JP2018150502A - Detergent composition, rinse agent composition, and cleaning method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a stable detergent containing cis-1-chloro-3,3,3-trifluoropropene.SOLUTION: A detergent composition contains cis-1-chloro-3,3,3-trifluoropropene (A), and a stabilizer (X) comprising a linear or branched alkene with carbon atoms of 5 or 6.SELECTED DRAWING: None

Description

  The present invention relates to a novel detergent composition, a novel rinse agent composition, and a novel washing method.

  Various processing oils used when processing precision machine parts, optical machine parts, etc., such as cutting oils, press oils, drawing oils, heat treatment oils, rust preventive oils, lubricating oils, greases, waxes, etc. The dirt must be finally removed, and removal with a solvent is generally performed. Similarly, fluxes used when soldering electrical and electronic parts, inks or pastes attached to the screen used during substrate manufacture, or resins attached to the mixing head of the resin discharge device can also be removed with a solvent. Generally done.

  These washing and removal have many characteristics such as nonflammability, low toxicity, and excellent solubility, so that 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as “removable”) CFC113) or a mixture of CFC113 and alcohol. However, global environmental pollution problems such as ozone depletion were pointed out, and production of CFC113 was abolished in Japan at the end of 1995. As an alternative to the CFC 113, a mixture of 3,3-dichloro-1,1,1,2,2-pentafluoropropane and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (hereinafter referred to as “CFC 113”) Hydrochlorofluorocarbons such as HCFC225 and 1,1-dichloro-1-fluoroethane (hereinafter referred to as HCFC141b) have been proposed, but these are also slightly depleted in the ozone layer, so in Japan in 2020 It is scheduled to be banned.

  In recent years, non-flammable fluorine-based solvents have been proposed that have no ozone depletion potential, such as hydrofluorocarbons (hereinafter referred to as HFC) and hydrofluoroethers (hereinafter referred to as HFE) that do not contain any chlorine atoms. Since it does not contain atoms, it has low solubility and cannot be used alone as a cleaning agent. In Patent Documents 1 to 3, after washing with a cleaning agent obtained by adding a high-boiling solvent to HFC or HFE, HFC or HFE is used as a rinsing agent. The technology used is disclosed.

  In addition, since it has a double bond in the molecule and generally has high reactivity with OH radicals in the atmosphere, it has a low ozone depletion potential (ODP) and global warming potential (GWP), and contains chlorine atoms. Thus, a technology using fluoropropenes exhibiting oil solubility has been developed.

  Cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)) is known to be useful as a fluoropropene for cleaning agents. For example, Patent Document 4 discloses 1,1 A cleaning solvent comprising an azeotropic or azeotrope-like composition comprising dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) and HCFO-1233zd (Z) is disclosed. Patent Documents 5 to 7 also disclose cleaning agents made of an azeotropic or azeotrope-like composition comprising HCFO-1233zd (Z) and other components.

  However, since fluoropropenes are easily decomposed, they are inferior in stability, and there is a problem that they are decomposed and acidified when used as cleaning solvents. Under such problems, Patent Document 4 lists various compounds such as β-isoamylene as stabilizers, but does not disclose specific examples (examples) of cleaning solvents containing stabilizers. . Patent Documents 5 to 7 also describe that unsaturated hydrocarbons may be added as a stabilizer to the cleaning agent.

  Furthermore, in order to solve this stability problem, Patent Document 8 discloses 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) as a fluoropropene, phenols, A solvent composition containing at least one stabilizer selected from the group consisting of ethers, epoxides and amines is disclosed. This composition was completed based on the knowledge that the conventional technology for stabilizing fluoroolefins cannot stabilize any fluoroolefin, and the stabilization technology differs depending on the type of fluoroolefin. For example, Table 8 of Patent Document 8 shows that stabilizers such as β-isoamylene (2-methyl-2-butene) listed in Patent Document 4 are not effective against CFO-1214ya. ing.

JP 10-036894 A Japanese Patent Laid-Open No. 10-192797 Japanese Patent No. 4267911 JP, 2006-079224, A JP 2008-133438 A JP 2010-248443 A International Publication No. 2016/052562 International Publication No. 2014/073372

  As described above, the conventional technology for stabilizing fluoroolefins cannot stabilize any fluoroolefin, and the stabilization technology differs depending on the type of fluoroolefin, and the stability including HCFO-1233zd (Z) No cleans or rinses were known.

This invention makes it a subject to provide the stable cleaning composition and rinse agent composition containing HCFO-1233zd (Z) in view of the problem of such a prior art.
Furthermore, this invention makes it a subject to provide the method of wash | cleaning, suppressing decomposition | disassembly of HCFO-1233zd (Z).

  The present inventors have intensively studied to achieve the above-mentioned problems. As a result, HCFO-1233zd (Z) is blended with an unsaturated hydrocarbon compound having 5 or 6 carbon atoms as a stabilizer. The present invention has been completed.

The gist of the present invention is as follows.
[1]
Cis-1-chloro-3,3,3-trifluoropropene (A);
A detergent composition comprising a stabilizer (X) comprising a linear or branched alkene having 5 or 6 carbon atoms.

[2]
The cleaning composition of [1], wherein the alkene is a branched alkene.

[3]
The cleaning composition according to [1] or [2], wherein the alkene is 2-methyl-2-butene.

[4]
The cleaning composition according to any one of [1] to [3], further comprising a stabilizer (Y) other than the stabilizer (X).

[5]
The cleaning composition according to [4], wherein the stabilizer (Y) is at least one selected from the group consisting of epoxides, amines, and phenolic antioxidants.

[6]
The above-mentioned further containing one or more compounds (Z) selected from the group consisting of organic compounds having an ether bond and / or an ester bond, hydrocarbons (excluding the component (X)), alcohol compounds and ketones [ The cleaning composition according to any one of 1] to [5].

[7]
As the compound (Z), an organic compound having an ether bond and / or an ester bond with a vapor pressure at 20 ° C. of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa, a vapor pressure at 20 ° C. of 1 .33 × 10 ⁻² Pa to 1.33 × 10 ³ Pa hydrocarbons and polyhydric alcohol compounds having a vapor pressure at 20 ° C. of 1.33 × 10 ⁻² Pa to 1.33 × 10 ³ Pa The cleaning composition according to [6] above, which contains one or more compounds (B) selected from the group consisting of:

[8]
Examples of the compound (B) include fatty acid esters (b1), polyhydric alcohols (b2), glycol ethers (b3), hydrocarbons having 7 to 16 carbon atoms (b4), and compounds having an ester bond (however, The fatty acid ester (b1) is excluded.) The cleaning composition according to [7] above, which contains one or more compounds selected from the group consisting of (b5).

[9]
As the compound (Z), one or more compounds (C) selected from the group consisting of alcohols, ketones, esters, and hydrocarbons having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more are contained. The cleaning composition according to any one of [6] to [8].

[10]
The cleaning composition according to [9] above, which contains alcohols as the compound (C).

[11]
[10] The cleaning composition of [10], wherein the alcohols contain isopropyl alcohol.

[12]
Cis-1-chloro-3,3,3-trifluoropropene (A);
The rinse agent composition containing the stabilizer (X) which consists of a linear or branched alkene whose carbon atom number is 5 or 6.

