JPS58164698A - Active gas resistant rotary pump oil - Google Patents

Abstract

PURPOSE:To provide the titled rotary pump oil containing a specified perfluoroalkoxy cyclic phosphonitrilic ester as effective ingredient and exhibiting excellent resistance to active gas such as halogen compd. CONSTITUTION:The rotary pump oil consists mainly of a compd. of the formula where (CF2CF2)m segment indicates single (CF2CF2) or a mixture of the segments with different chain lengths; in the former case, m is 2 and in the latter case, m indicates average number of (CF2CF2) repeating units which represents average length, and is 1.3-2.8; n is the number of PN repeating units in the phosphonitrile ring structure of compd. of the formula, and is 3-4 obtained by interaction of an oligomer (trimer and/or tetramer) of phosphonitrilic halide and fluoroalcohol.

Description

[Detailed description of the invention]

This invention relates to rotary pump oil that has excellent durability. In general, rotary pump oil requires petroleum-based lubricating oil with extremely low vapor pressure and excellent heat resistance, which is obtained by further fractionating and refining a petroleum lubricating oil fraction with a kinematic viscosity of 40 oO and a kinematic viscosity of 30 to 150 centistokes by molecular distillation, etc. It is widely used as it has satisfactory performance. However, in recent years, the field of application of vacuum has expanded! 1, the performance required of rotary pump oil has become extremely high, and there are many cases in which petroleum-based rotary pump oil cannot satisfy these demands. In particular, with the expansion of the use of vacuum in thin film manufacturing technology, the emergence of rotary pump oil with excellent resistance to active gases such as nitrogen compounds is strongly desired.For example, dry etching in semiconductor manufacturing processes is strongly desired. The equipment's rotary pump oil uses a mixed gas of Freon-14 and oxygen as the active gas, so conventional petroleum-based rotary pump oil causes oil viscosity to increase and sludge to precipitate in a short period of time. 1. Requires frequent oil changes, and rotary pumps:
. A lot of time and effort for maintenance! , N1 forced to ease
1: It is worn out. Therefore, rotary pump oil that is particularly resistant to these active gases is required. Currently, equipment that requires the use or exhaust of active gases include semiconductor manufacturing equipment such as various dry etching equipment, ion implantation equipment windows, plasma OVN equipment, etc., and OVN% settings for cemented carbide cutting tools. , sponge titanium fabrication equipment, halogen lamp manufacturing equipment, steel degassing equipment, superconducting material manufacturing equipment, etc. Active gases include phosphine, arsine, diborane, hydrogen selenide, arsenic trichloride, silane, silicon tetrachloride, hydrogen chloride, dichlorosilane, Freon-14, ammonia, phosphorus pentafluoride, silicon tetrafluoride, and carbon tetrachloride. , oxygen, etc. are used singly or in combinations of Class 211 or higher depending on the purpose. The rotary pump oils used in the above equipment are all ts-conventional pump oils that react with active substances, etc.
7. If the oil deteriorates severely, for example, □・. In the case of chlorine-based active gas, the viscosity force S1 of the pump oil decreases, and in the case of fluorine-based active gas, changes such as an increase in viscosity and precipitation of sludge occur, so it cannot be used for a long time. Therefore, it is desired to develop a new pump oil with excellent active gas resistance to replace this. The present invention has been made with the object of providing a novel rotary pump oil with excellent gas resistance suitable for use in vacuum pumps of devices that use chemically active gases. That is, the present invention relates to a rotary pump oil containing a perfluoroalkoxy cyclic phosphonitrile ester (hereinafter referred to as perfluoroalkoxyphosphonitrile) as an active ingredient. The present inventors have discovered that conventional petroleum-based rotary pump oil has a short lifespan and is used in various equipment that uses active gases such as halogen compounds, especially equipment for l1fiL8 production, which has been rapidly increasing in recent years. In view of the current situation where it is necessary to spend a lot of time and effort on replacement and maintenance of vacuum pumps, which is the biggest bottleneck in improving the operating rate of equipment, it is necessary to improve the resistance to active gases and the physical properties required of rotary pump oil. As a result of extensive research on active-resistant rotary pump oils with excellent performance, we have found that perfluoroalkoxyphosphonitrite has the most suitable properties as the rotary pump oil, and that it can solve the above problems. The present invention was completed based on this discovery. Perfluoroalkoxyphosphonitrilates are known materials, and methods of synthesis and possible uses of the compounds are described in US Pat. No. 2,876.247. Examples of applications include high-temperature lubricating oil and hydraulic oil. Perfluoroalkoxyphosphonitrilate has since been studied for its practicality as a flame-retardant pressure-working fluid, especially for U.S. naval vessels, and its specific gravity is somewhat high, and other suitable flame-retardant hydraulic fluids are being developed. It seems that it was not put into practical use for reasons such as the fact that it was The present inventors have found that although the structure of perfluoroalkoxyphosphonitrite has hydrogen atoms, it is fluorinated with high carbon and is thought to have high halogen resistance, and that it has a low vapor pressure and suitability necessary as a vacuum oil. Focusing on the point that it is presumed that there are compounds with various properties such as We have conducted various studies on the desirable structure of perfluoroalkoxyphosphonitrilate, the physical properties that should be maintained, and its application characteristics as an active gas-resistant rotary pump oil. found that it is compatible with The perfluoroalkoxyphosphonitrilate used as the active gas-resistant rotary pump oil of the present invention satisfies various properties of teleology. "It is a substance obtained by reacting one or more kinds of fluoroalcohols that are widely distributed, and among these substances, the following formula (I):

