JP6588769B2 - Cleaning solvent composition - Google Patents

Description

  The present invention relates to a cleaning solvent composition.

  Various processing oils such as cutting oils, press oils, heat treatment oils, rust prevention oils, lubricating oils, greases, waxes, etc. are used when processing precision machine parts, optical machine parts, etc. These stains need to be finally removed, and removal with a solvent is generally performed. Soldering is the most commonly used method for joining electronic circuits, but rosin is used to remove and clean oxides on the metal surface to be soldered, prevent reoxidation, and improve solder wettability. In general, the soldering surface is pre-treated with a flux containing as a main component. For soldering, the substrate is immersed in a solution-like flux to attach the flux to the substrate surface, and then a molten solder is supplied, or the flux and solder powder are mixed in advance to form a paste There is a method of heating after supplying the solder to the place to be soldered, but in any case, flux residue will cause corrosion of metal and deterioration of insulation, so it should be removed sufficiently after soldering is finished There is.

  As the cleaning agent used for removing the soldering flux, a chlorofluorocarbon solvent, for example, a chlorofluorocarbon solvent containing chlorine represented by 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) is used. It is used. A chlorofluorocarbon-based solvent is combined with other solvents (eg, methanol) in the form of an azeotropic or pseudo-azeotrope where the composition in the gas phase is substantially the same as the composition in the liquid phase. Has been. However, since it has become impossible to use it as a causative substance that destroys the ozone layer, an alternative cleaning agent for a cleaning agent using a chlorofluorocarbon-based solvent is widely desired.

  Hydrofluorocarbons (HFC) and hydrofluoroethers (HFE) have been proposed as alternative cleaning agents that do not contain chlorine atoms, and these have a low ozone layer depletion potential (ODP), are less toxic, It has a low global warming potential (GWP) and is environmentally clean. However, 1,1,1,3,3-pentafluorobutane (365mfc), which is one of the alternative cleaning agents that do not contain chlorine atoms, does not contain chlorine atoms, so that it is sufficient as a cleaning agent alone. There was a problem that could not be obtained.

  For such a problem, Patent Document 1 proposes a cleaning technique in which 1,1,1,3,3-pentafluorobutane and propylene glycol monomethyl ether, which is a glycol ether, are combined.

JP 2003-129090 A

  The flux cleaning agent needs to clean dirt containing rosin that is a flux component, amine compound hydrochloride that causes ionic residue, organic acid, and the like together. According to the present inventors, there was room for improving the cleaning effect on the rosin flux for the cleaning agent described in Patent Document 1. Furthermore, in an apparatus including steam cleaning, the cleaning agent needs to have an azeotropic-like composition in order to maintain the cleaning effect to some extent.

  An object of the present invention is to provide a cleaning solvent composition having an azeotrope-like composition and having a high cleaning effect against various soils.

  As a result of intensive studies to solve the above problems, the present inventors have determined that 1,1,1,3,3-pentafluorobutane, n-propyl alcohol and propylene glycol monomethyl ether have a specific blending weight ratio. It has been found that the cleaning solvent composition contained in can solve the above-mentioned problems, and has reached the present invention.

The present invention includes the following aspects.
(1) (A) 1,1,1,3,3-pentafluorobutane 60-80% by weight, (B) n-propyl alcohol 6.7-20% by weight, and (C) propylene glycol monomethyl ether 10-10 A cleaning solvent composition comprising only 20% by weight, wherein the content of (B) is less than twice the content of (C).
(2) (A) 1,1,1,3,3-pentafluorobutane 60-80 parts by weight, (B) n-propyl alcohol 6.7-20 parts by weight, and (C) propylene glycol monomethyl ether 10-10 A cleaning solvent composition comprising 20 parts by weight, wherein the total of (A) to (C) is 100 parts by weight, wherein the amount of (A) to (C) in the cleaning solvent composition is 95% by weight The solvent composition for washing | cleaning which is% -100 weight% and whose content of (B) is less than 2 times of content of (C).

  According to the present invention, it is possible to provide a cleaning solvent composition having an azeotrope-like composition and having a high cleaning effect against various stains.

