JP7044514B2 - Grease for refrigerating machine oil - Google Patents

Grease for refrigerating machine oil Download PDF

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JP7044514B2
JP7044514B2 JP2017208378A JP2017208378A JP7044514B2 JP 7044514 B2 JP7044514 B2 JP 7044514B2 JP 2017208378 A JP2017208378 A JP 2017208378A JP 2017208378 A JP2017208378 A JP 2017208378A JP 7044514 B2 JP7044514 B2 JP 7044514B2
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refrigerating machine
grease
machine oil
oil
resin
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JP2019081817A (en
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典久 洞口
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Mitsubishi Heavy Industries Thermal Systems Ltd
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Mitsubishi Heavy Industries Thermal Systems Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/003—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/003—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • C10M2205/0265—Butene used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/017—Specific gravity or density
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Description

本発明は、冷凍機油用グリースに関する。 The present invention relates to grease for refrigerating machine oil.

冷凍サイクルでは、冷媒が液体から気体、気体から液体へと変化を繰り返しながら循環している。この冷媒が循環する循環ライン中に、冷媒を圧縮する圧縮機が配置されている。
圧縮機には、潤滑するための冷凍機油が収容されている。例えば特許文献１には、冷凍機油としてエステル油、エーテル油、カーボネート油の少なくとも１つを使用した冷凍圧縮機が開示されている。 In the refrigeration cycle, the refrigerant circulates while repeatedly changing from liquid to gas and from gas to liquid. A compressor that compresses the refrigerant is arranged in the circulation line in which the refrigerant circulates.
The compressor contains refrigerating machine oil for lubrication. For example, Patent Document 1 discloses a refrigerating compressor using at least one of an ester oil, an ether oil, and a carbonate oil as a refrigerating machine oil.

冷凍機油は冷媒に溶解しやすく、冷凍機油を溶解した冷媒が圧縮機から吐出され、冷凍サイクル内を循環する。このとき、冷媒に溶解した冷凍機油の一部が析出し、冷凍サイクル内の管壁や熱交換機等に付着して油膜を形成することで、熱伝導率が下がり、熱交換能力が低下することがあった。
そこで、近年では冷媒に相溶しにくい冷凍機油が用いられている。 The refrigerating machine oil is easily dissolved in the refrigerant, and the refrigerant in which the refrigerating machine oil is dissolved is discharged from the compressor and circulates in the refrigerating cycle. At this time, a part of the refrigerating machine oil dissolved in the refrigerant is deposited and adheres to the pipe wall or the heat exchanger in the refrigerating cycle to form an oil film, so that the thermal conductivity is lowered and the heat exchange capacity is lowered. was there.
Therefore, in recent years, refrigerating machine oil that is difficult to be compatible with the refrigerant has been used.

特開平９－３０３２７８号公報Japanese Unexamined Patent Publication No. 9-303278

しかしながら、冷媒に相溶しにくい冷凍機油を用いたとしても、冷媒の流れに伴って冷凍機油が流動し、冷媒と共に圧縮機から吐出されることがあった。その結果、冷凍サイクル内の管壁や熱交換機等に冷凍機油が付着して油膜が形成され、熱交換能力が低下する。
圧縮機の吐出口側に油分離器を設けて、圧縮機より吐出された冷媒と冷凍機油とを分離すれば、管壁や熱交換機等への油膜の形成を抑制できるが、冷凍サイクルの大型化につながってしまう。
そのため、冷凍機油には、冷媒に相溶しにくく、かつ、冷媒に流されにくいことが求められている。 However, even if refrigerating machine oil that is difficult to be compatible with the refrigerant is used, the refrigerating machine oil may flow with the flow of the refrigerant and may be discharged from the compressor together with the refrigerant. As a result, the refrigerating machine oil adheres to the pipe wall or the heat exchanger in the refrigerating cycle to form an oil film, and the heat exchange capacity is lowered.
If an oil separator is provided on the discharge port side of the compressor to separate the refrigerant discharged from the compressor from the refrigerating machine oil, the formation of an oil film on the pipe wall or heat exchanger can be suppressed, but the refrigeration cycle is large. It will lead to the conversion.
Therefore, the refrigerating machine oil is required to be difficult to be compatible with the refrigerant and to be difficult to be washed away by the refrigerant.

