JP5236913B2 - Aerosol composition - Google Patents

Description

  The present invention relates to an aerosol composition, and more particularly to an aerosol composition having excellent heat resistance and lubricating properties, having excellent coating properties without adversely affecting rubbers and resins, and having little environmental impact.

  Conventionally, oil and grease have been applied to lubricated portions of office equipment, automobiles, industrial machines, and other devices that are difficult to disassemble.

  However, when performing maintenance of such equipment, it was necessary to disassemble and apply oil or grease each time.

  In order to perform maintenance, disassembly and assembling work are required, and it takes time to acquire the technology and work for that, and the burden on the worker is increased.

  In recent years, resin and rubber are frequently used in products, and petroleum-based aerosols and the like need to confirm compatibility with resin and rubber.

As a countermeasure, Patent Document 1 solves the compatibility problem by aerosolizing a fluorine-based lubricant.
Japanese Patent No. 2638102

  In Patent Document 1, Freon gas made of chlorine-fluorine gas is used as a preferred propellant. However, since this chlorofluorocarbon gas causes the destruction of the ozone layer, it is subject to regulation and cannot be used at present.

  Moreover, although patent document 1 has the description that the use of pressurized air and pressurized inert gas (nitrogen gas) is also possible, the usage-amount of the propellant is 10 to 99.93 weight%. .

  However, if it exceeds 10% by weight, the proportion of the propellant increases, the amount of the lubricating component contained in the aerosol can decreases, and the necessary lubricating component after injection cannot be secured, so film forming properties There is a problem inferior to

Furthermore, Patent Document 1 does not describe an optimum base oil viscosity. In the example of Patent Document 1, demnum S-65 and S-20 (both are trade names) are used. These kinematic viscosity Demnum S-65 is 58-72mm ² / s, S-20 is 20-30 mm ² / s.

  However, when such a low-viscosity base oil is used, heat resistance and lubricating performance under oil film strength become major issues.

  Patent Document 1 does not describe the thickener particle size. If a thickener with an average primary particle size exceeding 10 μm is used in the aerosol composition, clogging in a small path within the aerosol occurs, and a uniform grease film cannot be formed. There is a disadvantage of poor film properties.

  Accordingly, an object of the present invention is to provide an aerosol composition which is excellent in film forming property, excellent in heat resistance, excellent in lubricating performance under oil film strength, and environmentally friendly.

  Other problems of the present invention will become apparent from the following description.

  The above problems are solved by the following inventions.

(Claim 1)
In an aerosol composition comprising a base oil (component A), a thickener (component B), a fluorine-based diluent (component C), and a propellant (component D),
The base oil is a perfluoropolyether oil having a viscosity (kinematic viscosity at 40 ° C.) of 75 to 1200 mm ² / sec,
The thickener is polytetrafluoroethylene (PTFE) or tetrafluoroethylene-hexafluoropropylene copolymer (FEP) having an average primary particle size of 10 μm or less,
The fluorine-based diluent is hydrofluoroether or tetrafluoropentane, and is added in a proportion of 50 to 96% by weight in the total amount of the composition,
The propellant is an inert compressed gas selected from carbon dioxide gas, nitrogen gas or nitrous oxide gas, and the propellant is added in an amount of 0.2 to 5 % by weight (provided that the amount is 5 % by weight). grease aerosol composition, characterized by using a ratio of the excluded).

(Claim 2)
2. The grease aerosol composition according to claim 1, wherein the thickener is added at a ratio of 0.01 to 10% by weight in the total amount of the composition.

(Claim 3 )
The grease aerosol composition according to claim 1 or 2, which is used as a maintenance grease.

(Claim 4 )
In an aerosol composition comprising a base oil (component A), a fluorine-based diluent (component C), and a propellant (component D),
The base oil is a perfluoropolyether oil having a viscosity (kinematic viscosity at 40 ° C.) of 75 to 1200 mm ² / sec,
The fluorine-based diluent is hydrofluoroether or tetrafluoropentane, and is added in a proportion of 50 to 96% by weight in the total amount of the composition,
The propellant is an inert compressed gas selected from carbon dioxide gas, nitrogen gas or nitrous oxide gas, and the propellant is added in an amount of 0.2 to 5 % by weight (provided that the amount is 5 % by weight). oil aerosol composition, characterized by using a ratio of the excluded).

(Claim 5 )
The oil aerosol composition according to claim 4, which is used as a maintenance oil.