[Seal (Oν, O12), 0H2O]gPI), --・-
---・-(1) (However, in formula (1), < ay, t
y2) mts rel segment is (oh, oν2)
a single segment or an integer that is an integer multiple of the unit
It shows a mixture of segments with chain lengths that are double, and a single
In the case of the segment, deliberation = 2, and different
In cases where segments with different chain lengths are mixed, this is not an issue.
is the average chain length in units of (OF20F2)
It means the uniform number of repetitions, and the oboro value is 1.3 r ml (2
, 8, and l is within the range of (the host of the compound of formula 13)
Sulfonitrile ring skeleton? Indicates the number of repetitions for 1 unit.
Given a mixture of rings with a given number of repeats, the average number of repeats is
is a J that takes a real value within the range of 3≦n≦4.
The chemical compounds shown are listed below.1. Particularly preferred among these
6), yo, formula (1), cW'・-1, a1. . ,. 1. Segment 2 2 is a single chain length segment of 2 points,
(and Otori = 3 hexakis(1,1,5-)hydride
octafluoropentoxy) lI octafluoropentoxy)
Al with ester. Among various lubricating oils, rotary pump oil is of high quality.
demanding low vapor pressure and appropriate viscosity index and
In addition to having low viscosity at room temperature, it has excellent oxidation stability and heat resistance.
Good lubricating properties are required. (1
The compound of the formula ) satisfies the various requirements mentioned above.
It was discovered. (1) The value of 臘 in the formula is 1.3 to 2.
Those within the range of 8 are those that synthesize the compound of formula (l).
H (Oν2ff?23mOH, OR
A perfluoroalcohol having the structure = 1.
2. So-called terrorism with an integer value of 3 or more
It is a mixture of fluorinated alcohols and its average
The value of relaxation falls within the range of 1.3 to 2.8.
It means that. In this case, the type is less than 1.3.
Perfluoroalkoxyphosphonitrilate when taking
Because the vapor pressure of
do! It may not be a big problem, but rotary pump oil
This is not preferable because the minimum pressure reached is higher than 2.8.
The starting power of the rotary pump increases (necessary).
(If the value of l is 3, then the type is 3 or less)
or higher compounds are solid at room temperature and can be used as general lubricants.
In the above cases (m or
3), but if n becomes 4, the compound becomes a liquid at room temperature.
However, it is quite viscous and does not serve the purpose.
stomach. - value is another value of the compound of formula (I)
The number of repeating units of a cyclic phosphonitrile halide, commonly
Otori is 3.4 for regular phosphonitrile halide oligomers.
．． Cyclic or linear with an integer value of 5t or more
It contains a compound of (true) formula, but it is a synthetic origin of a compound of formula
As a material, a cyclic n=3 or 4 phosphonitri
that ruhalides alone or in mixtures should be used.
It means. , linear phosphonitrile halide as raw material
If so, is the balance of the rotary pump oil characteristics mentioned above?
If it becomes bad and the melon size is 5 or more, it is liquid.
However, since the viscosity at room temperature is too high, the purpose of the present invention is
It is not in accordance with Among them, hexakis (1,1,5-trihydrofluoride)
(cutafluoropentoxy) fJM triphosphonitrile
Esters are the best in terms of viscosity and vapor pressure balance.
Is it also the preferred active gas resistant rotary pump oil?
found. This is a compound with a single structural formula.
The molecular weight distribution spreads like general rotary pump oil.
Since it is not a sticky oil, its viscosity properties are also very good.
It has a sharp vapor pressure characteristic that is much lower than that of other materials. Hexaki
(1,1,5-)lihydrooctafluoropentoxy
) Temperature of cyclic triphosphonitrile ester - steam pressure kneading
is shown in Figure 1. These perfluoroalkoxyphosphonitrilates
Synthesis can be carried out by known methods. metal sodium
An example of synthesis using the so-called Alcorado method using
However, the synthesis method is limited to the following.
It's not a thing. i.e. a four-wheel drive system equipped with a condenser, a stirring device and a temperature needle.
% 1,115-trihydrooctaful in a turophore flask
Oropentanol 479y (2,06 mol) and toluene