[13]
A cleaning method comprising a step (1) of cleaning an object to be cleaned, which is contaminated with the cleaning composition according to any one of [1] to [11].

[14]
[13] The method further includes the 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 composition and / or the condensate of the vapor. ] The cleaning method of description.

[15]
The step (2) is a step of rinsing at least the article to be cleaned that has undergone the step (1). In the step (2), the rinse agent composition of [12] is used as the rinse agent. ] Cleaning method.

The cleaning composition and the rinsing composition of the present invention are stable and exhibit an excellent cleaning effect.
Moreover, according to the cleaning method of the present invention, cleaning can be performed while suppressing decomposition of HCFO-1233zd (Z).

  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. And this invention can be deform | transformed suitably and implemented within the range of the summary.

  In this specification, the term “cleaning” refers to removing dirt adhering to an object to be cleaned to a level that does not affect the next process. Rinse means that after cleaning, a cleaning agent containing a dirt component adhering to an object to be cleaned is replaced with a solvent containing no dirt component. In addition, the shower rinsing means that after cleaning, a liquid or mist solvent is discharged from a single or a plurality of discharge ports and applied to the object to be cleaned, and the cleaning agent adhering to the object to be cleaned is replaced with the solvent. . Further, the steam cleaning is to remove a slightly contaminated component 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 a temperature difference between the object to be cleaned and the steam.

  The cleaning composition and the rinsing composition according to the present invention are composed of cis-1-chloro-3,3,3-trifluoropropene (A) and an unsaturated hydrocarbon compound having 5 or 6 carbon atoms. And a stabilizer (X).

Hereinafter, each component will be described.
《Cleaner component》
[Component (A)]
The cleaning composition and the rinsing composition of the present invention contain cis-1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)) as an essential cleaning component.

[Component (Z)]
The cleaning composition and the rinsing composition of the present invention can be used depending on the object to be cleaned, for example, whether to clean a soil containing a large amount of a poorly soluble component or to clean a soil containing a large amount of a water-soluble component. In addition to the component (A), the detergent component is selected from the group consisting of organic compounds having an ether bond and / or ester bond, hydrocarbons (excluding the component (X)), alcohol compounds and ketones. One or more selected compounds (Z) (also referred to as component (Z)) may be included.
Examples of the compound (Z) include a compound (B) (also referred to as component (B)) and a compound (C) (also referred to as component (C)) described below.

[Component (B)]
The cleaning composition and the rinsing composition of the present invention comprise, as the compound (Z), an ether bond having a vapor pressure at 20 ° C. of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa and / or Organic compounds having an ester bond, polyhydric alcohols having a vapor pressure at 20 ° C. of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa, and a vapor pressure at 20 ° C. of 1.33 × 10 ⁻² One or more compounds (B) (component (B)) selected from the group consisting of hydrocarbons of Pa or more and less than 1.33 × 10 ³ Pa may be included.

The component (B) may be one or more compounds selected from the group consisting of the organic compounds and the hydrocarbons (hereinafter also referred to as “component (b)”), and the polyhydric alcohols. (Hereinafter also referred to as “component (b2)”), component (b) and component (b2). When the vapor pressure of the component (B) is within this range, the cleaning composition excellent in rinsing properties and cleaning properties according to this embodiment is obtained. A preferable range of the vapor pressure is 6.66 × 10 ⁻² or more and 6.66 × 10 ² Pa or less at 20 ° C., more preferably 1.33 × 10 ⁻¹ Pa or more and 1.33 × 10 ² Pa or less. is there. Hereinafter, component (B) is illustrated for every kind of solvent.

  The specific gravity of the component (B) is preferably in 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 preferable to fall within 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 compatibility at low temperatures, the difference between the specific gravity of the component (A) and the specific gravity of other components used in combination is reduced. This is very important.

  The organic compound having an ether bond used in the cleaning agent and the rinse agent of the present embodiment is a compound containing at least one ether bond (C—O—C) in the molecular structure, and an organic compound having an ester bond. The compound is a compound containing one or more ester bonds (—COO—) in the molecular structure. Therefore, among the components (B), the organic compound having an ether bond and / or an ester bond is a compound having an ether bond and / or an ester bond.

  In addition, as component (B) demonstrated below, fatty acid ester (b1) (henceforth "component (b1)") which can improve a cleaning effect more, and polyhydric alcohol (b2) (henceforth "component"). (B2) ”) and a component (b ′) selected from a specific compound group.

  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 are collectively referred to as“ glycol ethers (b3) ”or“ component (b3) ”).

Examples of the component (b ′) include hydrocarbons (b4) (hereinafter also referred to as “component (b4)”).
Furthermore, 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 referred to as “component (b5-)”. 2) ").).

  Although 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) Each of them can be used alone as the component (b), or a plurality of types of components can be mixed and used depending on the application. Next, these components will be described.

<< Compound having 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, in order to exhibit a particularly excellent cleaning effect, the component (b) may contain a fatty acid ester (b1) (hereinafter sometimes simply referred to as component (b1)). Among them, it is preferable to include 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 include a fatty acid ester represented by the following general formula (1).

（式中、Ｒ⁴は炭素数５〜１５の炭化水素基であり、Ｒ⁵は炭素数１〜４の炭化水素基である。）

(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. Especially, in order to exhibit the outstanding cleaning effect, it is preferable that it is a C5-C15 chain saturated hydrocarbon group or a C5-C15 chain unsaturated hydrocarbon group. 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. And more preferably an alkyl group having 8 to 12 carbon atoms or an alkenyl group having 10 to 12 carbon atoms.

R ⁵ is a hydrocarbon group having 1 to 4 carbon atoms, such as a hydrocarbon group having 1 to 2 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and a methyl group. Particularly preferred. The reason why these are preferable is that the impact on the elastomer material contained in the packings used in the cleaning apparatus or the like or the article to be cleaned is small.

  Specific examples of the fatty acid ester represented by the general formula (1) 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 pelargonate, butyl pelargonate, methyl caprate, ethyl caprate, propyl caprate, butyl caprate, decene Methyl acrylate, ethyl decenoate, propyl decenoate, butyl decenoate, methyl undecanoate, ethyl undecanoate, propyl undecanoate, butyl undecanoate, methyl laurate, ethyl laurate, propyl laurate, butyl laurate, methyl dodecenoate , Ethyl dodecenoate, propyl dodecenoate, butyl dodecenoate, methyl tridecanoate, ethyl tridecanoate, methyl myristate, ethyl myristate, methyl pentadecanoate, ethyl pentadecanoate, methyl palmitate, ethyl palmitate, etc. it can.

  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 is preferred, and methyl caprate, methyl laurate, methyl decenoate, and methyl dodecenoate are preferred, and methyl decenoate and methyl dodecenoate having lower melting points are more preferred. In addition, the said fatty acid ester can also use one type, and can also use it in combination of 2 or more types.

  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).

<Component (b2): Polyhydric alcohol>
The polyhydric alcohol (b2) preferably has two hydroxyl groups in one molecule.
Carbon number of polyhydric alcohol (b2) becomes like this. Preferably it is 4-8, More preferably, it is 5-7.

