil-soluble.

Japanese Unexamined Patent Publication No. 10-36894 Japanese Unexamined Patent Publication No. 10-192977 Japanese Patent No. 4267911 Japanese Unexamined Patent Publication No. 2-221388 Japanese Patent No. 5563357

However, since the GWP of HFCs and HFEs is large in the techniques of Patent Documents 1 to 3, there is a high possibility that their use will be restricted based on legal regulations from the viewpoint of preventing global warming.

The techniques of Patent Documents 4 and 5 are suitable for cleaning processing oils such as machine oils and cutting oils in which fluoropropenes are mainly composed of mineral oils, which are relatively easy to clean. On the other hand, press oils and the like, which are used under high temperature and high pressure conditions and have severe processing conditions, have a further problem in detergency because they contain a large amount of poorly soluble components such as oily agents and extreme pressure additives.

As described above, the cleaning agents proposed so far as alternatives to CFC113 have a small ozone depletion potential (ODP) and global warming potential (GWP), and are sparingly soluble in oily agents and extreme pressure additives. It has not been possible to achieve both excellent detergency for processing oils containing a large amount of components.

Therefore, the present invention exhibits high detergency especially for processing oils, fluxes, inks, pastes, resins, etc. containing a large amount of sparingly soluble components, and may cause ozone layer depletion and global warming. It is an object of the present invention to provide a small amount of cleaning agent and rinsing agent and a cleaning method suitable for the cleaning agent and / or rinsing agent.

Further, the present invention exhibits high detergency against stains containing a large amount of water-soluble components such as processing oils, fluxes, inks, pastes or resins containing a large amount of water-soluble components, and particularly stains containing a large amount of water-soluble components such as water-soluble processing oils. It is also an object to provide a cleaning agent and a rinsing agent having less risk of ozone layer depletion and global warming, and a cleaning method suitable for the cleaning agent and / or the rinsing agent.

In order to achieve the above problems, the present inventors have an organic compound having an ether bond and / or an ester bond having a vapor pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C. Evaporation suppression possessed by one or more compounds selected from the group consisting of hydrocarbons of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa (hereinafter, also referred to as “component (b)”). Taking advantage of the effect (that is, (A) the effect of suppressing the evaporation of the fluoropropen compound represented by the following general formula (1)) and the excellent stain dissolving property, a diligent study was conducted to find a cleaning agent having low flammability.

As a result, by using the fluoropropene compound (hereinafter, also referred to as "component (A)") represented by the following general formula (1) and the component (b) having different evaporation rates, the component (A) It was found that the detergency against dirt can be improved while maintaining the excellent drying characteristics of the above, and that it has a high detergency effect on the processing oil containing a large amount of sparingly soluble components.

Further, when the fatty acid ester (b1) is used as the component (b), alcohols, ketones, esters and hydrocarbons having a vapor pressure of 1.33 × 10 ³ Pa or more at 20 ° C. with the component (b). When used in combination with one or more compounds (C) selected from the group consisting of, or from the group consisting of fatty acid esters (b1) and glycol ethers, glycol ether acetates, hydroxycarboxylic acid esters, and hydrocarbons. It has been found that a higher cleaning effect can be obtained when used in combination with one or more selected compounds (b').

Further, in order to achieve the above-mentioned problems, the present inventors suppress evaporation of polyhydric alcohols (b2) having a vapor pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C. Taking advantage of its effectiveness and excellent stain-dissolving properties, we diligently studied to find a cleaning agent with low flammability.

As a result, by using the component (A) having a different evaporation rate and the polyhydric alcohol (b2) in combination, the detergency against stains can be improved while maintaining the excellent drying characteristics of the component (A), and the water solubility can be improved. It was found that it has a high cleaning effect on processing oils containing a large amount of components.

In addition, the cleaning agent composition of the present invention described later and the steam and condensate of the cleaning agent composition generated by heating the cleaning agent composition or the rinsing agent composition of the present invention are used for rinsing and / or We have found a cleaning method that can obtain a high cleaning effect by steam cleaning.

Based on the above findings, the present inventors have completed the present invention.

That is, the present invention is as follows.

[1]
(A) Fluoropropene compound represented by the following general formula (1) and (B) ether bond and / or ester bond having a vapor pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C. Organic compounds having an ester pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C., and vapor pressure at 20 ° C. of 1.33 × 10 ⁻² Pa or more 1 A cleaning agent composition containing one or more compounds selected from the group consisting of polyhydric alcohol compounds of less than .33 × 10 ³ Pa.

C ₃ H _{(6-ab) Fa} Cl _b (1)
(In the equation, a is an integer of 1 to 5, b is an integer of 1 to 3, but a + b is an integer of 2 to 6.)
[2]
The cleaning composition according to the above [1], wherein the compound (A) has a boiling point of 35 ° C. or higher and 60 ° C. or lower.

[3]
In the above [1] or [2], the content of the compound (B) is 20 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B). The cleaning agent composition described.

[4]
Further, (C) contains one or more compounds selected from the group consisting of alcohols, ketones, esters, and hydrocarbons having a vapor pressure of 1.33 × 10 ³ Pa or more at 20 ° C. [1]. The cleaning agent composition according to any one of [3].

[5]
The cleaning composition according to the above [4], which contains the compound (C) in an amount of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B). ..

[6]
The cleaning composition according to any one of [1] to [5] above, which contains the fluoropropene compound represented by the following general formula (2) as the compound (A).

(In the formula, R ¹ , R ² , and R ³ are hydrogen, fluorine, or chlorine, respectively. However, any one of R ¹ , R ² , and R ³ is chlorine.)
[7]
The cleaning composition according to the above [6], which contains one or more compounds selected as the compound (A) from the group consisting of HCFO-1233zd (Z), HCFO-1223za and CFO-1214ya.

[8]
The compound (B) includes one or more compounds selected from the group consisting of fatty acid esters (b1), polyhydric alcohols (b2), glycol ethers (b3), and hydrocarbons (b4). 1] The cleaning agent composition according to any one of [7].

[9]
The cleaning composition according to the above [8], which comprises the fatty acid esters (b1) as the compound (B).

[10]
The cleaning composition according to the above [8], which comprises the polyhydric alcohols (b2) as the compound (B).

[11]
The cleaning composition according to the above [8], which comprises the glycol ethers (b3) as the compound (B).

[12]
The cleaning composition according to the above [8], which comprises the hydrocarbons (b4) as the compound (B).

[13]
The cleaning composition according to any one of the above [8] to [12], further comprising a compound having an ester bond as the compound (B) (excluding the fatty acid esters (b1)) (b5).

[14]
As the compound (B),
(B1) fatty acid esters, and (b') glycol ether monoalkyl ethers (b3-1), glycol ether dialkyl ethers (b3-2), hydrocarbons (b4), glycol ether acetates (b5-1) ), And the cleaning agent composition according to any one of [1] to [8] above, which comprises a compound selected from one or more compounds selected from the group consisting of hydroxycarboxylic acid esters (b5-2).
Composition.

[15]
The cleaning composition according to the above [14], which comprises the fatty acid ester represented by the following general formula (3) as the fatty acid ester (b1).

(In the formula, R ⁴ is a hydrocarbon group having 5 to 15 carbon atoms, and R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms.)
[16]
Examples of the compound (b') include diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-n-butyl ether. [14] or [15] above, which comprises one or more compounds selected from the group consisting of 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, butyl lactate, decane, decene, dodecane, and dodecene. ] The cleaning agent composition according to.

[17]
The cleaning composition according to any one of [14] to [16], which comprises both the fatty acid esters (b1) and the compound (b') as the compound (B).

[18]
(A) Fluoropropene compound represented by the following general formula (1) and (B) ether bond and / or ester bond having a vapor pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C. Organic compounds having an ester pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C., and vapor pressure at 20 ° C. of 1.33 × 10 ⁻² Pa or more 1 .33 × 10 Containing one or more compounds (B) selected from the group consisting of polyhydric alcohol compounds of less than ³ Pa,
A rinse agent composition in which the content of the compound (B) is 0.01 part by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B).

C ₃ H _{(6-ab) Fa} Cl _b (1)
(In the equation, a is an integer of 1 to 5, b is an integer of 1 to 3, but a + b is an integer of 2 to 6.)
[19]
Further, (C) contains one or more compounds selected from the group consisting of alcohols, ketones, esters, and hydrocarbons having a vapor pressure of 1.33 × 10 ³ Pa or more at 20 ° C. [18]. The rinse agent composition according to.

[20]
The rinsing agent according to the above [19], which contains the compound (C) in an amount of 0.01 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B). Composition.

[21]
The rinse agent composition according to any one of [18] to [20] above, which contains the fluoropropene compound represented by the following general formula (2) as the compound (A).

(In the formula, R ¹ , R ² , and R ³ are hydrogen, fluorine, or chlorine, respectively. However, any one of R ¹ , R ² , and R ³ is chlorine.)
[22]
The rinse agent composition according to the above [21], which contains one or more compounds selected from the group consisting of HCFO-1233zd (Z), HCFO-1223za and CFO-1214ya as the compound (A).

[23]
The compound (B) includes one or more compounds selected from the group consisting of fatty acid esters (b1), polyhydric alcohols (b2), glycol ethers (b3), and hydrocarbons (b4). 18] The rinse agent composition according to any one of [22].

[24]
The cleaning composition according to the above [23], further comprising a compound having an ester bond as the compound (B) (excluding the fatty acid esters (b1)) (b5).

[25]
As the compound (B),
(B1) fatty acid esters, and (b') glycol ether monoalkyl ethers (3-1), glycol ether dialkyl ethers (3-2), hydrocarbons (b4), glycol ether acetates (b5-1) ), And the rinse agent composition according to any one of [18] to [23] above, which comprises a compound selected from one or more compounds selected from the group consisting of hydroxycarboxylic acid esters (b5-2).