Prepare 1000 ■ I of Nin and cut into 11 small pieces while cooling.
45.3 g (1,977 l) was added, and the sodium
The reaction was carried out at 40oO for 4 hours until complete dissolution. this
Add phosphonite dissolved in 500+ml of toluene to the reaction solution.
Lyl chloride trimer 891 (0,25656 7 l) liquid
was added dropwise at about 50'O, and the reaction was stirred under reflux for 4 hours.
It was. Rinse with water to remove IJium (formed chloride).
After , dehydration and concentration, an oily crude product 3301 was obtained. this
Distilled under reduced pressure, 203-2100O/0.03-0.0
8mmH, 4F) fraction 280f was collected. colorless and transparent
As a result of analysis, this oily substance was found to be hexakis, (1, IJ -
) Cyclic triphos
Honitrile 1 Stel is the main ingredient! Confirm that it is there, then press R and MMR. The spectra of M8 are also shown in Figures 2 to 4.
It showed the structure. The northern weight of this material is 1.791 (
15/4°0), kinematic viscosity is 89.52ast (40°
0), the viscosity index was 88, and the pour point was -4500 (
This product is hereinafter referred to as [activated gas resistant rotary pump oil].
say). Same as above, 1,1.3-) Lihi dried Rochitrafluo
Lopropatur and 1.1.5-trihydrooctafluoro
Alcolade using an equimolar mixture of lopentanol
synthesized and reacted with this and phosphonitrile chloride trimer.
□Set up and treat in the same way, 174-178°O/0
．． A fraction of 0.04 to 0.08 wamHg was collected. This too
It is GOJ Koyoru emplacement and M/ of each acid in Go-M8
・From the value, 1 = 1 or 0.9%, mm for the compound of formula (1)
= 1.17 or 5.8%, m = 1.33 or 15.
1%, IB = 1.5 is 25.8%, m = 1
．． 67 is 27.2%, Ia = 1.83 or 15.2%
, check that weight = 2 is a mixture with a ratio of 9.9.
Therefore, the mixture as a whole is (the value of the meal of formula 13 or 1.595
I found out that it is very similar to . The physical properties of this compound are specific gravity: 1.736, viscosity #: 1
84ape (40'O), vapor pressure: 1mm1ly/
Ivy at 198°a (hereinafter referred to as "active gas resistant rotor")
(referred to as "Tary Pump Oil B"). Similarly, 1.1.3-) dahydrotetrafluoropropro
panol and 1.1.5-)lihydrooctafluorope
Equimolar mixture of tantanol and phosphonidosylchloride
Dotrimer 80% and phosphonitrile chloride tetramer
The compound obtained by reacting 20% of the mixture is (1)
A mixture of multiple components (theoretically 16 formulas) shown by the formula
Yes, this thing is 172~197° o/o, os ~
0.07mmHy f) The physical properties of the fraction are the ratio 11:1
．． 736, viscosity Ml: 215aps (40oO eight vaporization
Qi FE' 1+amHy/20! ! °O was
This is hereinafter referred to as "active gas resistant rotary pump oil a."
UJ. Same (, If (01201,) mOH20H't' table t
) 71 tL lef. Mixture of Merrick 7t alcohol (+=1°2.3.
Each ratio of 4.5 or 33.42.17.5.3
% (Go analysis value, average (F) w, (D value or 2.0
3) and phosphonitrile chloride trimer 80%
It is a mixture of 2° and phosphonitrile chloride tetramer.
The obtained product was distilled under reduced pressure to give a concentration of 175-253°/
0.03~0.06mmHy (D fraction is separated and
, W1 degree'1.770y/am'(2G'OJ
: 246ops, vapor pressure" 1mmHy/211°0
The above two examples and the compound represented by the silk-like formula (I) are
obtained (hereinafter referred to as "active gas resistant rotary pump").
J, such as "Poil p" (the synthesized compound is
The suitability of the pump oil for this purpose is determined by the examples.
It was confirmed that Comparative Example 1 Commercially available mineral oil rotary pump for direct-coupled oil rotary vacuum pump
Oil (Neovac MR200% 40oO kinematic viscosity W 74o
si) was injected and a mixed gas of Freon-14 and hydrogen was used.
The test plasma generator used was operated. 10
The motor current showed an abnormality after a few days had passed.
, the rotary pump stopped. Remove the oil and put it on the side
Filter sludge is generated, and the viscosity is 163o at 40 degrees.
It had become st. Comparative Example 2,'1 In Comparative Example 1, the city of 68ost at a viscosity of 4000
Except for using commercially available synthetic hydrocarbon rotary pump oil.
Comparative Example 1 and all (under similar conditions, the plasma generator
I operated the station. After 20 days, the motor
Rotary pump operation was stopped because the current value increased.