Polyhydric alcohols (b2) The total number of carbon atoms bonded to a plurality of carbon atoms to which a hydroxyl group is bonded per molecule (for example, C ^a H ₃ —C ^b H (OH) —C ^In the case of polyhydric alcohols represented by ^c H ₂ —C ^d H ₂ (OH), this value is ((number of carbon atoms bonded to carbon atom C ^b ) + (bonded to carbon atom C ^d ). Number of carbon atoms) = 2 + 1 =) 3. The number of carbon atoms C ^c is counted redundantly.) Is preferably 3-6, more preferably 4-5. Also preferably, all hydroxyl groups are bonded to carbon atoms bonded to 2 or 3 carbon atoms.

The hydrocarbon constituting the polyhydric alcohol (b2) is preferably a saturated hydrocarbon.
Specific examples of the polyhydric alcohols (b2) include 2,3-butanediol, 2-methyl-1,2-propanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, , 4-pentanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, and the like. Among these, 3-methyl-1,3-butanediol and 2-methyl-2,4-pentanediol are preferable, and 2-methyl-2,4-pentanediol is particularly preferable.

<< Compound having an 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 component (b) is used as component (B), glycol ether monoalkyl ethers (component (b3-1)), glycol ether dialkyl ethers (component (b3-2)), etc. are used alone as component (b ) Can be used. Among these, it is particularly preferable to use in combination with the component (b1). However, among glycol ether monoalkyl ethers (component (b3-1)), a plurality of types of compounds can be used alone or in combination. Similarly, among glycol ether dialkyl ethers (component (b3-2)), a plurality of types of compounds can be used alone or in combination.

(Component (b3-1); glycol ether monoalkyl ethers)
Glycol ether 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 atom of the hydroxyl group. Are substituted with a hydrocarbon residue or a hydrocarbon residue containing an ether bond. Although not particularly limited, glycol ether monoalkyl ethers having 3 to 14 carbon atoms are preferred.

  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, 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 Ethylene glycol mono-n-butyl ether, triethylene glycol mono-i-butyl ether, diethylene glycol monome 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 Non-i-propyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-i-butyl ether, tripropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol and the like can be mentioned. .

  Furthermore, glycol ether monoalkyl ethers such as 3-methoxybutanol and 3-methyl-3-methoxybutanol are compounds that have particularly good detergency against various stains and provide an excellent detergency effect.

(Component (b3-1-1); hydrophilic glycol ether monoalkyl ethers)
Among the above glycol ether monoalkyl ethers (component (b3-1)), as a component suitable for washing water-soluble dirt such as water-soluble processing oil,
Requirement (1): A component satisfying the condition that phase separation does not occur when 60 parts by mass of glycol ether monoalkyl ether and 40 parts by mass of water are mixed at 30 ° C. (hereinafter referred to as hydrophilic glycol ether monoalkyl ethers) (Component (b3-1-1)) may be mentioned, and this component (b3-1-1) is preferably
Requirement (2): At 30 ° C., it can be mixed with water at an arbitrary ratio.

  Specific examples of hydrophilic glycol ether monoalkyl ethers (component (b3-1-1)) 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, 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, triethyl 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, etc. be able to. These hydrophilic glycol ether monoalkyl ethers (component (b3-1-1)) are components that satisfy not only the 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, and 3-methyl-3-methoxybutanol have a detergency against various stains. It is an excellent compound.

(Component (b3-2); glycol ether dialkyl ethers)
Glycol ether dialkyl ethers (component (b3-2)) are aliphatic or alicyclic compounds in which two hydroxyl groups are bonded to two different carbon atoms. Are 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 with respect to processing oils containing a large amount of poorly soluble components, and have an excellent detergency effect.

(Component (b3-2-1); hydrophilic glycol ether dialkyl ethers)
Among the above glycol ether dialkyl ethers (component (b3-2)), as a component suitable for washing water-soluble dirt such as water-soluble processing oil,
Requirements (1 ′): a component satisfying that phase separation does not occur when 60 parts by mass of glycol ether dialkyl ether and 40 parts by mass of water are mixed at 30 ° C. (hereinafter referred to as hydrophilic glycol ether dialkyl ethers) (Component (b3-2-1) may be mentioned), and this component (b3-2-1) is preferably a requirement (2); it can be mixed with water at 30 ° C in an arbitrary ratio. 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, and diethylene glycol diethyl ether. .

  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 and alicyclic hydrocarbons having 7 to 16 carbon atoms, preferably 10 to 16 carbon atoms. Hydrocarbons (component (b4)) can be used alone as component (b). Among these, it is particularly preferable to use in combination with the component (b1). However, the hydrocarbons can be used alone or in combination with a plurality of types of compounds.

  Specific examples of hydrocarbons include nonane, decane, decene, undecane, undecane, dodecane, dodecene, tridecane, tetradecane, pentadecane, menthane, bicyclohexyl, cyclododecane, 2,2,4,4,6,8, Examples include 8-heptamethylnonane. Among these, decane, decene, undecane, undecane, dodecane, dodecane, tridecane, and tetradecane are preferable, and decane, decene, dodecane, and dodecene are more preferable because they are excellent in detergency, drying property, and compatibility.

<< Compound having ester bond >>
As the compound having an ester bond, in addition to the fatty acid ester (b1), n-butyl acetate, isoamyl acetate, 2-ethylhexyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, ethyl lactate, propyl lactate, Examples include 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. It is done. In particular, glycol ether acetates and hydroxycarboxylic acid esters are preferred. Among these, there are preferred compounds, which will be described.

<Component (b5); Compound having an ester bond (excluding the component (b1))>
Among the compounds having an ester bond, in addition to the component (b1), compounds that exhibit particularly excellent effects include glycol ether acetates (component (b5-1)), or hydroxycarboxylic acid esters (component ( b5-2)) and the like. Glycol ether acetates (component (b5-1)) or hydroxycarboxylic acid esters (component (b5-2)) can be used alone as component (b). Among these, it is particularly preferable to use in combination with the component (b1). However, among 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 plurality of types of compounds can be used alone or in combination.

(Component (b5-1); glycol ether acetates)
Glycol ether acetates are compounds obtained by acetylating glycol ethers having a hydroxyl group. 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, and 3-methyl-3-methoxybutyl acetate. 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, dipropylene glycol mono-n-butyl ether acetate that do not produce alkoxyacetic acid in the metabolic system in the human body. 3-methoxybutyl acetate and 3-methyl-3-methoxybutyl acetate are preferred because of their lower toxicity.

(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 preferred. Specific examples include lactic acid ester, malic acid ester, tartaric acid ester, citric acid ester, glycol monoester, glycerin monoester, glycerin diester, ricinoleic acid ester and castor oil.

  Among the above 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.

[Preferred combination (1) of component (B); when using component (b1)]
In the present invention, the component (B) exemplified above can be used. Among them, when used in combination with the component (A), the component (B) is the component (b) and the component (b) in order to have excellent compatibility with the component (A) and exhibit a particularly excellent cleaning effect. ) Is preferably used as the component (b1) (fatty acid ester), particularly preferably the fatty acid ester represented by the general formula (1).