[26]
The rinse agent composition according to the above [25], which comprises the fatty acid ester represented by the following general formula (3) as the fatty acid ester (b1).

(In the formula, R ⁴ is a hydrocarbon group having 5 to 15 carbon atoms, and R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms.)
[27]
Examples of the compound (b') include diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-n-butyl ether. [25] or [26] above, which comprises one or more compounds selected from the group consisting of 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, butyl lactate, decane, decene, dodecane, and dodecene. ] The rinse agent composition according to.

[28]
The rinse agent composition according to any one of [25] to [27], which comprises both the fatty acid esters (b1) and the compound (b') as the compound (B).

[29]
A cleaning method comprising the step (1) of cleaning a dirty object to be cleaned with the cleaning agent composition according to any one of [1] to [17].

[30]
The step (2) of rinsing and / or steam-cleaning the object to be cleaned which has undergone the step (1) using the vapor of the cleaning agent composition and / or a condensate of the vapor is further included in the above [29]. ] The cleaning method described in.

[31]
The cleaning method according to [30], wherein in the step (2), the rinse agent composition according to any one of [18] to [28] is used as the rinse agent.

According to the present invention, it is possible to provide a cleaning agent composition and / or a rinsing agent composition that exerts an excellent cleaning effect. In particular, a cleaning agent composition, a rinsing agent composition, and a cleaning agent composition thereof, which exhibit high detergency for processing oils containing a large amount of sparingly soluble components and have excellent detergency with less risk of ozone layer depletion and global warming. And / or a cleaning method suitable for the rinse composition can be provided. Further, a cleaning agent composition and a rinsing agent composition which show high detergency against stains containing a large amount of water-soluble components such as water-soluble processing oil, and have excellent detergency with less risk of ozone layer depletion and global warming. A cleaning method suitable for the cleaning agent composition and / or the rinsing agent composition can also be provided.

Hereinafter, a mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of the gist thereof.

In the present specification, cleaning means removing dirt adhering to an object to be cleaned to a level that does not affect the next step. Further, rinsing is to replace the cleaning agent containing a stain component adhering to the object to be cleaned with a solvent containing no stain component after cleaning. In addition, shower rinsing is to discharge a liquid or mist-like solvent from one or more discharge ports after cleaning and apply it to the object to be cleaned to replace the cleaning agent adhering to the object to be cleaned with the solvent. .. Further, steam cleaning is to remove a small amount of dirt components remaining on the surface of the object to be cleaned with a liquid that condenses on the surface of the object to be cleaned due to the temperature difference between the object to be cleaned and steam.

The cleaning agent composition and the rinsing agent composition of the present embodiment have (A) a fluoropropene compound (component (A)) represented by the following general formula (1) and (B) a vapor pressure of 1.33 × 10 at 20 ° C. ^-2 Pa or more and 1.33 x 10 ³ Pa or more and organic compounds having ether bonds and / or ester bonds, vapor pressure at 20 ° C is 1.33 x 10 ^-2 Pa or more and 1.33 x 10 less than ³ Pa hydrocarbons One or more compounds selected from the group consisting of hydrogens and polyhydric alcohols having a vapor pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C (hereinafter, “component (B)”). It may be described as).

C ₃ H _{(6-ab) Fa} Cl _b (1)
(In the equation, a is an integer of 1 to 5, b is an integer of 1 to 3, but a + b is an integer of 2 to 6.)
These components will be described.

[Component (A)]
The component (A) is a compound having 3 carbon atoms and having a part or all of hydrogen atoms of hydrocarbons containing a double bond in the molecule substituted with a fluorine atom or a chlorine atom, and has the following general formula. Any type of fluoropropene compound shown in (1) may be used.

C ₃ H _{(6-ab) Fa} Cl _b (1)
(In the formula, a is an integer of 1 to 5, b is an integer of 1 to 3, but a + b is an integer of 2 to 6.) Among them, in order to exhibit an excellent cleaning effect, It is preferable that a is an integer of 2 to 5, b is an integer of 1 to 2, and a + b is an integer of 3 to 6. The component (A) is illustrated below.

Specific examples of the fluoropropene compound include chlorofluoropropene which does not contain hydrogen in the molecule and hydrochlorofluoropropene which contains hydrogen in the molecule.

Specific examples of chlorofluoropropene (CFO) include
CFO-1214ya (CF ₃ -CF = CCl ₂ ),
E-form and Z-form of CFO-1214xb (CF ₃ -CF = CClF),
CFO-1215yb (CF _3- CCl = CClF) E-form and Z-form,
CFO-1215xc (CF ₃ -CCl = CF ₂ ),
And so on.

Specific examples of hydrochlorofluoropropene (HCFO) include
E-form and Z-form of HCFO-1223xd (CF ₃ -CCl = CHCl),
E-form and Z-form of HCFO-1223zb (CCLF _2- CH = CClF),
E-form and Z-form of HCFO-1223yd (CCLF ₂ -CF = CHCl),
HCFO-1223zc (CCl ₂ F-CH = CF ₂ ),
HCFO-1223za (CF _3- CH = CCl ₂ ),
HCFO-1232xf (CCLF ₂ -CCl = CH ₂ ),
HCFO-1232yf (CCl ₂ F-CF = CH ₂ ),
HCFO-1233xf (CF _3- CCl = CH ₂ ),
E-form and Z-form of HCFO-1233zd (CF _3- CH = CHCl),
E-form and Z-form of HCFO-1241yd (CH ₃ -CF = CHCl),
And so on.

In the cleaning agent composition and the rinsing agent composition of the present embodiment, the component (A) may be one kind of fluoropropene compound or a combination of two or more kinds of fluoropropene compounds. Among them, when used as a steam cleaning agent, the boiling point (usually the boiling point at 1 atm) is 30 ° C. or higher and 70 ° C. in consideration of the balance between drying property and evaporation consumption. It is preferable to use the following component (A), and further preferably the component (A) having a boiling point of 35 ° C. or higher and 60 ° C. or lower, particularly the component (A) having a boiling point of 40 ° C. or higher and 60 ° C. or lower. ) Is preferably used.

In addition, the component (A) is preferably a fluoropropene compound represented by the following general formula (2) in that it has excellent metal stability and exhibits an excellent cleaning effect.

(In the formula, R ¹ , R ² , and R ³ are hydrogen, fluorine, or chlorine, respectively. However, any one of R ¹ , R ² , and R ³ is chlorine.)
Among the fluoropropene compounds represented by the general formula (2), R ¹ is preferably hydrogen or chlorine, R ² is preferably hydrogen or fluorine, and R ³ is preferably hydrogen or chlorine. , R ¹ or R ³ is preferably chlorine.

Specific examples of the CFO and HCFO specified by the general formula (2) include HCFO-1233zd (Z), HCFO-1223za and CFO-1214ya. Among them, HCFO having more excellent metal stability is preferable, and HCFO-1233zd (Z) is particularly preferable.

[Component (B)]
In the cleaning agent and rinsing agent of the present embodiment, an organic compound having an ether bond and / or an ester bond having a vapor pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C., 20 ° C. Polyhydric alcohols having a vapor pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa, and a vapor pressure of 1.33 × 10 ⁻² Pa or more and 1.33 × 10 ³ Pa at 20 ° C. One or more compounds (B) (component (B)) selected from the group consisting of less than or less hydrocarbons are used. The component (B) may be one or more compounds selected from the group consisting of the organic compound and the hydrocarbons (hereinafter, also referred to as “component (b)”), and the polyhydric alcohols. (Hereinafter, it may also be referred to as “component (b2)”), and may be component (b) and component (b2). When the vapor pressure of the component (B) is in this range, the cleaning agent composition having excellent rinsability and detergency according to the present embodiment can be obtained. The preferred range of vapor pressure is 6.66 × 10 ⁻² or more and 6.66 × 10 ² Pa or less, more preferably 1.33 × 10 ^-1 Pa or more and 1.33 × 10 ² Pa or less at 20 ° C. is there. Hereinafter, the component (B) will be exemplified for each type of solvent.

The specific gravity of the component (B) is preferably within the range of ± 0.8 of the specific gravity of the component (A) to be used in combination in order to improve the compatibility of the component (B) with the component (A). It is preferably in the range of ± 0.7. In particular, the compatibility of the component (A) with other components is highly temperature-dependent, and in order to maintain the compatibility at low temperatures, the difference between the specific gravity of the component (A) and the specific gravity of the other component used in combination is reduced. This is very important.

The organic compound having an ether bond used in the cleaning agent and the rinsing agent of the present embodiment is a compound containing one or more ether bonds (COC) in the molecular structure, and is an organic compound having an ester bond. A compound is a compound containing one or more ester bonds (-COO-) in its molecular structure. Therefore, among the component (B), the organic compound having an ether bond and / or an ester bond is a compound having one or both of an ether bond and an ester bond.

The component (B) described below includes a fatty acid ester (b1) (hereinafter, also referred to as “component (b1)”) capable of further improving the cleaning effect, and polyhydric alcohols (b2) (hereinafter, “component”). (B2) ”) and the component (b ′) selected from a specific compound group can be mentioned.

As the component (b'), as a compound having an ether bond, glycol ether monoalkyl ethers (hereinafter, also referred to as "component (b3-1)") and glycol ether dialkyl ethers (hereinafter, "component (b3-)"). 2) ”(These may also be collectively referred to as“ glycol ethers (b3) ”or“ component (b3) ”).

Further, examples of the component (b') include hydrocarbons (b4) (hereinafter, also referred to as "component (b4)").

Further, as the component (b'), as a compound having an ester bond, glycol ether acetates (hereinafter, also referred to as "component (b5-1)") and hydroxycarboxylic acid esters (hereinafter, "component (b5-)"). 2) ”is also described.)