(Solvent composition for cleaning)
The cleaning solvent composition (hereinafter also simply referred to as “solvent composition”) is (A) 1,1,1,3,3-pentafluorobutane 60 to 80% by weight, (B) n-propyl alcohol 6 0.7 to 20% by weight, and (C) 10 to 20% by weight of propylene glycol monomethyl ether, and the content of (B) is less than twice the content of (C). Here, “cleaning” means removing dirt from an object to be cleaned.

  The solvent composition does not destroy the ozone layer, and exhibits the same detergency and low toxicity as compared with those containing fluorocarbon and chlorinated hydrocarbons.

  (A) is 1,1,1,3,3-pentafluorobutane (also referred to as “365mfc”). (A) is a component that imparts low toxicity to the composition. The amount of (A) in the solvent composition is 60 to 80% by weight. When the amount of (A) is less than 60% by weight, there is a tendency that an azeotrope-like composition is not obtained, and when the amount of (A) is more than 80% by weight, the detergency tends to be inferior.

  (B) is n-propyl alcohol. (B) is a component that imparts high detergency to the composition. The amount of (B) in the solvent composition is 6.7 to 20% by weight. When the amount of (B) is less than 6.7% by weight, the detergency tends to be inferior, and when the amount of (B) is more than 20% by weight, there is a tendency that an azeotrope-like composition is not obtained.

  (C) is propylene glycol monomethyl ether. (C) is a component that imparts high detergency to the composition. The amount of (C) in the solvent composition is 10 to 20% by weight. When the amount of (C) is less than 10% by weight, the detergency tends to be poor, and when the amount of (C) is more than 20% by weight, there is a tendency that an azeotrope-like composition is not obtained.

  In the solvent composition, the content of (B) is less than twice the content of (C). When the content of (B) is twice or more of the content of (C), there is a tendency that the detergency is inferior. This is because dirt usually contains many oil-soluble components, and in the combined use of (A) to (C), the amount of (C) having higher lipophilic properties compared to (B) is a predetermined amount or more. By doing so, it is considered that a high cleaning effect is exhibited. Therefore, the solvent composition does not include a solvent composition consisting of only 70% by weight of (A), 20% by weight of (B), and 10% by weight of (C). The content of (B) is preferably 0.2 to 1.5 times, more preferably 0.3 to 1.2 times the content of (C) from the point that the detergency tends to increase. .5 to 1.0 times is particularly preferable.

  The solvent composition may contain (D) a further component as long as the effects of the present invention are not impaired. Such a component is not particularly limited as long as it is a component commonly used in the field of cleaning agents, and examples thereof include an ultraviolet absorber and an antioxidant. The further components can be used alone or as a mixture.

  The ultraviolet absorber and the antioxidant are components that improve the stability of the solvent composition during long-term storage. An ultraviolet absorber will not be specifically limited if it melt | dissolves in a solvent composition, A benzotriazole type ultraviolet absorber, a benzophenone type ultraviolet absorber, and a hindered amine type ultraviolet absorber are mentioned. The antioxidant is not particularly limited as long as it is soluble in the solvent composition, and examples thereof include phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.

  The amount of (D) is such that the amount of (A) to (C) in the solvent composition is 95% to 100% by weight. Thus, the solvent composition comprises (A) 1,1,1,3,3-pentafluorobutane 60-80 parts by weight, (B) n-propyl alcohol 6.7-20 parts by weight, and (C) propylene glycol. 10 to 20 parts by weight of monomethyl ether, the total of (A) to (C) is 100 parts by weight, and the amount of (A) to (C) in the solvent composition is 95% to 100% by weight. It can also be a solvent composition in which the content of (B) is less than twice the content of (C).

  The solvent composition is an azeotrope-like composition. Here, the “azeotropic-like composition” means that the vapor composition and the liquid composition are almost the same, and the change in the composition after repeated evaporation and condensation changes only to a negligible level. A composition that exhibits similar properties (boiling point, etc.). Specifically, the azeotrope-like composition refers to a composition in which the difference between the liquid temperature and the vapor temperature is within 5 ° C. in the boiling state. Therefore, even when the solvent composition is used in a cleaning apparatus including steam cleaning, the cleaning effect can be maintained for a long time.

  The solvent composition can be produced by mixing the raw material components 1,1,1,3,3-pentafluorobutane, n-propyl alcohol, propylene glycol monomethyl ether and optionally further components. A commercially available thing can be used for the raw material component used for a solvent composition.