  In this invention, when a component (B) is a component (b), the whole quantity of a component (b) can be comprised with a component (b1). In the component (b), the total amount of the component (b) can be composed of components other than the component (b1). However, depending on the object to be cleaned and the cleaning apparatus to be used, the component (b1) and glycol ethers (component (b3)) (specifically, glycol ether monoalkyl ethers (components) may be used as the component (b). (B3-1)) and / or glycol ether dialkyl ethers (component (b3-2))), hydrocarbons (component (b4)), glycol ether acetates (component (b5-1)), and hydroxycarbon One or more compounds (component (b ′)) selected from the group consisting of acid esters (component (b5-2)) can also be used in combination.

  When combining the component (b1) and the component (b ′), when the total amount of the component (b) (the total mass of the component (b1) and the component (b ′)) is 100% by mass, the component (b1) It is preferable that 10 mass% or more and 90 mass% or less and a component (b ') shall be 10 mass% or more and 90 mass% or less. More preferable oil solubility is obtained when the mass ratio of the component (b1) in the component (b) is 10% by mass or more, and more preferable detergency for various types of dirt is obtained when the mass ratio is 90% by mass or less. . When considering the oil solubility and the balance of cleaning properties against various stains, the component (b1) is more preferably 20% by mass or more and 80% by mass or less, and the component (b1) is further 30% by mass or more and 70% by mass. % Or less is preferable. In addition, the suitable mixture ratio of this component (b1) and component (b ') does not change even if it is any of a cleaning composition and a rinse agent composition.

  When a member containing an elastomer or other resin (hereinafter sometimes referred to as a resin member) is used for an object to be cleaned, a cleaning device, etc., the damage given 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 include 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 to 90% by mass, the glycol ethers (b3) are 10% by mass to 90% by mass, and the component It is preferable that the other component (bx) selected from (b4), the component (b5-1), and the component (b5-2) is 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) is 10% by mass or more and 50% by mass. More preferably, the content of the other component (bx) is 0% by mass to 10% by mass, the component (b1) is 55% by mass to 95% by mass, and the glycol ethers (b3) are 15%. More preferably, the content of the other component (bx) is 0% by mass to 45% by mass. In addition, the suitable mixture ratio in these components (b) may not be any of a cleaning composition and a rinse agent composition. The cleaning composition and the rinsing agent composition satisfying the blending ratio can of course be used for cleaning and rinsing other than the resin member.

  Furthermore, in the case of cleaning water-soluble dirt, for example, water-soluble processing oil used when processing precision machine parts, optical machine parts, etc., as component (b), component (b1) and the above Glycol ethers (component (b3-1) and / or component (b3-2)), and among the glycol ethers, the hydrophilic glycol ether monoalkyl ether (component (b3-1-1)) ), And 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 to 90% by mass, the hydrophilic glycol ethers are 10% by mass to 90% by mass, and the other The component (bx) is preferably 0% by mass or more and 40% by mass or less. By satisfying this range, it is possible to further improve the cleaning performance for soluble soil and the cleaning performance for other soils. In order to further enhance the cleaning effect, the component (b1) is 50% by mass to 90% by mass, the hydrophilic glycol ethers are 10% by mass to 50% by mass, and the other components (bx) are 0% by mass. It is more preferable to set it as% or more and 10 mass% or less, a component (b1) is 55 mass% or more and 95 mass% or less, said glycol ethers are 15 mass% or more and 45 mass% or less, and said other component (bx) is 0. More preferably, the component (b1) is 55% by mass to 75% by mass, the glycol ethers are 25% by mass to 45% by mass, and the other component (bx) is 0% by mass. It is particularly preferred. In addition, the suitable mixture ratio in these components (b) may not be any of a cleaning composition and a rinse agent composition. In addition, the cleaning composition and the rinsing composition that satisfy the blending ratio can of course be used for cleaning and rinsing other than dirt such as water-soluble processing oil.

[Preferable combination (2) of component (B); when component (b2) is used]
When cleaning water-soluble dirt, for example, water-soluble processing oil used during processing of precision machine parts, optical machine parts, and flux components adhering during the manufacture of electronic parts, polyhydric alcohol is used as component (B). It is preferable to use a class (component (b2)). In this case, the total amount of component (B) can also be used as 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., especially poorly soluble components such as oil-based agents and extreme pressure additives, etc. When washing a large amount of dirt or the like, it is preferable to use the component (b2) in combination with at least one of the component (b1) and the component (b4) (preferably the component (b1)). Further, depending on the object to be cleaned and the cleaning apparatus used, as component (B), in addition to component (b2) and at least one of component (b1) and component (b4) (preferably component (b1)) , Other component (bz) (specifically, one or more selected from the group consisting of component (b3-1), component (b3-2), component (b5-1), and component (b5-2)) Component) 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 to 80% by mass, and the total of the component (b1) and the component (b4) is 20% by mass. It is preferable that the content (bz) is 0% by mass or more and 30% by mass or less, and 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 to 70% by mass, the component (bz) is preferably 0% by mass to 30% by mass, and the component (b2) is 40% by mass to 60% by mass. It is preferable that the sum total of b1) and the said component (b4) is 40 to 60 mass%, and a component (bz) is 0 to 20 mass%. Most preferably, the component (bz) is 0% by mass, the component (b2) is 40% by mass to 60% by mass, and the total of the component (b1) and the component (b4) is 40% by mass to 60% by mass. % Or less.

[Preferred combination (3) of component (B); when component (b4) is used]
In addition, various processing oils used in the processing of dirt, such as precision machine parts and optical machine parts such as cutting oils, presses, etc. Oil, drawing oil, heat treated oil, rust preventive oil, lubricating oil, etc., such as grease or waxes, especially when cleaning dirt that contains a lot of poorly soluble components such as oil agents and extreme pressure additives The component (B) is the component (b), and it is preferable to use hydrocarbons (component (b4)) as the component (b). In this case, the total amount of the component (b) can be used as the component (b4). Further, depending on the object to be cleaned and the cleaning apparatus to be used, as component (b), component (b4) and other components (by) (specifically, component (b1), component (b3-1), One or more components selected from the group consisting of component (b3-2), component (b5-1), and 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 to 100% by mass, and the other component (by) is 0%. It is preferable to set it as mass% or more and 90 mass% or less. By satisfying the blending ratio, the cleaning effect can be further enhanced. In order to further improve the cleaning effect on the soil containing a large amount of the hardly soluble component, the component (b4) is 30% by mass to 100% by mass, and the other component (by) is 0% by mass to 70% by mass. More preferably, the component (b4) is 40% by mass or more and 100% by mass or less, the other component (by) is more preferably 0% by mass or more and 60% by mass or less, and the component (b4) is 70% by mass or more. More preferably, the content is 100% by mass or less, the other component (by) is 0% by mass to 30% by mass, and the component (b4) is particularly preferably 100% by mass.

  Further, when the object to be cleaned is such that the hardly soluble component is adhered 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 content of the other component (by) 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 hardly soluble component while suppressing deterioration of the resin member. In order to further enhance the effect of preventing the deterioration of the resin member and enhance the cleaning effect of the hardly soluble component, the component (b4) is 30% by mass to 70% by mass, and the other component (by) is 30. It is more preferable to set the mass to 70% by mass or less.