, tested the oil. Sludge is formed in the oil, and the viscosity is 142 at 40 cka.
It had become ast. Fact 11: A direct-coupled oil rotary vacuum pump that has been strictly cleaned with a solvent has a life-resistant
Same as Comparative Example 1 by applying gaseous rotary pump oil B.
The test plasma generator was operated. 30 days
No abnormality was observed in the motor current value during operation.
. When I drained the oil and examined it, I found a small amount of reddish brown liquid on top of the oil.
However, the viscosity was 180o at 4ooa.
p-, and the viscosity of new oil in isothermal coal is 184 op fermentation.
Almost no changes were observed in comparison. XR, MMR%MB (mass spectrum) of oil after use
The results of each analysis are compared with the spectrum of the oil before use.
I was not able to use it in comparison. The reddish-brown liquid is Prazu.
Or perhaps it comes from the object being etched.
However, it is enough to interfere with the operation of the rotary pump.
It wasn't. Example 2 Mixed gas of Freon-14 and oxygen gas in semiconductor manufacturing process
is used to perform etching work on silicon substrates.
Directly connected oil rotary vacuum pump (exhaust) for dry etching equipment
Speed 9604'/++aim, oil amount 2.217
Inject a gaseous rotary pump oil and operate.
Ta. 3i! If after driving for a while, I drained the oil and checked the results.
Remove the fruit and oil, and there may be some reddish-brown contaminants or a little floating on the top of the oil.
The viscosity of the oil itself is $7s.
st (40'O), 90sst (40oO) of new oil
There is almost no change compared to
There is no difference in the results of each spectrum from those before use (, above)
[Active gas resistant rotary pump oil]
was found to have extremely excellent resistance. In addition,
Cloudiness and reddish-brown floating matter are caused by external contaminants such as etchings.
It was determined that the problem was caused by an item entering the room. Implementation Example 3 Cleaning of the rotary pump using the same equipment as in Example 2
After that, the oil is treated with an active gas resistant rotary pump.
The same operation was carried out for 3 weeks after switching to 0". So
As a result, the rotary pump oil in Example 2 and
Similarly, rotary pump oil a has no change in chemical structure and viscosity.
Rotary pump oil with low temperature change and excellent active gas resistance
It was recognized that Comparative Example 3 In Example 3, the direct-coupled oil rotary vacuum pump was thoroughly cleaned.
Later, commercially available mineral oil-based rotary pump oil (Neovac
8T-200) was injected under exactly the same conditions.
I did the driving. The kinematic viscosity was 78·-t (40 J) before use.
- After 10811st (400OJic increase)
However, the appearance was dark brown and floating precipitates were observed, indicating progress of deterioration.
I was introduced to what I do. The load increases from around the second checkpoint.
However, an abnormality was detected. Forced to drive for up to 3 weeks
If you do this, the oil will completely turn into grease at room temperature.
Very fluid at 000O (488ast, 100°O
) had deteriorated to the point where it was visible. Naturally 2
After the first operation, it is not a normal operating condition, but due to the life of the oil.
It was determined that the culm was 1 week old. Example 4 Oil rotor lubricated with [Active gas resistant rotary pump oil D]
Chemical reactants subjected to bromination reaction using a vacuum pump
Concentration and distillation were performed. After 6 batches of 10 hour operation, the pump and
When we inspected the oil, we found that the oil was a dark red liquid suspended in it.
There was nothing wrong with the pump. The suspension is allowed to stand still.
Since the oil was aliquoted into the upper layer, it could be easily separated from the oil in the lower layer.
Ta. The oil in the lower layer is determined to be used based on the analysis results of MMR and MMR%MS.
It has been confirmed that the chemical structure is the same as before use, and the upper layer is
Determine whether it is a mixture of water containing bromine and low molecular weight organic matter.
I made it clear. If the oil in the lower layer was refined, it could be reused.
.