As will be described below, the component (b1), the component (b3-1), the component (b3-2), the component (b4), the component (b5-1), and the component (b5-2) are Each of them can be used alone as the component (b), or a plurality of types of each component can be mixed and used depending on the intended use. Next, these components will be described.

<< Compound with ester bond >>
Examples of the compound having an ester bond include fatty acid esters.

<Component (b1); Fatty acid ester>
Among the compounds having an ester bond, the component (b) may contain a fatty acid ester (b1) (hereinafter, may be simply referred to as a component (b1)) in order to exhibit a particularly excellent cleaning effect. Among them, it is preferable to contain a saturated or unsaturated fatty acid alkyl ester having a total carbon number of 5 to 20. Among the components (b1), it is particularly preferable to contain the fatty acid ester represented by the following general formula (3).

(In the formula, R ⁴ is a hydrocarbon group having 5 to 15 carbon atoms, and R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms.)
R ⁴ is a hydrocarbon group having 5 to 15 carbon atoms. Above all, in order to exhibit an excellent cleaning effect, a chain-type saturated hydrocarbon group having 5 to 15 carbon atoms or a chain-type unsaturated hydrocarbon group having 5 to 15 carbon atoms is preferable. Among them, an alkyl group having 6 to 15 carbon atoms or an alkenyl group having 7 to 15 carbon atoms is preferable, and an alkyl group having 7 to 12 carbon atoms or an alkenyl group having 7 to 12 carbon atoms is more preferable. , An alkyl group having 8 to 12 carbon atoms or an alkenyl group having 10 to 12 carbon atoms is more preferable.

R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms, for example, a hydrocarbon group having 1 to 2 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and preferably a methyl group. Especially preferable. The reason why these are preferable is that the influence on the packings used in the cleaning apparatus and the like and the elastomer material contained in the object to be cleaned is small.

Specific examples of the fatty acid ester represented by the general formula (3) include methyl caproate, ethyl caproate, propyl caproate, butyl caproate, methyl enanthate, ethyl enanthate, propyl enanthate, butyl enanthate, and capryl. Methyl acid, ethyl caprylate, propyl caprylate, butyl caprylate, methyl pelargonate, ethyl pelargonate, propyl pelargone, butyl pelargone, methyl caprate, ethyl caprate, propyl caprate, butyl caprate, decene Methyl acid, ethyl decenoate, propyl decenoate, butyl decenoate, methyl undecanoate, ethyl undecanoate, propyl undecanoate, butyl undecanoate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, methyl dodecate , Ethyl dodecenoate, propyl dodecate, butyl dodecate, methyl tridecanoate, ethyl tridecanoate, methyl myristate, ethyl myristate, methyl pentadecanoate, ethyl pentadecanoate, methyl palmitate, ethyl palmitate and the like. ..

Among these, as a component (b1) having particularly excellent oil solubility and a relatively low boiling point, methyl caprate, ethyl caprate, methyl laurate, ethyl laurate, methyl decenoate, ethyl decenoate, methyl dodecenoate, todecene Ethyl acid acid and the like are preferable, and methyl caprate, methyl laurate, methyl decenoate and methyl dodecenoate are preferable, and methyl decenoate and methyl dodecenoate having a lower melting point are preferable. As the fatty acid ester, one type may be used, or two or more types may be used in combination.

This fatty acid ester (b1) can be used alone as the component (b), or can be used in combination with the component (b') described in detail below. In addition, the component (b1) can be used in combination with the component (b2) described in detail below, or can be used in combination with the component (b') and the component (b2).

<Ingredient (b2): Multivalent alcohols>
The polyhydric alcohols (b2) preferably have two hydroxyl groups in one molecule.

The carbon number of the polyhydric alcohol (b2) is preferably 4 to 8, more preferably 5 to 7.

The total number of carbon atoms bonded to a plurality of carbon atoms to which a hydroxyl group is bonded per molecule of polyvalent alcohol (b2) (for example, C ^a H _3- C ^b H (OH) -C). ^c H _2- C ^{d In} the case of polyvalent alcohols represented by H ₂ (OH), this value is ((the number of carbon atoms bonded to carbon atom C ^b ) + (bonded to carbon atom C ^d ). The number of carbon atoms) = 2 + 1 =) 3. The number of carbon atoms C ^c is counted in duplicate.) Is preferably 3 to 6, more preferably 4 to 5. Also, preferably, all hydroxyl groups are bonded to carbon atoms bonded to two or three carbon atoms.

The hydrocarbons constituting the polyhydric alcohols (b2) are preferably saturated hydrocarbons.

Specific examples of the polyhydric alcohols (b2) include 2,3-butanediol, 2-methyl-1,2-propanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, and 2, , 4-Pentanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol and the like. Of these, 3-methyl-1,3-butanediol and 2-methyl-2,4-pentanediol are preferable, and 2-methyl-2,4-pentanediol is particularly preferable.

<< Compound with ether bond >>
Examples of the compound having an ether bond include glycol ether monoalkyl ethers (component (b3-1)) and glycol ether dialkyl ethers (component (b3-2)).

<Component (b3); Glycol ethers>
When the component (b) is used as the component (B), the glycol ether monoalkyl ethers (component (b3-1)), the glycol ether dialkyl ethers (component (b3-2)), etc. are used alone as the component (b). ) Can be used. Above all, it is particularly preferable to use it in combination with the component (b1). However, among the glycol ether monoalkyl ethers (component (b3-1)), a single compound or a plurality of types of compounds can be used in combination. Similarly, among glycol ether dialkyl ethers (component (b3-2)), a single compound or a plurality of types of compounds can be used in combination.

(Component (b3-1); Glycol ethers Monoalkyl ethers)
Glycol ethers Monoalkyl ethers (component (b3-1)) are aliphatic or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms, and one hydrogen of the hydroxyl group. Is a compound in which is substituted with a hydrocarbon residue or a hydrocarbon residue containing an ether bond. Although not particularly limited, glycol ethers and monoalkyl ethers having 3 to 14 carbon atoms are preferable.

Specific examples of glycol ether monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, and ethylene. Glycol mono-i-butyl ether, ethylene glycol mono-n-hexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol mono-i-propyl ether, tri Ethylene glycol mono-n-butyl ether, triethylene glycol mono-i-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol Mono-i-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-i-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-i-butyl ether , Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-i-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-i- Examples thereof include butyl ether, tripropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol and the like.

Further, glycol ether monoalkyl ethers such as 3-methoxybutanol and 3-methyl-3-methoxybutanol are compounds which have particularly good detergency against various stains and can obtain an excellent detergency effect.

(Component (b3-1-1); Hydrophilic glycol ethers Monoalkyl ethers)
Among the above glycol ether monoalkyl ethers (component (b3-1)), as a component suitable for cleaning water-soluble stains such as water-soluble processing oils,
Requirement (1): A component that satisfies the condition that phase separation does not occur when 60 parts by mass of glycol ether monoalkyl ethers and 40 parts by mass of water are mixed at 30 ° C. (hereinafter, hydrophilic glycol ether monoalkyl ethers). (In some cases, it may be referred to as component (b3-1-1)), and this component (b3-1-1) is preferably used.
Requirement (2); Satisfies that it can be mixed with water in any proportion at 30 ° C.

Specific examples of hydrophilic glycol ether monoalkyl ethers (component (b3-1-1)) are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-. i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-i-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, diethylene glycol mono-n -Butyl ether, diethylene glycol mono-i-butyl ether, triethylene glycol monomethyl ether, triethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether , 3-methoxybutanol, 3-methyl-3-methoxybutanol and the like can be mentioned. These hydrophilic glycol ether monoalkyl ethers (component (b3-1-1)) are components that satisfy not only the above requirement (1) but also the requirement (2).

Among these, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-i-butyl ether, diethylene glycol mono-n- Butyl ether, diethylene glycol mono-i-butyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol have detergency against various stains. It is an excellent compound.

(Component (b3-2); glycol ether dialkyl ethers)
Glycol ethers Dialkyl ethers (component (b3-2)) are aliphatic or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms, and both of the hydrogens of the two hydroxyl groups are Is a compound in which is substituted with a hydrocarbon residue or a hydrocarbon residue containing an ether bond. Although not particularly limited, glycol ether dialkyl ethers having 4 to 17 carbon atoms are preferable.

Specific examples of glycol ether dialkyl ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. Diethylene glycol diethyl ether and dipropylene glycol dimethyl ether have good detergency against various stains.

Furthermore, glycol ether dialkyl ethers such as diethylene glycol di-n-butyl ether are compounds that have good detergency against processing oils containing a large amount of sparingly soluble components and can obtain excellent detergency.

(Component (b3-2-1); Hydrophilic glycol ethers Dialkyl ethers)
Among the above glycol ether dialkyl ethers (component (b3-2)), as a component suitable for cleaning water-soluble stains such as water-soluble processing oils,
Requirement (1'); A component that satisfies the condition that phase separation does not occur when 60 parts by mass of glycol ether dialkyl ethers and 40 parts by mass of water are mixed at 30 ° C. (hereinafter, hydrophilic glycol ether dialkyl ethers). (It may be referred to as a component (b3-2-1)), and this component (b3-2-1) is preferably mixed with water at an arbitrary ratio at 30 ° C. (2). Fulfill.

Specific examples of hydrophilic glycol ether dialkyl ethers (component (b3-2-1) include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and the like. ..

Among these, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and diethylene glycol diethyl ether are compounds having excellent detergency against various stains.

<Component (b4); Hydrocarbons>
Examples of the hydrocarbons (component (b4)) include aliphatic hydrocarbons having 10 to 16 carbon atoms and alicyclic hydrocarbons. Hydrocarbons (component (b4)) can be used alone as component (b). Above all, it is particularly preferable to use it in combination with the component (b1). However, among the hydrocarbons, a single compound or a plurality of types of compounds can be used in combination.