  In addition, the suitable mixture ratio in these components (B) or a component (b) may not be any of a cleaning composition and a rinse agent composition. In addition, the cleaning composition and the rinsing agent composition satisfying the blending ratio can of course be used for cleaning and rinsing other than dirt such as poorly soluble components.

[Component (C)]
The cleaning composition and the rinsing composition of the present invention comprise, as the compound (Z), alcohols, ketones, esters and hydrocarbons having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more. One or more compounds selected from the group may contain a compound (hereinafter sometimes simply referred to as component (C)).

Specific examples of alcohols include methanol, ethanol, n-propanol, and isopropanol (isopropyl alcohol).
Examples of ketones include acetone and methyl ethyl ketone.

Examples of the esters include ethyl formate, propyl formate, isobutyl formate, methyl acetate, ethyl acetate, methyl propionate, and ethyl propionate.
As hydrocarbons, 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 within a range of ± 0.8 of the specific gravity of the component (A) to be used in combination in order to improve compatibility with the component (A). Is preferably within 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 compatibility at low temperatures, the difference between the specific gravity of the component (A) and the specific gravity of other components used in combination is reduced. This is very important.

  The boiling point of component (C) is preferably in the range of ± 40 ° C., more preferably in the range of ± 30 ° C., in order to reduce composition fluctuation during use. .

Moreover, when using a component (C), it is preferable that the component (A) is a component (C) used together is an azeotropic composition or an azeotrope-like composition having a composition close to it.
Among the components (C), particularly preferable components are hydrocarbons. Especially, it is preferable to use hydrocarbons as a component (C) with respect to washing | cleaning of processing oil.

<Stabilizer>
[Component (X)]
The detergent composition and rinse agent composition of the present invention contain a linear or branched alkene having 5 to 6 carbon atoms (hereinafter also referred to as “component (X)”) as an essential stabilizer. To do.
Among them, the alkene having 5 carbon atoms is more preferable, and among the alkenes having 5 carbon atoms, a branched alkene is more preferable, and 2-methyl-2-butene is particularly preferable.

[Component (Y)]
The cleaning composition and the rinsing agent composition of the present invention contain an optional stabilizer (hereinafter also referred to as “component (Y)”) other than the component (X) as long as the effects of the present invention are not impaired. May be.
Examples of the optional stabilizer include nitroalkanes, epoxides, amines, and triazoles (excluding benzotriazoles as ultraviolet absorbers described later). Moreover, you may use antioxidant (component which can prevent the oxidation of a washing | cleaning agent) as arbitrary stabilizers.

Nitroalkanes refer to aliphatic nitro compounds that contain one or more nitro groups. Specific examples include nitromethane, nitroethane, and nitropropane.
Epoxides refer to compounds having one or more epoxy groups that are 3-membered cyclic ethers. Specifically, 1,2-propylene oxide, 1,2-epoxy-2-methylpropane, 1,2-butylene oxide, 1,2-epoxy-3-phenoxypropane, butyl glycidyl ether, methyl glycidyl ether, ethyl Examples thereof include glycidyl ether, butyl glycidyl ether, vinyl glycidyl ether, allyl glycidyl ether, diethylene glycol diglycidyl ether, epichlorohydrin, and limonene oxide. Of these, 1,2-propylene oxide, 1,2-butylene oxide, and 1,2-epoxy-2-methylpropane are preferable, and 1,2-propylene oxide and 1,2-epoxy-2-methylpropane are more preferable. 1,2-propylene oxide is particularly preferred.

  The amines are compounds having one or more primary to tertiary amino groups. The amines may be acyclic amines or cyclic amines. Acyclic amines include aliphatic amines and aromatic amines. Examples of the aliphatic amine include a benzene nucleus-containing compound 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, picoline (mixture of three isomers), 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, benzene Ruamine, dibenzylamine, α-methylbenzylamine, propylenediamine, diethylhydroxyamine, pyrrole, N-methylpyrrole, ethanolamine, diethanolamine, triethanolamine, propanolamine, dipropanolamine, isopropanolamine, diisopropanolamine, N -Methylethanolamine, N, N-dimethylethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, diphenylamine and ethylenediamine. As the amines, alkylamines and cyclic amines are preferable. Among them, pyrrole, N-methylpyrrole, 2-methylpyridine, n-propylamine, diisopropylamine, diisobutylamine, N-methylmorpholine and N-ethylmorpholine are preferable. preferable.

  As the antioxidant, a phenol-based antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, or a sulfur-based antioxidant may be added. Specific examples are shown below. For the purpose of preventing the oxidation of the cleaning agent, for example, phenolic antioxidants include 1-oxy-3-methyl-4-isopropylbenzene, 2-tert-butyl-4-methoxyphenol, 2,6-bis (hydroxy Methyl) -p-cresol, p-cresol, 4-methoxyphenol, 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-hydroxymethylphenol, 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] may be the octadecyl-3- (3,5-di -t- butyl-4-hydroxyphenyl) compound such as propionate.

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

  Phosphorous antioxidants include phenyl isodecyl phosphite, diphenyl diisooctyl phosphite, diphenyl diisodecyl phosphite, triphenyl phosphite, trisnonyl phenyl phosphite, bis (2,4-di-tbutylphenyl) penta Mention may be made of compounds such as erythritol diphosphite.

  Examples of sulfur-based antioxidants include dilauryl-3, 3′-thiodipropionate, ditridecyl-3, 3′-thiodipropionate, dimyristyl-3, 3′-thiodipropionate, distearyl- Examples of the compound include 3,3′-thiodipropionic acid ester.

Among them, 2,6-di-t-butyl-p-cresol is preferable as the antioxidant.
Triazoles have an effect of suppressing corrosion or discoloration of a member or an object to be cleaned when contacted with the cleaning composition or the object to be cleaned is made of copper or a copper alloy (hereinafter referred to as “stability to copper and copper alloy”). From the viewpoint of exhibiting the properties of 1, 2,3-benzotriazole, carboxybenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole, 1- [N, N Mention may be made of -bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, 2,2 '-[[methyl-1H-benzotriazol-1-yl] methyl] imino] bisethanol. Among these, when 2-methyl 2-butene is used as the component (X), it is preferable to use 1,2,3-benzotriazole in order to further enhance the stability to copper and copper alloys. .
These components mentioned as arbitrary stabilizers may be used individually by 1 type, and may use 2 or more types together.

  As the optional stabilizer, the epoxides, the amines and the phenolic antioxidant are preferable, and 1,2-propylene oxide, 1,2-butylene oxide, diisopropylamine and 2,6-di-t are preferable. -Butyl-p-cresol is more preferred, 1,2-propylene oxide and 2,6-di-t-butyl-p-cresol are more preferred, and 1,2-propylene oxide is particularly preferred.