(Dirt)
The solvent composition is used for cleaning an object to be cleaned to which dirt is attached. As dirt, as dirt, processing oil (such as cutting oil, press oil, heat treatment oil, rust prevention oil, lubricating oil, etc.), oils, greases, waxes, water, One or more types of dirt selected from the group consisting of flux and the like can be mentioned. These soils may include at least one of oil-soluble and ion-contaminated (water-soluble) soils.

  Here, examples of the flux include rosin-based, organic acid-based, and inorganic acid-based fluxes. The rosin flux is composed of rosin (resin acid mainly composed of abietic acid) and non-active rosin flux mainly composed of rosins such as modified rosin; the rosin and an inorganic acid salt of an amine compound (for example, hydrochloride) , Sulfate) and an active rosin flux mainly composed of one or more activators selected from the group consisting of organic acids. Examples of the inorganic acid salt of the amine compound include triethanolamine hydrochloride, triethylenetetraamine hydrochloride, cyclohexylamine hydrochloride, and aniline hydrochloride. Examples of the organic acid include carboxylic acids (including dicarboxylic acids) such as succinic acid, adipic acid, glutaric acid, sebacic acid and maleic acid; and oxyacids (hydroxycarboxylic acids).

  Fouling of the flux includes rosin that is a flux component, an inorganic acid salt of an amine compound, an organic acid, and a component that is partially altered or carbonized by reflow at a high temperature. Here, the soil based on rosin is an oil-soluble soil, and the soil based on an inorganic acid salt of an amine compound and an organic acid is an ion-contaminating soil and causes an ionic residue.

(Object to be cleaned)
The object to be cleaned is not particularly limited, and examples thereof include precision machine parts, optical machine parts, metal processing apparatuses, and electronic parts manufacturing apparatuses. The article to be cleaned is preferably a part affected by flux, for example, a soldered electronic part or product. The type of such an object to be cleaned is not particularly limited, and examples thereof include a printed wiring board, a ceramic wiring board, a semiconductor element, and a semiconductor element mounting board. The material of the object to be cleaned is not particularly limited, and may be metal, plastic, or the like.

(Cleaning method)
The cleaning method using the solvent composition is a method for cleaning an object to be cleaned on which dirt is attached, and includes bringing the solvent composition into contact with the object to be cleaned. When the solvent composition is brought into contact with the object to be cleaned, the dirt attached to the object to be cleaned is peeled or removed from the object to be cleaned. The method for bringing the solvent composition into contact with the object to be cleaned is not particularly limited, and examples thereof include hand wiping, immersion cleaning (liquid phase cleaning), spraying, ultrasonic cleaning, and vapor cleaning (vapor phase cleaning). It is done.

  Immersion cleaning includes bringing a solvent composition into contact with an object to be cleaned by immersing part or all of the object to be cleaned in the solvent composition. The temperature of the solvent composition in the immersion cleaning is not particularly limited, and may be a temperature from room temperature (for example, 26 ° C.) to the boiling point of the solvent composition. There is also a method including bringing the solvent composition into contact with the object to be cleaned by immersing a part or all of the object to be cleaned in the solvent composition such as so-called boiling cleaning. Included in immersion cleaning. Steam cleaning includes bringing the solvent composition into contact with the object to be cleaned by bringing part or all of the object to be cleaned into contact with the vapor of the solvent composition.

  The cleaning time corresponding to the contact time between the solvent composition and the object to be cleaned is not particularly limited as long as it can remove dirt from the object to be cleaned.

(Use)
Solvent compositions include resist strippers, flux cleaners, degreasing cleaners, buffing cleaners, adhesive solubilizers, dry cleaning solvents, grease / oil / wax / ink removers, drainers, etc. It can be used for dirt cleaning agents, particularly rosin flux cleaning agents.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited by these Examples. Examples 3, 4, 10, 11, and 15 are examples, and examples 1, 25 to 9, 12 to 14, 16, and 17 are comparative examples. The cleaning solvent compositions of Examples 1 to 17 were prepared by mixing the components.

(Flux cleaning test)
The cleaning power of the cleaning solvent compositions of Examples 1 to 17 was evaluated by the following method.