Specific examples of hydrocarbons are decane, decane, undecane, undecane, dodecane, dodecane, tridecane, tetradecane, pentadecane, mentan, bicyclohexyl, cyclododecane, 2,2,4,4,6,8,8- Examples thereof include heptamethylnonane. Among them, decane, decene, undecane, undecene, dodecane, dodecane, tridecane, and tetradecane are preferable, and decane, decene, dodecane, and dodecene are more preferable, from the viewpoint of excellent detergency, drying property, and compatibility.

<< Compound with ester bond >>
Examples of the compound having an ester bond include -n-butyl acetate, isoamyl acetate, -2-ethylhexyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, ethyl lactate, and propyl lactate, in addition to the fatty acid ester (b1). Butyl lactate, γ-butyrolactone, dimethyl succinate, dimethyl glutarate, dimethyl adipate, 3-methyl-3-methoxybutyl acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monobutyl ether acetate, etc. Be done. In particular, glycol ether acetates and hydroxycarboxylic acid esters are preferable. Among these, there are preferable compounds, which will be described below.

<Component (b5); Compound having an ester bond (excluding the component (b1))>
Among the compounds having an ester bond, in addition to the above component (b1), as a compound exhibiting a particularly excellent effect, glycol ether acetates (component (b5-1)) or hydroxycarboxylic acid esters (component (component (b1)). b5-2)) and the like can be mentioned. Glycol ether acetates (component (b5-1)), hydroxycarboxylic acid esters (component (b5-2)) and the like can be used alone as component (b). Above all, it is particularly preferable to use it in combination with the component (b1). However, among the glycol ether acetates (component (b5-1)), a single compound or a plurality of types of compounds can be used in combination. Similarly, among the hydroxycarboxylic acid esters (component (b5-2)), a single compound or a plurality of types of compounds can be used in combination.

(Component (b5-1); Glycol ether acetates)
Glycol ether acetates are compounds in which glycol ethers having a hydroxyl group are acetylated. Although not particularly limited, glycol ether acetates having 5 to 12 carbon atoms are preferable. Specific examples include acetates of monoalkyl ethers such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like. be able to. The glycol ether acetates used in the present embodiment include dipropylene glycol monomethyl ether acetate, dipropylene glycol mono-n-propyl ether acetate, and dipropylene glycol mono-n-butyl ether acetate, which do not produce alkoxyacetic acid in the metabolic system in the human body. , 3-Methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate and the like are less toxic and preferred.

(Component (b5-2); Hydroxycarboxylic Acid Esters)
Hydroxycarboxylic acid esters are ester compounds having a hydroxyl group. Although not particularly limited, hydroxycarboxylic acid esters having 4 to 20 carbon atoms are preferable. Specific examples include lactic acid ester, malic acid ester, tartrate ester, citric acid ester, glycol monoester, glycerin monoester, glycerin diester, ricinolic acid ester, castor oil and the like.

Among the above-mentioned hydroxycarboxylic acid esters, lactic acid esters are particularly preferable, and specific examples thereof include methyl lactate, ethyl lactate, propyl lactate, butyl lactate, and pentyl lactate.

[Preferable combination of component (B) (1); when component (b1) is used]
In the present invention, the above-exemplified component (B) can be used. Above all, when used in combination with the component (A), the component (B) is the component (b) and the component (b) is excellent in compatibility with the component (A) and particularly excellent cleaning effect is exhibited. ), It is preferable to use the component (b1) (fatty acid ester), and it is particularly preferable to use the fatty acid ester represented by the general formula (3).

In the present invention, when the component (B) is the component (b), the entire amount of the component (b) can be composed of the component (b1). Further, in the above-mentioned component (b), the entire amount of the component (b) may be composed of a component other than the component (b1). However, depending on the object to be cleaned and the cleaning device used, the component (b) includes the above component (b1) and glycol ethers (component (b3)) (specifically, glycol ether monoalkyl ethers (component). (B3-1)) and / or glycol ether dialkyl ethers (component (b3-2))), hydrocarbons (component (b4)), glycol ether acetates (component (b5-1)), and hydroxycarboxylics. It is also possible to use in combination with one or more compounds (component (b')) selected from the group consisting of acid esters (component (b5-2)).

When the component (b1) and the component (b') are combined, the component (b1) is set to 100% by mass when the total amount of the component (b) (the total mass of the component (b1) and the component (b')) is 100% by mass. It is preferable that the content is 10% by mass or more and 90% by mass or less, and the component (b') is 10% by mass or more and 90% by mass or less. When the mass ratio of the component (b1) in the component (b) is 10% by mass or more, more preferable oil solubility can be obtained, and when it is 90% by mass or less, more preferable detergency against various stains can be obtained. .. Considering the balance between oil solubility and detergency against various stains, it is more preferable that the component (b1) is 20% by mass or more and 80% by mass or less, and the component (b1) is 30% by mass or more and 70% by mass or more. % Or less is preferable. The suitable blending ratio of the component (b1) and the component (b') does not change regardless of whether the cleaning agent composition or the rinsing agent composition is used.

When a member containing an elastomer or other resin (hereinafter, may be a resin member) is used for the object to be cleaned, the cleaning device, etc., damage to the resin member is suppressed and excellent. In order to exert a cleaning effect, the component (b) is at least one selected from glycol ether monoalkyl ethers (component (b3-1)) and glycol ether dialkyl ethers (component (b3-2)). It is particularly preferable to contain glycol ethers (b3). In this case, when the total amount of the component (b) is 100% by mass, the component (b1) is 10% by mass or more and 90% by mass or less, the glycol ethers (b3) is 10% by mass or more and 90% by mass or less, and the component. It is preferable that the component (b4), the component (b5-1), and the other component (x) selected from the component (b5-2) are 0% by mass or more and 40% by mass or less. By satisfying this range, good oil solubility (cleanability) can be exhibited while suppressing damage to the resin member. In order to further enhance the damage suppressing effect of the resin member and the oil solubility (cleanability), the component (b1) is 50% by mass or more and 90% by mass or less, and the glycol ethers (b3) are 10% by mass or more and 50. It is more preferable that the mass% or less, the other component (x) is 0% by mass or more and 10% by mass or less, the component (b1) is 55% by mass or more and 95% by mass or less, and the glycol ethers (b3) are 15. It is more preferable that the mass% or more and 45% by mass or less, and the other component (x) is 0% by mass. The suitable blending ratio in these components (b) does not change regardless of whether the cleaning agent composition or the rinsing agent composition is used. Further, the cleaning agent composition and the rinsing agent composition satisfying the blending ratio can be naturally used for cleaning and rinsing other than the resin member.

Further, when cleaning water-soluble stains, for example, stains such as water-soluble processing oil used during processing of precision machine parts, optical machine parts, etc., the component (b1) is used as the component (b). Glycol ethers (component (b3-1) and / or component (b3-2)) are used, and among the glycol ethers, the hydrophilic glycol ether monoalkyl ether (component (b3-1-1)) is used. ), And hydrophilic glycol ethers selected from hydrophilic glycol ether dialkyl ethers (component (b3-2-1)) can also be used. In this case, when the total amount of the component (b) is 100% by mass, the component (b1) is 10% by mass or more and 90% by mass or less, the hydrophilic glycol ethers are 10% by mass or more and 90% by mass or less, and the others. The component (x) of is preferably 0% by mass or more and 40% by mass or less. By satisfying this range, the detergency against soluble stains and the detergency against other stains can be further improved. In order to further enhance this cleaning effect, the component (b1) is 50% by mass or more and 90% by mass or less, the hydrophilic glycol ethers are 10% by mass or more and 50% by mass or less, and the other component (x) is 0% by mass. It is more preferably% or more and 10% by mass or less, the component (b1) is 55% by mass or more and 95% by mass or less, the glycol ethers are 15% by mass or more and 45% by mass or less, and the other component (x) is 0. It is more preferably mass%, and the component (b1) is 55% by mass or more and 75% by mass or less, the glycol ethers are 25% by mass or more and 45% by mass or less, and the other component (x) is 0% by mass. Is particularly preferred. The suitable blending ratio in these components (b) does not change regardless of whether the cleaning agent composition or the rinsing agent composition is used. Further, the cleaning agent composition and the rinsing agent composition satisfying the blending ratio can be naturally used for cleaning and rinsing other than stains such as water-soluble processing oil.

[Preferable combination of component (B) (2); when component (b2) is used]
When cleaning water-soluble stains, for example, water-soluble processing oil used when processing precision machine parts, optical machine parts, etc., flux components adhering during the manufacture of electronic parts, etc., polyhydric alcohol is used as component (B). It is preferable to use class (component (b2)). In this case, the entire amount of the component (B) can be used as the component (b2).

In addition, the above-mentioned water-soluble stains and sparingly soluble stains, for example, oil-based processing oils used during processing of precision machine parts, optical machine parts, etc., particularly sparingly soluble components such as oil-based agents and extreme pressure additives. When cleaning a large amount of dirt and the like, it is preferable to use the component (b2) together with the component (b1) and the component (b4). Further, depending on the object to be cleaned and the cleaning device used, the component (B) includes the component (b2), the component (b1) and the component (b4), and other components (z) (specifically, , Component (b3-1), component (b3-2), component (b5-1), and one or more components selected from the group consisting of component (b5-2)) can also be used in combination. In this case, when the total amount of the component (B) is 100% by mass, the component (b2) is 20% by mass or more and 80% by mass or less, and the total of the component (b1) and the component (b4) is 20% by mass. It is preferable that the content is 80% by mass or less and the component (z) is 0% by mass or more and 30% by mass or less, the component (b2) is 30% by mass or more and 70% by mass or less, the component (b1) and the component (b4). ) Is preferably 30% by mass or more and 70% by mass or less, the component (z) is preferably 0% by mass or more and 30% by mass or less, and the component (b2) is 40% by mass or more and 60% by mass or less. It is preferable that the total of b1) and the component (b4) is 40% by mass or more and 60% by mass or less, and the component (z) is 0% by mass or more and 20% by mass or less. Most preferably, the component (z) is 0% by mass, the component (b2) is 40% by mass or more and 60% by mass or less, and the total of the component (b1) and the component (b4) is 40% by mass or more and 60% by mass. It is a case where it becomes% or less.