Alternatively, any stabilizer
1,2-propylene oxide, 1,2-butylene oxide, diisopropylamine, 2-tert-butyl-4-methoxyphenol, butylhydroxyanisole, 2,6-bis (hydroxymethyl) -p-cresol, p-cresol, From the group consisting of 4-methoxyphenol and 2,6-di-t-butyl-p-cresol,
Preferably 1,2-propylene oxide, 2-tert-butyl-4-methoxyphenol, 2,6-bis (hydroxymethyl) -p-cresol, p-cresol, 4-methoxyphenol, and 2,6-di- From the group consisting of t-butyl-p-cresol,
More preferably, it is selected from the group consisting of 1,2-propylene oxide, 2-tert-butyl-4-methoxyphenol, 2,6-bis (hydroxymethyl) -p-cresol, p-cresol, and 4-methoxyphenol. It is also preferable.

  Moreover, in order to raise stability with respect to copper and a copper alloy, it is preferable to use triazole as above-mentioned, and it is preferable to use 1,2,3- benzotriazole especially. This 1,2,3-benzotriazole is preferably used in combination with any other stabilizer.

  Furthermore, in order to suppress the oxidation of the cleaning composition and increase the stability of the cleaning composition itself, 1,2-butylene oxide, 2,6-di-t-butyl-p-cresol, diisopropylamine And at least one stabilizer selected from the group consisting of 1,2,3-benzotriazole.

[Other ingredients]
In the cleaning composition and the rinsing composition of the present invention, various auxiliary agents such as non-chlorine fluorine compounds, ultraviolet absorbers, surfactants, antifoaming agents are used as long as the effects of the present application are not impaired. Etc. 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 compounds>
Non-chlorine fluorine compounds are fluorine compounds in which a part of hydrogen atoms of hydrocarbons and ethers are substituted with only fluorine atoms and do not contain chlorine atoms. For example, they are specified by the following general formula (2) A cyclic HFC, a chain HFC specified by (3), or an HFE specified by (4), which does not contain a chlorine atom, and is composed of a carbon atom, a hydrogen atom, an oxygen atom, a fluorine atom, and A combination of two or more compounds selected from can be mentioned.
C _n H _2n-m F _m (2)
(In the formula, integers of 4 ≦ n ≦ 6, 5 ≦ m ≦ 2n−1 are shown)
C _x H _{2x + 2-y} F _y (3)
(Wherein, 4 ≦ x ≦ 6, 5 ≦ y ≦ 2x + 2 represents an integer)
C _s F _{2s + 1} OR (4)
(Wherein 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 chain HFCs 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-perfluorohexane and the like can be mentioned.

  Specific examples of HFE include methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, methyl perfluoropentyl ether, methyl perfluorocyclohexyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, and ethyl perfluoropentyl ether. Can do.

<Ultraviolet absorber>
Examples of ultraviolet absorbers 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, phenyl salicylates such as phenyl salicylate, 4-t-butylphenyl salicylate, 4-octylphenyl salicylate, bisphenol A-di-salicylate and -(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- ( And benzotriazoles such as 2′-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 quaternary ammonium salts. Examples of nonionic surfactants include alkylphenols, ethylene oxide adducts of linear or branched aliphatic alcohols having 8 to 18 carbon atoms, and block polymers of polyethylene oxide polypropylene oxide. Examples of amphoteric surfactants include betaine type and amino acid type.

<Antifoaming agent>
Examples of antifoaming agents include self-emulsifying silicones, fatty acids, higher alcohols, polypropylene glycol polyethylene glycols, and fluorine-based surfactants.

[Preferred blending ratio of cleaning composition]
The cleaning composition of the present embodiment comprises the component (A) and the component (X), and if necessary, the component (B), the component (C), the component (Y), and the various auxiliary agents. Each component is obtained by mixing and homogenizing according to a conventional method.

  The mass ratio of each component is not particularly limited as long as the high detergency, metal corrosivity, low toxicity, and low flammability characteristic of the cleaning agent are not impaired, but the component (B) is not limited. When mix | blending, it is preferable to contain 20 mass parts or more and 80 mass parts or less of a component (B) with respect to 100 mass parts of total amounts of the said component (A) and the said 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 against various types of dirt can be obtained, and when it is 80 parts by mass or less, the cleaner component on the surface of the object to be cleaned is more preferable. Low persistence is obtained. A more preferable range of the content of the component (B) in consideration of the balance between the cleaning property 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, more preferably 40 parts by mass or more and 60 parts by mass or less.

  When component (B) is component (b) and component (b1) and component (b ′) are used in combination as component (b), component (b2), component (b), and component (B) When component (B) is component (b) and component (b4) and component (by) are used in combination as component (b), the preferred blending ratio of these components is as described above. As described. In addition, the compounding quantity in the case of using a multiple types of component (B) is based on the whole quantity of a component (B). That is, the total amount of the plurality of types of components (B) is set within the range of the amount of the components (B) described above.

  When the component (C) is used in combination, the mass ratio ranges from 1 part by mass to 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 optional component (B). It is preferable to set it as a mass part or less, and also it is preferable to set it as 1 to 30 mass parts. When the proportion of the component (C) by mass is 1 part by mass or more, a more preferable effect of improving solvency against various types of dirt is obtained, and when it is 50 parts by mass or less, a more preferable low flammability is obtained. In addition, the compounding quantity in the case of using a multiple types of component (C) is based on the whole quantity of a component (C). That is, the total amount of the plurality of types of components (C) is set within the range of the amount of the components (C) described above.

  Moreover, when mix | blending the said component (C), in the total amount of 100 mass parts of the said component (A) and arbitrary said components (B), the said component (B) may be 0 mass part. . However, in order to exhibit a higher cleaning effect, it is preferable to blend the component (B), and the blending ratio of the component (B) is the blending ratio of the component (A) and the component (B). It is preferable to satisfy the range described in.

  In the present invention, when the component (B) and / or the component (C) is blended in order to further improve the detergency and the like, a particularly excellent effect is exhibited. That is, when the said component (B) and / or the said component (C) are mix | blended, not only the outstanding cleaning effect is exhibited, but it was excellent in stability, especially the cleaning agent excellent in stability with respect to stainless steel. It can be a composition.

  The amount of component (X) (essential stabilizer) is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 2 parts by mass, with the amount of component (A) being 100 parts by mass. More preferably, it is 0.01-0.5 mass part. By setting the blending amount of the component (X) to 0.001 to 5 parts by mass, a detergent composition with higher stability can be obtained while having a high cleaning effect.

  The compounding amount of the component (Y) (optional stabilizer) is not particularly limited, but preferably 5 to 4000 parts by mass, more preferably 100 parts by mass of the component (X). The amount is 20 to 1000 parts by mass, more preferably 30 to 300 parts by mass.

Moreover, when using 2 or more types of arbitrary stabilizers (component (Y)) together, when the quantity of the largest component shall be 100 mass parts, the total amount of another component becomes like this. Preferably it is 10-300 mass parts, More preferably Is 20 to 200 parts by mass.
The compounding amount of the other compounding agent is not particularly limited, but when the amount of the component (X) is 100 parts by mass, it is preferably 5 to 4000 parts by mass, more preferably 20 to 1000 parts by mass, The amount is preferably 30 to 300 parts by mass.
Moreover, when using together with a stabilizer (component (Y)), when the quantity of a component with the largest component (Y) is 100 mass parts, the compounding quantity of other compounding agents is preferably 10-300 mass parts, for example. More preferably, it is 20-200 mass parts.