本発明は上記事情に鑑みてなされたもので、冷媒に相溶しにくく、かつ、冷媒に流されにくい冷凍機油用グリースを提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a grease for refrigerating machine oil that is difficult to be compatible with a refrigerant and is difficult to be washed away by a refrigerant.

上記課題を解決するために、本発明は以下の手段を提案している。
すなわち、本発明の一態様に係る冷凍機油用グリースは、炭化水素油と、融点が２７０℃以下の樹脂とを含み、２５℃における不混和ちょう度が１００～３４０である。 In order to solve the above problems, the present invention proposes the following means.
That is, the grease for refrigerating machine oil according to one aspect of the present invention contains a hydrocarbon oil and a resin having a melting point of 270 ° C. or lower, and has an immiscible consistency at 25 ° C. of 100 to 340.

上記構成によれば、基油である炭化水素油と、増ちょう剤である融点が２７０℃以下の樹脂とを含み、２５℃における不混和ちょう度が１００～３４０であることにより、本実施形態の冷凍機油用グリースは冷媒に相溶しにくく、かつ、冷媒に流されにくくなる。よって、圧縮機から冷凍機油が吐出されにくく、冷凍サイクル内の管壁や熱交換機等に付着して油膜を形成することを防止でき、熱伝導率を良好に維持でき、熱交換能力の低下を抑制できる。
しかも、本実施形態の冷凍機油用グリースは、圧縮機から吐出されにくいので、冷凍サイクル内に油分離器を設ける必要がない。よって、冷凍サイクルの大型化や部品点数の増加を抑制できる。
加えて、本実施形態の冷凍機油用グリースを用いた圧縮機は、冷凍機油用グリースが吐出されにくいので、あたかもオイルレス圧縮機のように見える。 According to the above configuration, the present embodiment comprises a hydrocarbon oil as a base oil and a resin having a melting point of 270 ° C. or lower as a thickener and having an immiscible consistency at 25 ° C. of 100 to 340. The grease for refrigerating machine oil is difficult to be compatible with the refrigerant and is not easily washed away by the refrigerant. Therefore, it is difficult for the refrigerating machine oil to be discharged from the compressor, it is possible to prevent the oil film from adhering to the pipe wall or the heat exchanger in the refrigerating cycle, the thermal conductivity can be maintained well, and the heat exchange capacity is reduced. Can be suppressed.
Moreover, since the grease for refrigerating machine oil of the present embodiment is difficult to be discharged from the compressor, it is not necessary to provide an oil separator in the refrigerating cycle. Therefore, it is possible to suppress an increase in the size of the refrigeration cycle and an increase in the number of parts.
In addition, the compressor using the grease for refrigerating machine oil of the present embodiment looks like an oilless compressor because the grease for refrigerating machine oil is difficult to be discharged.

また、前記炭化水素油の４０℃における動粘度が２００００ｍｍ２／ｓ以上であり、前記樹脂の含有量が４～１０質量％であることが好ましい。 Further, it is preferable that the kinematic viscosity of the hydrocarbon oil at 40 ° C. is 20000 mm 2 / s or more and the content of the resin is 4 to 10% by mass.

上記構成によれば、４０℃における動粘度が２００００ｍｍ２／ｓ以上である炭化水素油を用いたときに、冷凍機油用グリースの総質量に対する融点が２７０℃以下の樹脂の含有量を４～１０質量％とすることで、冷凍機油としての適度な粘度を維持しつつ、冷媒により流されにくくなる。 According to the above configuration, when a hydrocarbon oil having a kinematic viscosity of 20000 mm 2 / s or more at 40 ° C. is used, the content of the resin having a melting point of 270 ° C. or less with respect to the total mass of the grease for refrigerating machine oil is 4 to 10. By setting the mass%, it becomes difficult to be washed away by the refrigerant while maintaining an appropriate viscosity as the refrigerating machine oil.