  According to the aerosol composition of the present invention, since the base oil viscosity is controlled to an appropriate viscosity, it has excellent heat resistance, excellent lubrication performance while maintaining oil film strength, and forms a sufficient oil film.

  In addition, since the particle size of the thickener is controlled, a uniform film can be formed, occurrence of problems such as aerosol clogging with solid particles is reduced, and the film forming property is excellent.

  Furthermore, in consideration of environmental influences, the atomization state is good by using a fluorine-based diluent that is compatible with the fluorine-based lubricant.

  Moreover, since the inert compressed gas (D component) used for the aerosol composition of the present invention is not compatible with the main components A, B, and C, the straight component of the main component is obtained during coating. And can be applied accurately to the lubricated part. Furthermore, since the D component is used in a proportion of 0.2 to 8% by weight, a necessary lubricating component after injection can be sufficiently secured, and thus the film forming property is excellent.

  Furthermore, since a thickener having an average primary particle size of 10 μm or less is used in the aerosol composition, clogging in a small path within the aerosol does not occur, and a uniform grease film can be formed. Excellent film-forming properties.

  Embodiments of the present invention will be described below.

  The grease aerosol composition of the present invention comprises a base oil (component A), a thickener (component B), a fluorine-based diluent (component C), and a propellant (component D).

<A component>
In the present invention, the component A perfluoropolyether oil can be selected from perfluoropolyether oils represented by the following general formulas (I) to (IV).

General formula _{(I) Rf (CF 2 CF} 2 O) m (CF 2 O) n Rf
In the above formula, Rf is a perfluoro lower alkyl group (for example, CF ₃ , C ₂ F ₅ etc.), and the CF ₂ CF ₂ O group and the CF ₂ O group are randomly bonded in the main chain.

Formula (II) RfO [CF (CF ₃ ) CF ₂ O] _a (CF ₂ CF ₂ O) _b (CF ₂ O) _c Rf
In the above formula, Rf is a perfluoro lower alkyl group (for example, CF ₃ , C ₂ F _5, etc.), and the CF (CF ₃ ) CF ₂ O group, CF ₂ CF ₂ O group and CF ₂ O group are the main chain. It is combined randomly.

Formula (III) RfO [CF (CF ₃ ) CF ₂ O] _p (CF ₂ CF ₂ O) _q Rf
In the above formula, Rf is a perfluoro lower alkyl group (for example, CF ₃ , C ₂ F _5, etc.), and the CF (CF ₃ ) CF ₂ O group and the CF ₂ CF ₂ O group are randomly bonded in the main chain. Has been.

Formula (IV) F (CF ₂ CF ₂ O) _s C ₂ F ₅

  In the above general formulas (I) to (IV), m, n, a, b, c, p, q, and s are all integers, and are appropriately determined so as to obtain the following kinematic viscosity.

The perfluoropolyether oil used in the present invention has a kinematic viscosity at 40 ° C. of 75 to 1200 mm ² / sec, preferably 100 to 800 mm ² / sec. The method for measuring the kinematic viscosity is in accordance with the provisions of JIS K2283 Canon-Fenske viscometer.

When the kinematic viscosity is less than 75 mm ² / sec, there is a possibility of causing a decrease in life, wear, and seizure such as an increase in evaporation loss and a decrease in oil film strength. On the other hand, when it exceeds 1200 mm ² / sec, there is a possibility that power consumption and torque will increase, such as an increase in viscous resistance, and it will be difficult to make an aerosol.

  The mixing ratio of the perfluoropolyether oil used in the present invention is preferably in the range of 2 to 40% by weight, more preferably in the range of 3 to 30% by weight. If it is less than 2% by weight, a sufficient lubricating film cannot be formed. On the other hand, if it exceeds 40% by weight, it is difficult to apply due to an increase in the viscosity of the composition.

<B component>
As the thickener for component B, polytetrafluoroethylene (PTFE) or tetrafluoroethylene-hexafluoropropylene copolymer (FEP) having an average primary particle size of 10 μm or less is used.

  B component polytetrafluoroethylene (PTFE) is a polytetrafluoroethylene having a number average molecular weight Mn of about 1,000 to 1,000,000 by a method such as emulsion polymerization, suspension polymerization or solution polymerization of tetrafluoroethylene. Ethylene is produced, and it is subjected to low molecular weight treatment by methods such as thermal decomposition, electron beam irradiation decomposition, physical pulverization, etc., and a powdery product having a number average molecular weight Mn of about 1,000 to 500,000 is used. It is done.