[Preferred blending ratio of rinse agent composition]
The rinse agent composition of the present embodiment includes, for example, the component (A) and the component (X), and, if necessary, the component (B), the component (C), the component (Y), and the various assistants. Examples thereof include a method in which each component of the agent is obtained by mixing and homogenizing according to a conventional method, and a method in which the cleaning composition of the present embodiment is heated, steam is generated and cooled to obtain a condensate. When using the rinse agent composition of this embodiment continuously, it is preferable to utilize the condensate obtained by generating a vapor | steam.

Specific combinations of the components in the rinse agent composition include specific combinations of the components in the cleaning composition.
When the said component (B) is mix | blended, the suitable mixture ratio of the rinse agent composition of this invention is the said component with respect to 100 mass parts of total amounts of the said component (A) and the said component (B). (B) is preferably 0.01 parts by mass or more and 2.0 parts by mass or less. By satisfying this range, the rinse agent composition can balance the rinse effect and the ease of drying. Considering applicability of the apparatus, the blending ratio of the rinse agent composition is 0.01 parts 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 preferable to set it as 1.0 mass part or less, and it is still more preferable to set it as 0.01 mass part or more and 0.5 mass part or less. In addition, the compounding quantity in the case of using a some component (B) is based on the whole quantity of a component (B). The rinse agent composition can be used as it is if the condensate of the cleaning composition satisfies the above range, or the component (A) and component (B) can be added separately to adjust the mixing ratio. .

  Moreover, when mix | blending a component (C), the said component (C) is 0.01 mass part or more and 20 mass parts with respect to 100 mass parts of total amounts of the said component (A) and the said component (B). It is preferable to contain below. Especially, since it is close to a drying process to use a rinse agent composition, flammability must be lowered depending on the drying method. Therefore, the component (C) is more preferably 0.01 parts by mass or more and 10 parts by mass or less, and further preferably 0.01 parts by mass or more and 5 parts by mass or less. In addition, the compounding quantity in the case of using a some component (C) is based on the whole quantity of a component (C). The rinse agent composition can be used as it is if the condensate of the cleaning composition satisfies the above range, or the component (A), the component (B), and the component (C) are separately blended to obtain a blending ratio. It can also be adjusted.

  When component (B) is component (b) and component (b1) and component (b ′) are used in combination as component (b), component (b2), component (b), and component (B) When component (B) is component (b) and component (b4) and component (by) are used in combination as component (b), the preferred blending ratio of these components is as described above. As described.

  The amount of the component (X) (essential stabilizer), the amount of the component (Y) (optional stabilizer), and each component when two or more optional stabilizers (component (Y)) are used in combination The ratio of these and other compounding agents are the same as those described above in the cleaning composition.

[Cleaning method]
The cleaning method of the present embodiment includes a step of cleaning dirt adhered to an object to be cleaned with a cleaning composition. Furthermore, it is preferable to include a step of rinsing and / or steam cleaning using cleaning agent vapor and condensate generated by heating the cleaning composition after cleaning with the cleaning composition. In particular, the component (A) needs to be contained in order to make the cleaning composition and the rinsing composition non-flammable. The cleaning process can be effectively cleaned by combining physical methods such as wiping, dipping, and showering for the purpose of improving the cleaning performance. In the rinsing step, the rinsing property is further improved by combining physical methods such as dipping and showering for the purpose of improving the rinsing property. In addition, it is more preferable to use a solvent that does not substantially contain a soil component as a rinsing agent in order to improve rinsing properties. The discharge pressure when performing 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 cleaning properties and drying properties when using the cleaning composition. Furthermore, by using the steam and condensate obtained by heating the cleaning composition as the rinse composition and the replenishing liquid, it is possible to obtain stable cleaning properties by suppressing the composition variation of the cleaning composition. This is possible and has little influence on the material of the object to be cleaned, and can be said to be the most suitable cleaning method. Furthermore, a cleaning method and a cleaning apparatus as described in Patent Document 3 can be used.

  Hereinafter, the present embodiment will be described more specifically by way of examples. However, the present embodiment is not limited to the following examples.

[Examples 1 to 53, Comparative Examples 1 to 4]
In each Example and Comparative Example, each component was blended at the blending ratios shown in Tables 1, 2, and 3 and mixed to produce the intended cleaning composition. In Tables 1, 2, and 3, each symbol is as follows. The blending amount (parts by mass) of the component (Z), the component (X), and the component (Y) is the blending amount (parts by mass) when the component (A) is 100 parts by mass.
Ingredient (A)
1233Z; cis-1-chloro-3,3,3-trifluoropropene component (Z)
LM; methyl laurate (methyl dodecanoate)
HG; hexylene glycol (2-methyl-2,4-pentanediol)
IPA; isopropyl alcohol MC; methyl caprylate CM; methyl caprate DM DM; methyl decenoate DoM; methyl dodecenoate PGiPE; propylene glycol mono-i-propyl ether DPGME; dipropylene glycol monomethyl ether DPGDME; dipropylene glycol dimethyl ether DEGBE Mono-n-butyl ether DEGDBE; diethylene glycol di-n-butyl ether 3M3MB; 3-methyl-3-methoxybutanol LaM; methyl lactate LaB; butyl lactate DPGMEA; dipropylene glycol monomethyl ether acetate component (X)
MB; 2-methyl-2-butene component (Y)
PO; propylene oxide (1,2-propylene oxide)
1, 2-butylene oxide BHT; 2,6-di-tert-butyl-p-cresol DIPA; diisopropylamine αMS; α-methylstyrene MGE; methyl glycidyl ether BGE; butyl glycidyl ether IBO; 2-methylpropane RO; limonene oxide BMF; 2-tert-butyl-4-methoxyphenol BHA; butylhydroxyanisole BHMpC; 2,6-bis (hydroxymethyl) -p-cresol pC; p-cresol MF; Methoxyphenol DIBA; diisobutylamine MP; N-methylpyrrole MM; N-methylmorpholine BT; 1,2,3-benzotriazole Other compounding agents UV absorber HMB; 2-hydroxy-4-methoxybenzophenone For the detergent composition, the following (1), the test of (2) to evaluate the cleaning effect was performed to evaluate the stability by the tests described below (3). The results are summarized in Tables 1, 2, and 3.

(1) Metalworking oil solubility test 0.5 g of metalworking oil (trade name: Yusilon Former CF-6120, manufactured by Yushiro Chemical Industry Co., Ltd.) was added to 5.0 g of a detergent composition at 25 ° C., and shaken. The mixture was shaken with a stirrer for 2 minutes (60 times / minute), allowed to stand for 5 minutes, and 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 exist.

(2) Water-soluble processing oil solubility test 0.5 g of water-soluble processing oil (trade name: Hokat 795B, manufactured by Nippon Horton) is added to 5.0 g of the detergent composition, and shaken for 2 minutes with a shaker (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: Water-soluble oil component separation.