[Preferable combination of component (B) (3); when component (b4) is used]
In addition, stains containing a large amount of sparingly soluble components such as oil-based agents and extreme pressure additives, for example, various processing oils used when processing precision machine parts, optical machine parts, etc., specifically, cutting oils and presses. For stains such as oils, drawing oils, heat-treated oils, rust preventive oils, lubricating oils, greases, waxes, etc., especially when cleaning stains containing a large amount of sparingly soluble components such as oily agents and extreme pressure additives. It is preferable that the component (B) is the component (b) and hydrocarbons (component (b4)) are used as the component (b). In this case, the entire amount of the component (b) can be used as the component (b4). Further, depending on the object to be cleaned and the cleaning device to be used, the component (b) includes the component (b4) and other components (y) (specifically, the component (b1) and the component (b3-1). One or more components selected from the group consisting of the component (b3-2), the component (b5-1), and the component (b5-2)) can also be used in combination.

When the component (b4) is an essential component, when the total amount of the component (b) is 100% by mass, the component (b4) is 10% by mass or more and 100% by mass or less, and the other component (y) is 0. It is preferably mass% or more and 90 mass% or less. By satisfying the above-mentioned compounding ratio, the cleaning effect can be further enhanced. In order to further enhance the cleaning effect on stains containing a large amount of the poorly soluble component, the component (b4) is set to 30% by mass or more and 100% by mass or less, and the other component (y) is set to 0% by mass or more and 70% by mass or less. It is more preferable that the component (b4) is 40% by mass or more and 100% by mass or less, the other component (y) is 0% by mass or more and 60% by mass or less, and the component (b4) is 70% by mass or more. It is more preferably 100% by mass or less, the other component (y) is 0% by mass or more and 30% by mass or less, and the component (b4) is particularly preferably 100% by mass.

Further, when the object to be cleaned is a substance in which the poorly soluble component is attached to the resin member, the component (b4) is 20 when the total amount of the component (b) is 100% by mass. It is preferable that the mass% or more and 80% by mass or less, and the other component (y) is 20% by mass or more and 80% by mass or less. By satisfying the blending ratio, it is possible to enhance the cleaning effect of the poorly soluble component while suppressing the deterioration of the resin member. In order to further enhance the effect of preventing deterioration of the resin member and further enhance the cleaning effect of the poorly soluble component, the component (b4) is 30% by mass or more and 70% by mass or less, and the other component (y) is 30. It is more preferably mass% or more and 70% by mass or less.

It should be noted that the suitable blending ratio in these components (B) or component (b) does not change regardless of whether it is the cleaning agent composition or the rinsing agent composition. Further, the cleaning agent composition and the rinsing agent composition satisfying the blending ratio can be naturally used for cleaning and rinsing other than stains such as poorly soluble components.

[Component (C)]
In the cleaning agent composition and the rinsing agent composition of the present embodiment, if the component (A) and the component (B) are essential components, other components are blended as long as the effects of the present invention are not impaired. You can also do it. In particular, in the present invention, one or more compounds selected from the group consisting of alcohols, ketones, esters and hydrocarbons having a vapor pressure of 1.33 × 10 ³ Pa or more at 20 ° C. are compounded (hereinafter, hereinafter, It may be simply the component (C)).

Specific examples of alcohols include methanol, ethanol, n-propanol, isopropanol and the like.

Examples of the ketones include acetone having carbon atoms and methyl ethyl ketone.

Examples of the esters include ethyl formate, propyl formate, isobutyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate and the like.

Hydrocarbons include n-hexane, isohexane, cyclohexane, cyclohexene, 2-methylpentane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 2,4-dimethylpentane, isooctane. Etc. can be mentioned.

In the present invention, when the component (C) is used, the specific gravity of the component (C) is in the range of ± 0.8 of the specific gravity of the component (A) used in combination in order to improve the compatibility with the component (A). It is preferable to enter the range of ± 0.7. In particular, the compatibility of the component (A) with other components is highly temperature-dependent, and in order to maintain the compatibility at low temperatures, the difference between the specific gravity of the component (A) and the specific gravity of the other component used in combination is reduced. This is very important.

The boiling point of the component (C) is preferably in the range of ± 40 ° C., and further preferably in the range of ± 30 ° C., of the boiling point of the component (A) to be used in combination in order to reduce the composition fluctuation during use. ..

When the component (C) is used, it is preferable that the component (A) to be used in combination is an azeotropic composition or an azeotropic composition having a composition similar thereto.

Among the components (C), hydrocarbons are particularly preferable components. Above all, it is preferable to use hydrocarbons as the component (C) for cleaning the processing oil.

[Other compounding agents]
In the cleaning agent composition and the rinsing agent composition of the present embodiment, various auxiliary agents (hereinafter, also referred to as “component (D)”), for example, non-chlorine type, are used as necessary within a range that does not impair the effects of the present application. Fluorine compounds, stabilizers, antioxidants, ultraviolet absorbers, surfactants, antifoaming agents and the like may be added as necessary.

Specific examples of various auxiliary agents that can be added to the cleaning agent of the present invention are shown below.

<Non-chlorine fluorine compound>
The non-chlorine-based fluorine compound is a fluorine compound in which some of the hydrogen atoms of hydrocarbons and ethers are replaced only with fluorine atoms and does not contain chlorine atoms. For example, it is specified by the following general formula (4). Cyclic HFC, chain HFC specified in (5), or HFE specified in (6), a compound consisting of carbon atom, hydrogen atom, oxygen atom, fluorine atom, which does not contain chlorine atom, and among these Examples thereof include a combination of two or more compounds selected from the above.

C _n H _2n-m F _m (4)
(In the formula, an integer of 4 ≦ n ≦ 6, 5 ≦ m ≦ 2n-1 is shown)
C _x H _{2x + 2-y} F _y (5)
(In the formula, an integer of 4 ≦ x ≦ 6, 5 ≦ y ≦ 2x + 2 is shown)
C _s F _{2s + 1} OR (6)
(In the formula, 4 ≦ s ≦ 6, R is an alkyl group having 1 to 3 carbon atoms)
Specific examples of the cyclic HFC include 3H, 4H, 4H-perfluorocyclobutane, 4H, 5H, 5H-perfluorocyclopentane, 5H, 6H, 6H-perfluorocyclohexane and the like.

Specific examples of chained HFC include 1H, 2H, 3H, 4H-perfluorobutane, 1H, 2H-perfluorobutane, 1H, 3H-perfluorobutane, 2H, 3H-perfluorobutane, 4H, 4H-perfluoro. Butane, 1H, 1H, 3H-perfluorobutane, 1H, 1H, 4H-perfluorobutane, 1H, 2H, 3H-perfluorobutane, 1H, 1H, 4H-perfluorobutane, 2H, 2H, 4H, 4H, 4H-Perfluorobutane, 1H, 2H-Perfluoropentane, 1H, 4H-Perfluoropentane, 2H, 3H-Perfluoropentane, 2H, 4H-Perfluoropentane, 2H, 5H-Perfluoropentane, 1H, 2H, 3H-Perfluoropentane, 1H, 3H, 5H-Perfluoropentane, 1H, 5H, 5H-Perfluoropentane, 2H, 2H, 4H-Perfluoropentane, 1H, 2H, 4H, 5H-Perfluoropentane, 1H, 4H, 5H, 5H, 5H-perfluoropentane, 1H, 2H-perfluorohexane, 2H, 3H-perfluorohexane, 2H, 4H-perfluorohexane, 2H, 5H-perfluorohexane, 3H, 4H-perfluoro Examples thereof include hexane.

Specific examples of HFE include methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, methyl perfluoropentyl ether, methyl perfluorocyclohexyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, ethyl perfluoropentyl ether and the like. Can be done.

<Stabilizer>
Examples of the stabilizer include nitroalkanes, epoxides, amines and the like.

Nitro alkanes refer to aliphatic nitro compounds and refer to compounds containing one or more nitro groups. Specific examples thereof include nitromethane, nitroethane, and nitropropane.

The epoxides are compounds having one or more epoxy groups which are 3-membered cyclic ethers. Specifically, 1,2-propylene oxide, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, butyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, vinyl glycidyl ether, Included are allylglycidyl ethers, diethylene glycol diglycidyl ethers, epichlorohydrins, d-lymonene oxide and l-lymonen oxide. Of these, 1,2-propylene oxide and 1,2-butylene oxide are preferable.

Further, the amines refer to compounds having one or more primary to tertiary amino groups. Further, the amines may be acyclic amines or cyclic amines. Examples of acyclic amines include aliphatic amines and aromatic amines. Examples of the aliphatic amine include benzene nucleus-containing compounds having one or more primary to tertiary amino groups. Examples of the cyclic amines include 4- to 6-membered ring compounds having 1 to 3 nitrogen atoms constituting the ring. Specifically, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, isopropylamine, diisopropylamine, butylamine, dibutylamine, tributylamine, isobutylamine, diisobutylamine. , Secondary butylamine, tertiary butylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, 2-ethylhexylamine, allylamine, diallylamine, triallylamine, aniline, N-methylaniline, N, N-dimethylaniline, N, N -Diethylaniline, pyridine, picolin, morpholine, N-methylmorpholine, benzylamine, dibenzylamine, α-methylbenzylamine, propylenediamine, diethylhydroxyamine, pyrrole, N-methylpyrrole, 2-methylpyridine, 3-methyl Ppyridine, 4-methylpyridine, ethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, isopropanolamine, diisopropanolamine, N-methylethanolamine, N, N-dimethylethanolamine, morpholin, N-methylmorpholin , N-Ethylmorpholine, diphenylamine and ethylenediamine. As the amines, alkylamines and cyclic amines are preferable, and among them, pyrrole, N-methylpyrrole, 2-methylpyridine, n-propylamine, diisopropylamine, N-methylmorpholine and N-ethylmorpholine are preferable.