  The tetrafluoroethylene-hexafluoropropylene copolymer (FEP) polymerization method and molecular weight reduction treatment are performed in the same manner as in the above polytetrafluoroethylene, and the number average molecular weight Mn is about 1,000 to 50, A value of about 000 is selected.

  The obtained powdery polytetrafluoroethylene (PTFE) or tetrafluoroethylene-hexafluoropropylene copolymer (FEP) having an average primary particle size of 10 μm or less is used.

  In the present invention, the “average primary particle size” is an arithmetic average of particle sizes of particles (100 or more) observed with an electron microscope. The average primary particle size is the average particle size of particles such as polytetrafluoroethylene in the form of the smallest non-aggregated unit, and does not mean the particle size of the secondary aggregate formed by aggregation of the particles. Absent.

  When the average primary particle size exceeds 10 μm, clogging in a small path in the aerosol occurs and a uniform grease film cannot be formed. In contrast, in the present invention, by controlling the particle size, a uniform grease film can be formed without causing clogging in a small path within the aerosol.

  The blending ratio of component B to the aerosol composition is 0.01 to 10% by weight, preferably 0.01 to 8% by weight. If it is less than 0.01% by weight, the thickening effect of the fluororesin will not be exhibited, and no improvement in the retention capacity of the base oil is expected. On the other hand, if it exceeds 10% by weight, the composition becomes hard and aerosolization becomes difficult.

<C component>
Hydrofluoroether or tetrafluoropentane is used as the C component fluorine-based diluent.

  These fluorine-based diluents have an ozone layer depletion coefficient of 0 and are environmentally friendly diluents.

  As for the aerosol, the compatibility between the base oil and the diluent is important. In the case of a fluorine-based lubricant, the alcohol or petroleum-based diluent is separated from the base oil and is difficult to be aerosolized.

  Moreover, the atomization state at the time of spraying is important for aerosol, and by using hydrofluoroether or tetrafluoropentane, compatibility with a fluorine lubricant is good and the atomization state is also very good.

  It is preferable to add a fluorine-type diluent in the ratio which occupies 50 to 96 weight% in the composition whole quantity.

<D component>
As the propellant as the component D, an inert compressed gas selected from carbon dioxide gas, nitrogen gas, or nitrous oxide gas is used.

  Since the inert gas used in the present invention is not compatible with the A component, the B component, and the C component, the main component is less likely to be miniaturized during coating, and straightness can be obtained.

  When a liquefied gas typified by chlorofluorocarbon other than an inert compressed gas is used as in the prior art, the main component diffuses during injection and is applied over a wide range. For this reason, it is not possible to accurately apply to a necessary portion.

  It is important to use the propellant of the present invention in a proportion of 0.2 to 8% by weight in the total amount of the composition. Preferably it is 0.3 to 5 weight% of range. If the amount is less than 0.2% by weight, the entire amount cannot be applied or evenly applied due to a shortage of the amount of the injected gas. On the other hand, if the amount exceeds 8% by weight, the proportion of the propellant increases, the amount of the lubricating component contained in the aerosol can decreases, and the necessary lubricating component after injection cannot be ensured, resulting in film-forming properties. Inferior.

<Production method>
In the aerosol composition for grease of the present invention, an inert compressed gas (propellant) that is a D component is added to a mixture of the A component, the B component, and the C component (other additives may be added if necessary). It can be produced by mixing and adding.

  Other additives that can be added to the aerosol composition of the present invention include additives that have been added to conventional lubricants such as antioxidants, rust inhibitors, corrosion inhibitors, extreme pressure agents, oil agents, solid lubricants, etc. Agents.

  Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol and 4,4′-methylenebis (2,6-di-tert-butylphenol), alkyldiphenylamine, Examples include triphenylamine, phenyl-α-naphthylamine, phenothiazine, alkylated-α-naphthylamine, and alkylated phenothiazine.

  Examples of the rust preventive agent include fatty acids, fatty acid amines, alkylsulfonic acid metal salts, alkylsulfonic acid amine salts, oxidized paraffin, polyoxyalkyl ether, and the like.

  Examples of the corrosion inhibitor include benzotriazole, benzimidazole, thiadiazole and the like.