また、前記炭化水素油の４０℃における動粘度が２００００ｍｍ２／ｓ未満であり、前記樹脂の含有量が５～１５質量％であることが好ましい。 Further, it is preferable that the kinematic viscosity of the hydrocarbon oil at 40 ° C. is less than 20000 mm 2 / s and the content of the resin is 5 to 15% by mass.

上記構成によれば、４０℃における動粘度が２００００ｍｍ２／ｓ未満である炭化水素油を用いたときに、冷凍機油用グリースの総質量に対する融点が２７０℃以下の樹脂の含有量を５～１５質量％とすることで、冷凍機油としての適度な粘度を維持しつつ、冷媒により流されにくくなる。 According to the above configuration, when a hydrocarbon oil having a kinematic viscosity of less than 20000 mm 2 / s at 40 ° C. is used, the content of the resin having a melting point of 270 ° C. or lower with respect to the total mass of the grease for refrigerating machine oil is 5 to 15. By setting the mass%, it becomes difficult to be washed away by the refrigerant while maintaining an appropriate viscosity as the refrigerating machine oil.

本発明の冷凍機油用グリースは、冷媒に相溶しにくく、かつ、冷媒に流されにくい。 The grease for refrigerating machine oil of the present invention is difficult to be compatible with the refrigerant and is not easily washed away by the refrigerant.

以下、本発明に係る冷凍機油用グリースの一実施形態について詳細に説明する。 Hereinafter, an embodiment of the grease for refrigerating machine oil according to the present invention will be described in detail.

本実施形態の冷凍機油用グリースは、炭化水素油と、融点が２７０℃以下の樹脂（以下、「樹脂（Ａ）」ともいう。）とを含む。 The grease for refrigerating machine oil of the present embodiment contains a hydrocarbon oil and a resin having a melting point of 270 ° C. or lower (hereinafter, also referred to as “resin (A)”).

＜炭化水素油＞
炭化水素油は、基油としての役割を果たし、２５℃で液状を呈する。
冷凍機油用グリースが炭化水素油を含むことで、冷媒に相溶しにくくなる。加えて、摺動面に粘性の油膜を形成し、摺動面に働く応力を緩和できるので、潤滑性に優れる。 <Hydrocarbon oil>
Hydrocarbon oil serves as a base oil and exhibits a liquid at 25 ° C.
Since the grease for refrigerating machine oil contains hydrocarbon oil, it becomes difficult to be compatible with the refrigerant. In addition, a viscous oil film is formed on the sliding surface, and the stress acting on the sliding surface can be relaxed, so that the lubricity is excellent.

炭化水素油は、鎖式（非環式）であってもよいし、環式であってもよい。冷媒により相溶しにくく、かつ、冷媒により流されにくくなる観点から、脂肪族の炭化水素油が好ましく、鎖式の炭化水素油がより好ましい。
鎖式の炭化水素油としては、オレフィン系ポリマーが挙げられる。オレフィン系ポリマーとしては、炭素数４～１０のオレフィンの単独重合体または共重合体が挙げられる。オレフィンとしては、例えば、１－ブテン、２－ブテン、イソブチレン、イソプレン、４－メチル－１－ペンテン、１，５－ヘキサジエン、１，９－デカジエンなどが挙げられる。 The hydrocarbon oil may be a chain type (acyclic type) or a ring type. Aliphatic hydrocarbon oils are preferable, and chain-type hydrocarbon oils are more preferable, from the viewpoint that they are difficult to be compatible with the refrigerant and are not easily washed away by the refrigerant.
Examples of the chain hydrocarbon oil include olefin polymers. Examples of the olefin polymer include homopolymers and copolymers of olefins having 4 to 10 carbon atoms. Examples of the olefin include 1-butene, 2-butene, isobutylene, isoprene, 4-methyl-1-pentene, 1,5-hexadiene, 1,9-decadien and the like.