[Brief explanation of the drawing]

The first flash is ``Temperature of active gas resistant rotary pump oil A-
Vapor pressure diagram, Figure 2 is an infrared absorption spectrum diagram of [active gas resistant rotary pump oil], and the third leap is a proton spectrum diagram of [active gas resistant rotary pump oil J], Figure 4 is a mass spectrum diagram of “active gas resistant rotary pump oil”. Patent applicant Matsumura Petroleum Research Institute Co., Ltd. Continued from page 1 ■ Applicant Otsuka Chemicals Co., Ltd. 10 Bungo-cho, Higashi-ku, Osaka City Procedural amendment (method) % formula % Patent 1 Director Shima 1) Haruki Tono 1・Display of 11 cases Patent application No. 47680 of 1982 2 Name of the invention Rain T6 gaseous rotor ribbon 1-6J 3 Relationship with the case of person who straightens sleeves Patent applicant 4 Agent Postal code 540 5 Subject of amendment ( 1) Contents of amendment to the specification 6 (1) Engraving of the specification (no change in content) 7 List of attached documents (1) Description
1 procedural amendment (voluntary) 1 Indication of the case Patent Application No. 47680 of 1982 2 Name of the invention Activated gas resistant rotary pump oil 3 Person making the amendment Relationship with the case Patent applicant: 4 Agent 〒 Previous 0 ^ 5 Subject of amendment (1) "Claims" column of the specification (2) Contents of amendment 6 in the "Detailed description of the invention" column of the specification (1) Specification (April 1982) “4III
V-1 Scope of Claims” attached to “Amended Scope of Claims”
Correct as shown below. (2) "Activation-resistant rotary robot" on page 6, line 1 of the specification is corrected to "active gas-resistant rotary robot." (8) Correct “(by GO analysis value)” in the 6th line from the bottom of page 14 to “(by Go analysis value)”. (4) Change “r(20Cho) viscosity” from the last line of page 14 to [(
20'0), viscosity". (6) On page 17, line 9, "5 days of weekly driving" is corrected to "6 days of driving." 7. List of Attached Documents (1) Amended Claims 1. Amended Claims [1. The main component is perfluoroalkoxy cyclic phosphorus nitrile ester thread rotary pump oil. ((H(0・F201F2)IIIOH20)2pN)
n(1) However, in formula (I), the segment represented by (OF□ay2) is a single segment that is an integral multiple of the unit (0120)□) or a segment of different chain length that is an integral multiple of the unit. In the case of a single segment, rm = 2, and in the case of a mixture of 7-gumenes F with different chain lengths, the average chain length is (cF2opz) means the average repeating number of units, the value of haziness is within the range of 1.6≦≦2.8, and n is the PM of the phosphonitrile skeleton of the compound of formula (1). Indicates the number of repetitions of the unit and is a member of the antid[
In the case of a mixture of l rings, it indicates the average number of repetitions, and takes an inclusion value within the range of 6≦n≦4. 2. (01) of formula (1) described in claim 1
F20?2) The segment jll is a unit of m = 2.
An oil-resistant and gas-resistant rotary pump oil containing hexakis (1,1,5-)lihydrooctafluorobenxy) cyclic triphosphonitrile ester as a main component, which is a segment with a chain length and where n = 5. ” From E 74-

Claims (1)

[Scope of Claims] l A perfluoroalkoxy cyclic phosphonitrile ester rotary phono oil containing a compound of the following formula (1) as a main component and used in a rotary pump of a pressure reducing device that pumps chemically active gas. ((H(OF, 0P2), OH, O), PM),
(1) However, in formula (!), (01B”2)ws
The segment shown by indicates a single segment with an integer length of (OFF, 0F2) or a mixture of segments with different chain lengths that are multiples of an integer, and in the case of a single segment, O = 2, and in the case where segments of chain length are mixed, the average chain length is the average number of repeats in m, n, ) units,
The value of Otori is within the range of 1.3≦1162.8, and Otori indicates the repeating number of the PM unit in the phosphonitrile ring skeleton of the compound of formula (1), and it is a mixture of rings with increasing repeating numbers. indicates the average number of repetitions, and takes a real value within the range of 3(m(4fx).2.
at ) is a single-chain failure with ■ = 2 2
Hexakis (
Active gas-resistant rotary pump oil containing cyclic triphosphonitrile (1,1,5-trihydrooctafluoropentoxy) ester as a main component.