  Examples of extreme pressure agents include phosphorus compounds such as phosphate esters, phosphite esters, phosphate ester amine salts, sulfur compounds such as sulfides and disulfides, dialkyldithiophosphates, metal salts of dialkyldithiocarbamic acid, and the like. It is done.

  Examples of the oily agent include fatty acids or esters thereof, higher alcohols and polyhydric alcohols or esters thereof, aliphatic amines, and aliphatic monoglycerides.

  Examples of the solid lubricant include molybdenum disulfide, graphite, boron nitride, silane nitride, and silica.

  The aerosol composition of the present invention obtained as described above is preferably used for maintenance purposes, and therefore, for example, morphology is also important. The volume is desirably 50 to 350 ml.

  The aerosol composition of the present invention can be used not only for maintenance purposes as a fluorinated grease, but also for maintenance purposes as a fluorinated oil that does not use a thickener (component B).

  The aerosol composition of the present invention exhibits good performance when used for maintenance applications as described below. For example, for maintenance (regreasing), sliding parts with seal materials such as O-rings, oil seals, V-rings, D-rings, X-rings, and packings that require disassembly work or sliding that is difficult to disassemble. It requires a heating part of a fixing roll using resin and rubber near the part, a sliding part of office equipment such as a fixing roll part, a lubricating part that requires regular maintenance, and a resin material or It can be used in lubricated parts such as gears, valves, cocks, electrical contacts, rolling bearings, and sliding bearings that use rubber materials.

  Other information equipment such as personal computers, precision equipment such as cameras and watches, semiconductors that require chemical resistance, liquid crystal manufacturing equipment, industrial furnaces that require heat resistance, food furnaces, resin processing machines, papermaking machines, woodworking machines It is also applicable to.

  Examples of the present invention will be described below, but the present invention is not limited to such examples.

<A component (base oil)>
A-1 Rf (CF ₂ CF ₂ O) _m (CF ₂ O) _n Rf
Viscosity: (40 ° C.) 85 mm ² / sec A-2 Rf [CF (CF ₃ ) CF ₂ O] _m (CF ₂ O) _n Rf
Viscosity: (40 ° C.) 400 mm ² / sec A-3 RfO [CF (CF ₃ ) CF ₂ O] _n Rf
Viscosity: (40 ° C.) 1300 mm ² / sec A-4 RfO [CF (CF ₃ ) CF ₂ O] _n Rf
Viscosity: (40 ° C.) 1200 mm ² / sec A-5 RfO [CF (CF ₃ ) CF ₂ O] _n Rf
Viscosity: (40 ° C.) 15 mm ² / sec A-6 F (CF ₂ CF ₂ O) _s C ₂ F ₅
Viscosity: (40 ° C.) 65 mm ² / sec Rf is a perfluoro lower alkyl group

<Component B (Thickener)>
B-1 Emulsion polymerization polytetrafluoroethylene
(Molecular weight approximately 100,000 to 200,000, average primary particle size 0.2 μm)
B-2 Suspension polymerization polytetrafluoroethylene
(Molecular weight approximately 10,000-100,000, average primary particle size 8μm)
B-3 Suspension polymerization polytetrafluoroethylene
(Molecular weight approximately 10,000-100,000, average primary particle size 15 μm)
B-4 Solution-polymerized tetrafluoroethylene-hexafluoropropylene copolymer
(Molecular weight about 50,000-150,000, average primary particle size 0.2 μm)

<C component (fluorine-based diluent)>
C-1 Hydrofluoroether
("Novec HFE-7100" manufactured by Sumitomo 3M)
* Ozone depletion coefficient = 0.0
C-2 Tetrafluoropentane
(Mitsui / Dupont Fluoro Chemical “Bertrel XF”)
* Ozone depletion coefficient = 0.0
C-3 Hydrochlorofluorocarbon
("Asahi Klin AK-225" manufactured by Asahi Glass Co., Ltd.)
* Ozone depletion coefficient = 0.025 to 0.033

<D component (propellant)>
D-1 Carbon dioxide (inert compressed gas)
D-2 Nitrogen gas (inert compressed gas)
D-3 Freon gas ("R-134a" manufactured by Daikin)

Example 1-7 and Comparative Example 1-11
The A component, B component, C component, and D component were combined into aerosols as shown in Table 1, and the properties of the grease aerosol composition were evaluated by the following various test methods. The results are shown in Table 2.