(3) Stability test 300 g of the detergent composition was placed in a 500 ml eggplant flask and fixed so that the eggplant flask was immersed in about 1/3 of a normal temperature oil bath. Next, a balled cooling tube was set on the top of the eggplant flask, and cooling water adjusted to 10 ° C. was allowed to flow. Then, the oil bath was heated and maintained at 75 ° C., and the cleaning composition was refluxed. An SUS wire was inserted into the eggplant flask from the top of the condenser tube with a ball, and fixed so that the tip of the wire was immersed in the cleaning composition. In this state, the reflux operation was continued, and the wire surface was visually confirmed after a predetermined time had elapsed after the wire was inserted. If there was an abnormality or change such as discoloration or corrosion on the wire surface in a shorter time, it was judged that the SUS stability was poor.
<Evaluation criteria>
A: No change for 14 days.
B: Change in less than 14 days.
C: Change in less than 10 days.
D: Change in less than 6 days.
E: Change in less than 3 days.

  The cleaning composition containing component (A) (HCFO-1233zd (Z)) and component (X) (2-methyl-2-butene) is a comparative example between Comparative Example 1 and Examples 1-4, Comparative Example 3 and Examples 16 to 18 or Comparative Example 4 to Examples 22 to 30 and 46 to 49, etc., the oil solubility was excellent and the stability was high.

  Further, in the detergent composition containing an optional stabilizer component (Y), it is apparent from the results of Examples 5 to 15, Examples 17, 18, and 21, Examples 31 to 45, or Examples 50 to 53. In addition, higher stability was obtained.

[Examples 54 to 109, Comparative Examples 5 to 7]
In each of Examples (Examples 54 to 109) and Comparative Examples (Comparative Examples 5 to 7), each component is blended at a blending ratio shown in Tables 4, 5, and 6 and mixed to obtain a target cleaning agent. A composition was prepared. In Tables 4, 5, and 6, each symbol is as described above. Moreover, the compounding quantity (mass part) of a component (X), a component (Y), and another compounding agent is a compounding quantity (mass part) when a component (A) is 100 mass parts.
About the obtained cleaning composition, (1) metalworking oil solubility test, (2) water-soluble processing oil solubility test, and (Examples 1 to 53, Comparative Examples 1 to 4) and ( 3) The stability test was evaluated, and the results are shown in Tables 4, 5, and 6.

[Examples 110 to 113, Comparative Example 8]
In each of Examples (Examples 110 to 113) and Comparative Example 8, each component was blended at a blending ratio shown in Table 7 and mixed to produce a target cleaning composition. In Table 7, each symbol is as described above. Moreover, the compounding quantity (mass part) of a component (X), a component (Y), and another compounding agent is a compounding quantity (mass part) when a component (A) is 100 mass parts.
The obtained cleaning composition was evaluated in the following (4) accelerated oxidation test, and the results are shown in Table 7.

(4) Accelerated oxidation test 200 ml of the cleaning composition was placed in a 500 ml Erlenmeyer flask equipped with a Liebig condenser and an oxygen inlet pipe (inner diameter 3 mm). One piece of polished soft steel (2 mm × 6 mm × 20 mm) is immersed in the cleaning composition, and another piece of soft steel (2 mm × 13 mm × 50 mm) is connected to the oxygen introduction tube, It hung on the vapor layer above the liquid surface of the cleaning composition. The position of the oxygen inlet tube is adjusted so that the tip is located at a height within 6 mm from the bottom of the Erlenmeyer flask, water is passed through the Liebig condenser, and oxygen bubbles saturated with water are 10 to 12 per minute. The cleaning composition is heated with a 150 W bulb while passing through the cleaning composition at a rate of one piece, and the vapor is adjusted to condense at a height below its center in a Liebig condenser for 96 hours. Reflux was performed. The stability of the cleaning composition was evaluated by measuring the pH of the cleaning composition before and after the test (the smaller the change in pH, the less the cleaning composition was changed, and the cleaning composition itself) Can be evaluated as stable).
In the pH measurement, 50 ml of neutral distilled water was added to 50 ml of the detergent composition, shaken for 1 minute, and then left to stand, and the pH of the upper layer liquid (aqueous layer) separated into two layers was measured with a pH meter (HM-30R, Measured with Toa DK Corporation.

  The cleaning composition and the rinsing composition of the present invention are used for cleaning processing oils containing a large amount of hardly soluble components such as processing oils, greases and waxes used when processing precision machine parts and expensive machine parts. It can be used suitably.

Claims (15)

Cis-1-chloro-3,3,3-trifluoropropene (A);
A detergent composition comprising a stabilizer (X) comprising a linear or branched alkene having 5 or 6 carbon atoms.   The cleaning composition according to claim 1, wherein the alkene is a branched alkene.   The cleaning composition according to claim 1 or 2, wherein the alkene is 2-methyl-2-butene.   The cleaning composition according to any one of claims 1 to 3, further comprising a stabilizer (Y) other than the stabilizer (X).   The cleaning composition according to claim 4, wherein the stabilizer (Y) is at least one selected from the group consisting of epoxides, amines, and phenolic antioxidants.   An organic compound having an ether bond and / or an ester bond, a hydrocarbon (excluding the component (X)), an alcohol compound, and at least one compound (Z) selected from the group consisting of ketones. The cleaning composition as described in any one of 1-5. As the compound (Z), an organic compound having an ether bond and / or an ester bond with a vapor pressure at 20 ° C. of 1.33 × 10 ⁻² Pa or more and less than 1.33 × 10 ³ Pa, a vapor pressure at 20 ° C. of 1 .33 × 10 ⁻² Pa to 1.33 × 10 ³ Pa hydrocarbons and polyhydric alcohol compounds having a vapor pressure at 20 ° C. of 1.33 × 10 ⁻² Pa to 1.33 × 10 ³ Pa The cleaning composition of Claim 6 containing 1 or more types of compounds (B) chosen from the group which consists of.   Examples of the compound (B) include fatty acid esters (b1), polyhydric alcohols (b2), glycol ethers (b3), hydrocarbons having 7 to 16 carbon atoms (b4), and compounds having an ester bond (however, The detergent composition according to claim 7, comprising one or more compounds selected from the group consisting of (b5), excluding the fatty acid esters (b1). As the compound (Z), one or more compounds (C) selected from the group consisting of alcohols, ketones, esters, and hydrocarbons having a vapor pressure at 20 ° C. of 1.33 × 10 ³ Pa or more are contained. The cleaning composition according to any one of claims 6 to 8.   The cleaning composition according to claim 9, comprising an alcohol as the compound (C).   The cleaning composition according to claim 10, wherein the alcohols contain isopropyl alcohol. Cis-1-chloro-3,3,3-trifluoropropene (A);
The rinse agent composition containing the stabilizer (X) which consists of a linear or branched alkene whose carbon atom number is 5 or 6.   A cleaning method comprising the step (1) of cleaning an object to be cleaned with the cleaning agent composition according to any one of claims 1 to 11.   The method further comprises 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 composition and / or a condensate of the vapor. The cleaning method according to 1.   The said process (2) is a process of rinsing at least the said to-be-cleaned object which passed through the said process (1), The rinse agent composition of Claim 12 is used as a rinse agent in the said process (2). 14. The cleaning method according to 14.