<Antioxidant>
As the antioxidant, a phenolic antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, or a sulfur-based antioxidant may be added. A specific example is shown below. For the purpose of preventing oxidation of the cleaning agent, for example, as a phenolic antioxidant, 1-oxy-3-methyl-4-isopropylbenzene, 2,4-dimethyl-6-t-butylphenol, 2,6-di- t-butylphenol, butylhydroxyanisole, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-di-t-butyl-4-hydroxy Methylphenol, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl) -4-Hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and the like can be mentioned.

Examples of the amine-based antioxidant include compounds such as diphenyl-p-phenylene-diamine, 4-amino-p-diphenylamine, and p, p'-dioctyldiphenylamine.

Phosphorus antioxidants include phenylisodecylphosphine, diphenyldiisooctylphosphine, diphenyldiisodecylphosphine, triphenylphosphine, trisnonylphenylphosphine, and bis (2,4-di-tbutylphenyl) penta. Examples include compounds such as eristol diphosphite.

Examples of sulfur-based antioxidants include dilauryl-3, 3'-thiodipropionic acid ester, ditridecyl-3, 3'-thiodipropionic acid ester, dimyristyl-3, 3'-thiodipropionic acid ester, and distearyl-. Compounds such as 3,3'-thiodipropionic acid ester can be mentioned.

<UV absorber>
Examples of the ultraviolet absorber include 4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2, 2'. -Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,4-dihydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4' -Benzophenones such as dimethoxybenzophenone and 4-dodecyl-2-hydroxybenzophenone, phenylsalicylate, 4-t-butylphenylsalicylate, 4-octylphenyl salicylate, phenylsalicylate such as bisphenol A-di-salicylate and 2- (5) -Methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α'-didimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-) t-Butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-) 2-Hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-4'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'- Examples thereof include benzotriazoles such as hydroxy-5'-t-octylphenyl) benzotriazole.

<Surfactant>
As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant may be added. Examples of the anionic surfactant include fatty acids having 6 to 20 carbon atoms, alkali metals such as dodecylbenzenesulfonic acid, alkanolamines and amine salts. Examples of the cationic surfactant include a quaternary ammonium salt and the like. Examples of the nonionic surfactant include an alkylphenol, an ethylene oxide adduct of a linear or branched aliphatic alcohol having 8 to 18 carbon atoms, and a block polymer of polyethylene oxide polypropylene oxide. Examples of amphoteric surfactants include betaine type and amino acid type.

<Defoamer>
Examples of the defoaming agent include self-emulsifying silicones, fatty acids, higher alcohols, polypropylene glycol, polyethylene glycol, fluorine-based surfactants, and the like.

[Preferable blending ratio of cleaning agent composition]
The cleaning composition of the present embodiment is obtained by mixing and homogenizing each component of the above component (A), the above component (B), the above component (C) if necessary, and the above various auxiliary agents according to a conventional method.

The mass ratio of each component is not particularly limited as long as the characteristics of the cleaning agent, such as high detergency, metal corrosiveness, low toxicity, and low flammability, are not impaired, but the above component (A) and It is preferable that the component (B) is contained in an amount of 20 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the total amount of the component (B). When the mass ratio of the component (B) is 20 parts by mass or more, a more preferable effect of improving the dissolving power for various stains can be obtained, and when it is 80 parts by mass or less, a more preferable cleaning agent component on the surface of the object to be cleaned is obtained. Low persistence is obtained. The range of the content of the component (B), which is more preferable in consideration of the balance between the detergency of the cleaning agent and the persistence of the cleaning agent component on the surface of the object to be cleaned, is 30 parts by mass or more and 70 parts by mass or less, and more preferably. It is 40 parts by mass or more and 60 parts by mass or less.

Further, when the component (B) is the component (b) and the component (b1) and the component (b') are used in combination as the component (b), the component (b2) and the component (b) are used as the component (B). When the component (B) is the component (b) and the component (b4) and the component (y) are used in combination as the component (b), the preferable blending ratio of these components is described above. As described. When a plurality of types of components (B) are used, the blending amount is based on the total amount of the component (B). That is, the total amount of the plurality of types of components (B) is made to fall within the range of the amount of the above-mentioned component (B).

When the component (C) is used in combination, the range of the mass ratio is 1 part by mass or more and 50 parts by mass of the component (C) with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 1 part by mass or more and 30 parts by mass or less. When the proportion of the component (C) by mass is 1 part by mass or more, a more preferable effect of improving the dissolving power for various stains can be obtained, and when it is 50 parts by mass or less, a more preferable low flammability can be obtained. When a plurality of types of components (C) are used, the blending amount is based on the total amount of the component (C). That is, the total amount of the plurality of types of components (C) is made to fall within the range of the amount of the above-mentioned component (C).

The blending amount of the various auxiliaries may be appropriately set. For example, in the case of a stabilizer and an antioxidant, a total of 0.0001 mass with respect to a total of 100 parts by mass of the component (A) and the component (B). It may be more than 2 parts and 5 parts by mass or less. The same applies when various auxiliary agents are blended in the rinse agent composition.

[Preferable blending ratio of rinse agent composition]
The rinse agent composition of the present embodiment is obtained, for example, by mixing and homogenizing the above-mentioned components (A), (B), if necessary, the above-mentioned component (C), and the above-mentioned various auxiliary agents according to a conventional method. Examples thereof include a method and a method of obtaining a condensate by heating the cleaning agent composition of the present embodiment to generate vapor and cooling the composition. When the rinse agent composition of the present embodiment is continuously used, it is preferable to use a condensate obtained by generating steam.

A suitable blending ratio of the rinsing agent composition of the present invention is such that the component (B) is 0.01 part by mass or more with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably 0 parts by mass or less. By satisfying this range, the rinsing agent composition balances the rinsing effect and the ease of drying. Considering the applicability of the apparatus, the blending ratio of the rinse agent composition is 0.01 part by mass of the component (B) with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is more preferably 1.0 part by mass or less, and further preferably 0.01 part by mass or more and 0.5 part by mass or less. When a plurality of components (B) are used, the blending amount is based on the total amount of the component (B). The rinse agent composition can be used as it is as long as the condensate of the cleaning agent composition satisfies the above range, or the component (A) and the component (B) can be separately blended to adjust the blending ratio. ..

When the component (C) is blended, the component (C) is 0.01 part by mass or more and 20 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B). It is preferably contained below. Above all, since the use of the rinse agent composition is close to the drying step, the flammability must be lowered depending on the drying method. Therefore, the component (C) is more preferably 0.01 part by mass or more and 10 parts by mass or less, and further preferably 0.01 part by mass or more and 5 parts by mass or less. When a plurality of components (C) are used, the blending amount is based on the total amount of the component (C). The rinse agent composition can be used as it is if the condensate of the cleaning agent composition satisfies the above range, or the component (A), the component (B), and the component (C) are separately blended to adjust the blending ratio. It can also be adjusted.

Further, when the component (B) is the component (b) and the component (b1) and the component (b') are used in combination as the component (b), the component (b2) and the component (b) are used as the component (B). When the component (B) is the component (b) and the component (b4) and the component (y) are used in combination as the component (b), the preferable blending ratio of these components is described above. As described.

[Washing method]
The cleaning method of the present embodiment includes a step of cleaning dirt adhering to the object to be cleaned with a cleaning agent composition. Further, it is preferable to include a step of rinsing and / or steam cleaning using the vapor and condensate of the cleaning agent generated by heating the cleaning agent composition after cleaning with the cleaning agent composition. In particular, in order to make the cleaning agent composition and the rinsing agent composition non-flammable, it is necessary to contain the above component (A). Effective cleaning is possible by combining physical methods such as hand wiping, immersion, and shower for the purpose of improving the cleaning property in the cleaning process. Further, in the rinsing step, the rinsing property is further improved by combining physical methods such as immersion and shower for the purpose of improving the rinsing property. Further, it is more preferable to use a solvent that does not substantially contain a stain component as the rinsing agent in order to improve the rinsing property. The discharge pressure when shower rinsing for cleaning or rinsing is preferably 1 × 10 ³ to 2 × 10 ⁶ Pa, more preferably 1 × 10 ⁴ to 1 × 10 ⁶ Pa.

The cleaning method of the present embodiment is excellent in detergency and drying property in using the cleaning agent composition. Further, by using the vapor and the condensate obtained by heating the cleaning agent composition as the rinsing agent composition and the supplementary liquid, it is possible to obtain stable detergency by suppressing the composition fluctuation of the cleaning agent composition. This is possible and has little effect on the material of the object to be cleaned, so it can be said to be the most suitable cleaning method. Further, a cleaning method and a cleaning device as described in Patent Document 3 can be used.

Hereinafter, the present embodiment will be described in more detail with reference to Examples, but the present embodiment is not limited to the following Examples.

[Examples 1 to 20]
Each component was mixed with the composition shown in Table 1 to obtain the desired cleaning agent composition. Each cleaning agent composition was subjected to (1) oil solubility test described later, and the results are summarized in Table 1. By using the component (A) and the component (B) in combination, a cleaning agent having excellent oil solubility was obtained. Further, in the composition in which the component (b1) and the component (b5) are combined, a higher cleaning effect is obtained as is clear from the comparison result between Example 1 and Example 13 or the comparison result between Example 11 and Example 12. It was confirmed that

Further, by adding a compound selected from the group consisting of the component (C) alcohols, ketones, esters and hydrocarbons, as is clear from the comparison results between Example 1 and Example 20, the component (b) It was confirmed that the oil solubility of) was further improved.