Example 8 and Comparative Examples 12-17
The above A component, C component, and D component were combined into aerosols as shown in Table 3, and the properties of this oil aerosol composition were evaluated by the following various test methods. The results are shown in Table 4.

<Heat resistance>
After spraying for 5 seconds on an aluminum dish having a diameter of 50 mm and allowing to stand for 10 minutes, it was placed in a thermostatic bath at 200 ° C. and the evaporation loss rate (wt%) after 24 hours was measured.

<Abrasion test>
Test equipment: SRV tester Test piece:
Ball: 10mm in diameter (100Cr6)
Disc: 25mm in diameter (100Cr6)
Frequency: 50Hz
Load: 50N
Temperature: Room temperature Time: 60 minutes

  After the test under the above conditions, the wear depth was measured. As the measured value of the wear depth, five disc-side wear marks were measured with a direct contact surface roughness meter, and the maximum wear depth (μm) among the five points was adopted.

<Rubber / resin test>
Temperature: 70 ° C
Time: 70 hours Test piece:
Rubber: 25 × 25 × 2mm
Resin: 25 x 100 x 2mm

Evaluation method:
Rubber: sprayed on a rubber piece for 5 seconds, put into a constant temperature layer at a specified temperature, taken out after a specified time, and measured volume change rate (%).
Resin: Each resin was sprayed for 5 seconds under 5% stress, placed in a thermostatic bath at a specified temperature, taken out after a specified time, and cracks and cracks were visually observed. When the crack and the crack had generate | occur | produced, it was set as x, and when it did not generate | occur | produce, it was set as (circle).

<Environmental impact>
What did not contain an ozone layer destruction component in a composition was set as (circle), and what was contained was set as x.

<Atomization state>
The case where the mist when the aerosol was sprayed was fine and uniform in the form of a mist was marked with ◯, and the case where the particles were mixed and uneven in some places was marked with ×.

<Film-forming properties>
The aerosol can was sufficiently shaken on a 300 × 300 mm steel plate, sprayed for 10 seconds from a distance of 15 cm, and the degree of adhesion to the steel plate after application was visually confirmed. The case where it was uniformly applied was marked with ◯, and the case where it was uneven such as a mottled pattern was marked with ×.

<Injection stability>
A test similar to the film-forming property test is performed 5 times / day for 5 days to check whether the injection is stable. When all were applied uniformly, it was marked with ◯.

<Spray pattern>
The diameter (cm) of the main component adhering to the steel sheet was confirmed by the same test method as the film forming test.

  It can be seen that if the diameter is small, the straightness of the main component can be obtained at the time of application, and it can be applied accurately to the lubricated part.

Claims (5)

In an aerosol composition comprising a base oil (component A), a thickener (component B), a fluorine-based diluent (component C), and a propellant (component D),
The base oil is a perfluoropolyether oil having a viscosity (kinematic viscosity at 40 ° C.) of 75 to 1200 mm ² / sec,
The thickener is polytetrafluoroethylene (PTFE) or tetrafluoroethylene-hexafluoropropylene copolymer (FEP) having an average primary particle size of 10 μm or less,
The fluorine-based diluent is hydrofluoroether or tetrafluoropentane, and is added in a proportion of 50 to 96% by weight in the total amount of the composition,
The propellant is an inert compressed gas selected from carbon dioxide gas, nitrogen gas or nitrous oxide gas, and the propellant is added in an amount of 0.2 to 5 % by weight (provided that the amount is 5 % by weight). grease aerosol composition, characterized by using a ratio of the excluded).   2. The grease aerosol composition according to claim 1, wherein the thickener is added at a ratio of 0.01 to 10% by weight in the total amount of the composition. The grease aerosol composition according to claim 1 or 2, which is used as a maintenance grease. In an aerosol composition comprising a base oil (component A), a fluorine-based diluent (component C), and a propellant (component D),
The base oil is a perfluoropolyether oil having a viscosity (kinematic viscosity at 40 ° C.) of 75 to 1200 mm ² / sec,
The fluorine-based diluent is hydrofluoroether or tetrafluoropentane, and is added in a proportion of 50 to 96% by weight in the total amount of the composition,
The propellant is an inert compressed gas selected from carbon dioxide gas, nitrogen gas or nitrous oxide gas, and the propellant is added in an amount of 0.2 to 5 % by weight (provided that the amount is 5 % by weight). oil aerosol composition, characterized by using a ratio of the excluded). The oil aerosol composition according to claim 4, which is used as a maintenance oil.