<Detergency-Evaluation method>
(1) Preparation of cleaning test sample A rosin-based flux (HAKOOO-001 Hakuko Co., Ltd. product) is applied to a galvanized iron plate (equivalent to JIS G3302 length 30 mm, width 20 mm, thickness 0.3 mm) and hot at about 180 ° C The plate was baked for 10 minutes, further cooled to room temperature (26 ° C.), and allowed to stand at room temperature for 10 days to obtain a cleaning test sample (object to be cleaned to which rosin-based flux stains adhered).
(2) Cleaning test 20 g of the cleaning solvent composition was placed in a beaker, sealed with aluminum foil, adjusted to a liquid temperature of 40 ° C., and a cleaning test sample was immersed. After 3 minutes, the test sample was taken out from the beaker and allowed to dry naturally, and then the degree of whiteness was judged by visual judgment.

The evaluation of detergency in Tables 1, 2 and 3 is as follows.
○: There is no white residue. Δ: Some white residue remains. X: A white residue remains.

(Confirmation of azeotropic-like composition)
About the solvent composition for washing | cleaning of Example 3, Example 4, Example 9-Example 17, confirmation of the azeotrope-like composition was performed with the following method.

<Azeotropic composition-Evaluation method>
The boiling point of the liquid was measured in accordance with “Parallel reflux boiling point test method” defined in 7.1 of “Non-mineral oil brake fluid for automobile” (JIS K2233-1989). A thermometer plug was sealed from the side pipe of the flask between thick rubber, a cooling pipe was attached to the flask mouth, and water was cooled through the cooling pipe. Moreover, a thermometer was hung from the mouth of the cooling pipe, and the steam temperature was measured. Such an apparatus was prepared, and the cleaning solvent composition and boiling stone shown in Table 2 were placed in a flask and heated with a mantle heater. The heating temperature was adjusted so that the dropping rate of the vapor phase condensate was appropriate, and stable boiling was maintained for 30 minutes or more. After confirming that the liquid boiling point was stable, the vapor temperature and the liquid temperature were measured.

The evaluation of the azeotrope-like composition in Table 2 and Table 3 is as follows.
○: The difference between the liquid temperature and the vapor temperature is within 5 ° C. X: The difference between the liquid temperature and the vapor temperature is larger than 5 ° C.
The results are summarized in Tables 1-3.

  From Table 1, the solvent composition (Example 3, Example 4) of an Example had high detergency. On the other hand, a combination of 1,1,1,3,3-pentafluorobutane and propylene glycol monomethyl ether (Example 1) or a combination of 1,1,1,3,3-pentafluorobutane and n-propyl alcohol (Example 6) was inferior in detergency. Further, a combination in which the content of (C) in the solvent composition is more than 20% by weight (Example 2) and a combination in which the content of (B) is twice the content of (C) (Example 5) The detergency was inferior. Furthermore, the combination (Examples 7 and 8) of 1,1,1,3,3-pentafluorobutane with alcohols other than n-propyl alcohol was very poor in detergency.

  From Table 2 and Table 3, the solvent composition of an Example was azeotropic-like composition and was excellent in the washability. On the other hand, the solvent composition of the comparative example was not an azeotrope-like composition or was poor in cleanability.

  The solvent composition has an azeotrope-like composition and is excellent in detergency. In particular, since the solvent composition can clean rosin-based flux stains, it can be used as a cleaning agent for various stains including oil-soluble stains and ion-contaminated stains. Therefore, the solvent composition is extremely useful industrially as a cleaning agent for various soils using a cleaning device including steam cleaning.

Claims (2)

(A) 1,1,1,3,3-pentafluorobutane 60-80% by weight,
(B) n-propyl alcohol 6.7-20% by weight, and (C) propylene glycol monomethyl ether 10-20% by weight.
The solvent composition for flux cleaning which consists only of (B) and whose content of (B) is less than twice the content of (C). (A) 1,1,1,3,3-pentafluorobutane 60-80 parts by weight,
(B) Solvent for flux cleaning containing 6.7 to 20 parts by weight of n-propyl alcohol, and (C) 10 to 20 parts by weight of propylene glycol monomethyl ether, and the total of (A) to (C) is 100 parts by weight. The amount of (A) to (C) in the flux cleaning solvent composition is 95% to 100% by weight, and the content of (B) is 2 of the content of (C). Solvent composition for flux cleaning which is less than twice.