[Comparative Examples 1 to 4]
The same evaluation test as in Examples 1 to 20 was performed on the solvents listed in Table 1. The results are summarized in Table 1. The oil solubility of the component (A) alone and the mixture of the component (A) and the component (C) was insufficient.

[Examples 21 to 27]
Each component was mixed with the composition shown in Table 2 to obtain the desired cleaning agent composition. A degreasing detergency test, which will be described later, was carried out using the cleaning agent composition, and the results are summarized in Table 2. Excellent for oil by washing with a cleaning agent composition and a rinsing agent composition having different concentrations containing the component (A) and the component (B), and steam cleaning the cleaning agent composition with steam obtained by heating. Detergency was confirmed.

[Comparative Examples 5 and 6]
The same evaluation test as in Examples 21 to 27 was performed on the cleaning agents shown in Table 2. The results are summarized in Table 2. The cleaning property against oil was insufficient with the component (A) alone.

(1) Oil Solubility Test Add 0.5 g of metalworking oil (trade name: G3159SH, manufactured by Nippon Kogyo Oil Co., Ltd.) to 4.5 g of a cleaning agent composition at 25 ° C. and shake with a shaker for 2 minutes (1) 60 times / min), and after standing for 5 minutes, the solubility was visually evaluated. Evaluation is based on the following criteria.

<Evaluation criteria>
A: Uniform dissolution B: Uniform fine dispersion C: Uniform dispersion D: Some precipitates (2) Solvent degreasing detergency test A 30-mesh stainless wire mesh (10 mm x 20 mm) is impregnated with the following metalworking oil for testing at 100 ° C. A test piece was prepared by heating with. The test piece was washed with a cleaning agent composition heated to 40 ° C., immersed and rinsed with a rinsing agent, and then the cleaning agent composition was steam-washed with steam obtained by heating to 40 ° C. and dried. The detergency was visually evaluated. Evaluation is based on the following criteria.

<Cleaning conditions>
Metalworking oil used for the test: A liquid containing 0.1% by weight of dye (Zudan) and 25% by weight of G3159SH (trade name, manufactured by Nippon Kogei Co., Ltd.) in perchloroethylene was prepared and used as a test metal. It was used as processing oil.

Cleaning conditions Cleaning: Immersion ultrasonic cleaning for 2 minutes (28 kHz, 200 w)
Rinse: Immersion ultrasonic rinse for 2 minutes (28kHz, 200w)
Vapor: Let stand for 2 minutes <Rinse agent (rinse agent composition)>
In Examples 21 to 23 and Comparative Examples 5 to 6, component (A): HCFO-1233zd (Z) / component (b1): methyl caprylate / component (b5): 3-methyl-3-methoxybutanol = 99. A rinsing agent containing 9.9 parts by mass / 0.05 parts by mass / 0.05 parts by mass was used.

In Examples 24 to 25, a rinsing agent containing component (A): HCFO-1233 zd / component (b1): methyl enanthate = 99.9 parts by mass / 0.1 parts by mass was used.

In Examples 26 to 27, component (A): HCFO-1223 zc / component (b1): methyl caprylate / component (C): isopropanol = 99.9 parts by mass / 0.1 parts by mass / 5.0 parts by mass. A rinse agent containing was used.

<Evaluation criteria>
⊚: No residual processing oil, deemed ○: No residual processing oil, slight stain Δ: Slight residual processing oil ×: Residual processing oil [Examples 28 to 47]
Each component was mixed with the composition shown in Table 3 to obtain the desired cleaning agent composition. Each cleaning agent composition was subjected to (3) oil solubility test described later, and the results are summarized in Table 3. By using the component (A) and the component (B) in combination, a cleaning agent having excellent oil solubility was obtained. Further, in Examples 37 to 42, (4) a immersion test of butyl rubber, which will be described later, was carried out to confirm damage (weight change) to the resin member. The results are summarized in Table 3.

(3) Oil Solubility Test Add 0.5 g of metalworking oil (trade name: Yushiron Former CF-6120, manufactured by Yushiro Chemical Industry Co., Ltd.) to 4.5 g of a cleaning agent composition at 25 ° C. and shaker. The mixture was shaken for 2 minutes (60 times / minute) and allowed to stand for 5 minutes, and then the solubility was visually evaluated. Evaluation is based on the following criteria.

<Evaluation criteria>
A: Uniform dissolution B: Uniform fine dispersion C: Uniform dispersion D: Some precipitates (4) Immersion test of butyl rubber In 50 g of the cleaning agent composition kept at 40 ° C. in a constant temperature water bath, a butyl rubber test piece (2) × 13 × 50 mm) was immersed for 10 minutes, taken out, the cleaning agent composition on the surface of the test piece was wiped off, and then the weight of the test piece was measured. The weight change rate (%) expressed by the following formula from the weight of the test piece before and after immersion. ) Was calculated.

Weight change rate (%) = (weight after immersion-weight before immersion) / weight before immersion x 100
[Examples 48 to 59]
Each component was mixed with the composition shown in Table 4 to obtain the desired cleaning agent composition. Each cleaning agent composition was subjected to (5) oil solubility test and (6) water-soluble processing oil solubility test described later, and the results are summarized in Table 4.

[Comparative Examples 7 and 8]
Each component was mixed with the composition shown in Table 4 to obtain the desired cleaning agent composition. The same evaluation test as in Examples 48 to 59 was carried out for each cleaning agent composition. The results are summarized in Table 4.

(5) Oil Solubility Test Add 0.5 g of metalworking oil (trade name: Yushiron Former CF-6120, manufactured by Yushiro Chemical Industry Co., Ltd.) to 4.5 g of a cleaning agent composition at 25 ° C. and shaker. The mixture was shaken for 2 minutes (60 times / minute) and allowed to stand for 5 minutes, and then the solubility was visually evaluated. Evaluation is based on the following criteria.

<Evaluation criteria>
A: Uniform dissolution B: Uniform fine dispersion C: Uniform dispersion D: Some precipitates (6) Water-soluble processing oil solubility test Water-soluble processing oil: Water-soluble cutting oil Hokat 795B (trade name: manufactured by Nippon Horton) Pure water was mixed at a weight ratio of 1: 9 to obtain a water-soluble processing oil for testing.
0.05 g of the above water-soluble processing oil was added to 5.0 g of the cleaning agent composition, shaken with a shaker for 2 minutes (60 times / minute), allowed to stand for 5 minutes, and then the solubility was visually evaluated. Evaluation is based on the following criteria.

<Evaluation criteria>
A: Uniform dissolution B: Uniform fine dispersion C: Uniform dispersion D: Water-soluble oil separation [Examples 60 to 64]
Each component was mixed with the composition shown in Table 5 to obtain the desired cleaning agent composition. The same (6) water-soluble processing oil solubility test as in Examples 48 to 59 was carried out for each cleaning agent composition, and the results are summarized in Table 5. By using the component (A) and the component (b2) in combination, a cleaning agent having excellent solubility of the water-soluble processing oil was obtained.

[Examples 65-80]
The same (5) oil solubility test and (6) water-soluble processed oil solubility test as in Examples 48 to 59 were carried out except for the compositions shown in Table 5, and the results are summarized in Table 5. By combining (b2) and (b1) or (b4) as the component (A) and the component (B), a cleaning agent having excellent oil solubility and water-soluble processing oil solubility was obtained.

The cleaning agent composition and rinsing agent composition of the present invention are used for cleaning processing oils containing a large amount of sparingly soluble components such as processing oils, greases and waxes used when processing precision machine parts, high-priced machine parts and the like. It can be preferably used.

Claims (15)

(A) The following general formula (1) :
_{C 3 H (6-ab)} F a Cl b (1)
(In the equation, a is an integer of 1 to 5, b is an integer of 1 to 3, but a + b is an integer of 2 to 6.)
(B) An organic compound having an ether bond and / or an ester bond having a vapor pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C., and steam at 20 ° C. hydrocarbons pressure is less than 1.33 × 10 ^-2 Pa or 1.33 × 10 ³ Pa, and the vapor pressure at 20 ° C. is 1.33 × 10 ^-2 Pa or 1.33 × 10 ³ less than Pa multi A cleaning composition containing one or more compounds selected from the group consisting of hydrocarbon compounds.
As the fluoropropene compound (A) , one or more compounds selected from the group consisting of HCFO-1233zd (Z) and HCFO-1223za are contained.
As the compound (B),

(In the formula, R ⁴ is a hydrocarbon group having 5 to 15 carbon atoms, and R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms.) The fatty acid esters (b1),
Multivalent alcohol (b2) with 4 to 8 carbon atoms,
Glycol ethers with 3 to 14 carbon atoms Monoalkyl ethers (b3-1),
Glycol ethers dialkyl ethers having 4 to 17 carbon atoms (b3-2),
Hydrocarbons (b4), which are aliphatic hydrocarbons having 10 to 16 carbon atoms or alicyclic hydrocarbons having 10 to 16 carbon atoms.
Glycol ether acetates (b5-1) having 5 to 12 carbon atoms, and
Hydroxycarboxylic acid esters having 4 to 20 carbon atoms (b5-2)
Containing at least one compound selected from the group consisting of
The content of the compound (B) is 20 parts by mass or more and 70 parts by mass or less with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B).
Cleaning agent composition . The fatty acid esters (b1) are methyl caproate, ethyl caproate, propyl caproate, butyl caproate, methyl enanthate, ethyl enanthate, propyl enantate, butyl enanthate, methyl caprylate, ethyl caprilate, capryl. Propyl acid, butyl caprylate, methyl pelargonate, ethyl pelargonate, propyl pelargonate, butyl pelargone, methyl caprate, ethyl caprate, propyl caprate, butyl caprate, methyl decenoate, ethyl decenoate, propyl decenoate , Butyl decenoate, methyl undecanoate, ethyl undecanoate, propyl undecanoate, butyl undecanoate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, methyl dodecate, ethyl dodecate, propyl dodecenoate, dodecene At least one selected from the group consisting of butyl acid acid, methyl tridecanoate, ethyl tridecanoate, methyl myristate, ethyl myristate, methyl pentadecanoate, ethyl pentadecanoate, methyl palmitate, and ethyl palmitate.
The polyhydric alcohol (b2) is 2,3-butanediol, 2-methyl-1,2-propanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2,4-pentane. At least one selected from the group consisting of diols, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, and 2,4-dimethyl-2,4-pentanediol. Yes,
The glycol ether monoalkyl ethers (b3-1) are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, and ethylene glycol mono-n-butyl ether. , Ethylene glycol mono-i-butyl ether, ethylene glycol mono-n-hexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol mono-i-propyl ether , Triethylene glycol mono-n-butyl ether, triethylene glycol mono-i-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, diethylene glycol mono-n-butyl ether. , Diethylene glycol mono-i-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-i-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-i -Butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-i-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono- At least one selected from the group consisting of i-butyl ether, tripropylene glycol monomethyl ether, 3-methoxybutanol, and 3-methyl-3-methoxybutanol.
The glycol ether dialkyl ethers (b3-2) consist of a group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. At least one of the choices
The hydrocarbons (b4) are decane, decane, undecane, undecane, dodecane, dodecane, tridecane, tetradecane, pentadecane, mentan, bicyclohexyl, cyclododecane, and 2,2,4,4,6,8,8- At least one selected from the group consisting of heptamethylnonane,
The glycol ether acetates (b5-1) are monoalkyl ether acetates selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol, 3-methoxybutyl acetate, and 3-. At least one selected from the group consisting of methyl-3-methoxybutyl acetate,
The hydroxycarboxylic acid esters (b5-2) are selected from the group consisting of lactic acid ester, malic acid ester, tartrate acid ester, citric acid ester, glycol monoester, glycerin monoester, glycerin diester, ricinolic acid ester, and castor oil. At least one species
The cleaning composition according to claim 1. Further (C) a vapor pressure at 20 ° C. is 1.33 × 10 ³ Pa or more alcohols, ketones, containing esters, and one or more compounds selected from the group consisting of hydrocarbons,
The alcohols are at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol.
The ketones are at least one selected from the group consisting of acetone and methyl ethyl ketone.
The esters are at least one selected from the group consisting of ethyl formate, propyl formate, isobutyl formate, methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate.
The hydrocarbons are n-hexane, isohexane, cyclohexane, cyclohexene, 2-methylpentane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 2,4-dimethylpentane, and At least one selected from the group consisting of isooctane,
The cleaning composition according to claim 1. The cleaning composition according to claim 3 , wherein the compound (C) is contained in an amount of 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the total amount of the compound (A) and the compound (B). As the compound (B),
(B1) Fatty acid esters and
(B') Glycol ether monoalkyl ethers (3-1), glycol ether dialkyl ethers (3-2), hydrocarbons (b4), glycol ether acetates (b5-1), and hydroxycarboxylic acid esters. One or more compounds selected from the group consisting of (b5-2)
Contains compounds selected from
Examples of the compound (b') include diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-n-butyl ether. Includes one or more compounds selected from the group consisting of 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, butyl lactate, decane, decene, dodecane, and dodecene.
The cleaning composition according to claim 1 . The cleaning composition according to claim 5 , wherein the compound (B) contains both components of the fatty acid esters (b1) and the compound (b'). (A) The following general formula (1) :
_{C 3 H (6-ab)} F a Cl b (1)
(In the equation, a is an integer of 1 to 5, b is an integer of 1 to 3, but a + b is an integer of 2 to 6.)
(B) An organic compound having an ether bond and / or an ester bond having a vapor pressure of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa at 20 ° C., and steam at 20 ° C. hydrocarbons pressure is less than 1.33 × 10 ^-2 Pa or 1.33 × 10 ³ Pa, and the vapor pressure at 20 ° C. is 1.33 × 10 ^-2 Pa or 1.33 × 10 ³ less than Pa multi Containing one or more compounds (B) selected from the group consisting of hydrocarbon compounds,
A rinse agent composition in which the content of the compound (B) is 0.01 part by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B). There,
As the fluoropropene compound (A) , one or more compounds selected from the group consisting of HCFO-1233zd (Z) and HCFO-1223za are contained.
As the compound (B),

(In the formula, R ⁴ is a hydrocarbon group having 5 to 15 carbon atoms, and R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms.) The fatty acid esters (b1),
Multivalent alcohol (b2) with 4 to 8 carbon atoms,
Glycol ethers with 3 to 14 carbon atoms Monoalkyl ethers (b3-1),
Glycol ethers dialkyl ethers having 4 to 17 carbon atoms (b3-2),
Hydrocarbons (b4), which are aliphatic hydrocarbons having 10 to 16 carbon atoms or alicyclic hydrocarbons having 10 to 16 carbon atoms.
Glycol ether acetates (b5-1) having 5 to 12 carbon atoms, and
Hydroxycarboxylic acid esters having 4 to 20 carbon atoms (b5-2)
Containing at least one compound selected from the group consisting of
Rinse composition . The fatty acid esters (b1) are methyl caproate, ethyl caproate, propyl caproate, butyl caproate, methyl enanthate, ethyl enanthate, propyl enantate, butyl enanthate, methyl caprylate, ethyl caprilate, capryl. Propyl acid, butyl caprylate, methyl pelargonate, ethyl pelargonate, propyl pelargonate, butyl pelargone, methyl caprate, ethyl caprate, propyl caprate, butyl caprate, methyl decenoate, ethyl decenoate, propyl decenoate , Butyl decenoate, methyl undecanoate, ethyl undecanoate, propyl undecanoate, butyl undecanoate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, methyl dodecate, ethyl dodecate, propyl dodecenoate, dodecene At least one selected from the group consisting of butyl acid acid, methyl tridecanoate, ethyl tridecanoate, methyl myristate, ethyl myristate, methyl pentadecanoate, ethyl pentadecanoate, methyl palmitate, and ethyl palmitate.
The polyhydric alcohol (b2) is 2,3-butanediol, 2-methyl-1,2-propanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 2,4-pentane. At least one selected from the group consisting of diols, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, and 2,4-dimethyl-2,4-pentanediol. Yes,
The glycol ether monoalkyl ethers (b3-1) are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-i-propyl ether, and ethylene glycol mono-n-butyl ether. , Ethylene glycol mono-i-butyl ether, ethylene glycol mono-n-hexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol mono-n-propyl ether, triethylene glycol mono-i-propyl ether , Triethylene glycol mono-n-butyl ether, triethylene glycol mono-i-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-i-propyl ether, diethylene glycol mono-n-butyl ether. , Diethylene glycol mono-i-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-i-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-i -Butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-i-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono- At least one selected from the group consisting of i-butyl ether, tripropylene glycol monomethyl ether, 3-methoxybutanol, and 3-methyl-3-methoxybutanol.
The glycol ether dialkyl ethers (b3-2) consist of a group consisting of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. At least one of the choices
The hydrocarbons (b4) are decane, decane, undecane, undecane, dodecane, dodecane, tridecane, tetradecane, pentadecane, mentan, bicyclohexyl, cyclododecane, and 2,2,4,4,6,8,8- At least one selected from the group consisting of heptamethylnonane,
The glycol ether acetates (b5-1) are monoalkyl ether acetates selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol, 3-methoxybutyl acetate, and 3-. At least one selected from the group consisting of methyl-3-methoxybutyl acetate,
The hydroxycarboxylic acid esters (b5-2) are selected from the group consisting of lactic acid ester, malic acid ester, tartrate acid ester, citric acid ester, glycol monoester, glycerin monoester, glycerin diester, ricinolic acid ester, and castor oil. At least one species
The rinse agent composition according to claim 7. Further (C) a vapor pressure at 20 ° C. is 1.33 × 10 ³ Pa or more alcohols, ketones, containing esters, and one or more compounds selected from the group consisting of hydrocarbons,
The alcohols are at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol.
The ketones are at least one selected from the group consisting of acetone and methyl ethyl ketone.
The esters are at least one selected from the group consisting of ethyl formate, propyl formate, isobutyl formate, methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate.
The hydrocarbons are n-hexane, isohexane, cyclohexane, cyclohexene, 2-methylpentane, 2,3-dimethylbutane, n-heptane, 2-methylhexane, 3-methylhexane, 2,4-dimethylpentane, and At least one selected from the group consisting of isooctane,
The rinse agent composition according to claim 7 . The rinse agent composition according to claim 9 , wherein the compound (C) is contained in an amount of 0.01 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the compound (A) and the compound (B). Stuff. As the compound (B),
(B1) Fatty acid esters and
(B') Glycol ether monoalkyl ethers (b3-1), glycol ether dialkyl ethers (b3-2), hydrocarbons (b4), glycol ether acetates (b5-1), and hydroxycarboxylic acid esters One or more compounds selected from the group consisting of (b5-2)
Contains compounds selected from
Examples of the compound (b') include diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, dipropylene glycol dimethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-n-butyl ether. Includes one or more compounds selected from the group consisting of 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate, butyl lactate, decane, decene, dodecane, and dodecene.
The rinse agent composition according to claim 7 . The rinse agent composition according to claim 7 , wherein the compound (B) contains both components of the fatty acid esters (b1) and the compound (b'). A cleaning method comprising the step (1) of cleaning a dirty object to be cleaned with the cleaning agent composition according to claim 1. 13. Claim 13 further includes a step (2) of rinsing and / or steam-cleaning the object to be cleaned that has undergone the step (1) using the vapor of the cleaning agent composition and / or a condensate of the vapor. The cleaning method described in. The cleaning method according to claim 14 , wherein in the step (2), the rinse agent composition according to claim 7 is used as the rinse agent.