鎖式の炭化水素油としては、下記一般式（１）で表される単位を有するポリマー（以下、「ポリマー（ａ）」ともいう。）が好ましい。
－（ＣＨ２－Ｃ(ＣＨ３)２）－ ・・・（１） As the chain type hydrocarbon oil, a polymer having a unit represented by the following general formula (1) (hereinafter, also referred to as “polymer (a)”) is preferable.
-(CH 2 -C (CH 3 ) 2 )-... (1)

ポリマー（ａ）としては、イソブチレンの単独重合体（すなわち、ポリイソブチレン）や、イソブチレンと共重合可能なモノマー（以下、「モノマー（ｘ）」ともいう。）と、イソブチレンとの共重合体が挙げられる。すなわち、ポリマー（ａ）は、モノマー（ｘ）由来の単位をさらに有してもよい。
モノマー（ｘ）としては、先に例示したオレフィンのうち、イソブチレン以外のものが挙げられる。これらの中でも、１－ブデン、２－ブテン、イソプレンが好ましい。 Examples of the polymer (a) include a homobutylene homopolymer (that is, polyisobutylene), a monomer copolymerizable with isobutylene (hereinafter, also referred to as “monomer (x)”), and a copolymer with isobutylene. Be done. That is, the polymer (a) may further have a unit derived from the monomer (x).
Examples of the monomer (x) include those other than isobutylene among the olefins exemplified above. Among these, 1-butene, 2-butene and isoprene are preferable.

環式の炭化水素油としては、環状構造を有し、かつ上記一般式（１）で表される単位を有するポリマー（以下、「ポリマー（ｂ）」ともいう。）が好ましい。
ポリマー（ｂ）としては、イソブチレンと共重合可能であり、かつ環状構造を有するモノマー（以下、「モノマー（ｙ）」ともいう。）と、イソブチレンとの共重合体、モノマー（ｙ）とモノマー（ｘ）とイソブチレンとの共重合体が挙げられる。すなわち、ポリマー（ａ）は、モノマー（ｙ）由来の単位やモノマー（ｘ）由来の単位をさらに有してもよい。
モノマー（ｙ）としては、例えば、ジビニルベンゼン、スチレン、２－メチルスチレン、３－メチルスチレン、４－メチルスチレン、α－メチルスチレン、β－メチルスチレン、３，５－ジメチルスチレン、２，４－ジメチルスチレンなどが挙げられる。 As the cyclic hydrocarbon oil, a polymer having a cyclic structure and having a unit represented by the general formula (1) (hereinafter, also referred to as “polymer (b)”) is preferable.
As the polymer (b), a monomer copolymerizable with isobutylene and having a cyclic structure (hereinafter, also referred to as “monomer (y)”), a copolymer with isobutylene, a monomer (y) and a monomer ( Examples thereof include a copolymer of x) and isobutylene. That is, the polymer (a) may further have a unit derived from the monomer (y) or a unit derived from the monomer (x).
Examples of the monomer (y) include divinylbenzene, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, β-methylstyrene, 3,5-dimethylstyrene, and 2,4-. Examples include dimethylstyrene.

これら炭化水素油は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 These hydrocarbon oils may be used alone or in combination of two or more.

炭化水素油の４０℃における動粘度は１００～５００００ｍｍ２／ｓが好ましく、１０００～３００００ｍｍ２／ｓが好ましく、１５００～２５０００ｍｍ２／ｓがさらに好ましい。炭化水素油の動粘度が１００ｍｍ２／ｓ以上であれば、冷凍機油用グリースの耐摩耗性を良好に維持できる。炭化水素油の動粘度が５００００ｍｍ２／ｓ以下であれば、冷凍機油用グリースの粘性（粘度）の過度な上昇を抑制でき、圧縮機の潤滑油としての機能を充分に発現できる。
炭化水素油の動粘度は、ＪＩＳ Ｋ ２２８３に準拠し、測定温度４０℃にて測定される。 The kinematic viscosity of the hydrocarbon oil at 40 ° C. is preferably 100 to 50,000 mm 2 / s, preferably 1000 to 30000 mm 2 / s, and even more preferably 1500 to 25000 mm 2 / s. When the kinematic viscosity of the hydrocarbon oil is 100 mm 2 / s or more, the wear resistance of the grease for refrigerating machine oil can be well maintained. When the kinematic viscosity of the hydrocarbon oil is 50,000 mm 2 / s or less, an excessive increase in the viscosity (viscosity) of the grease for refrigerating machine oil can be suppressed, and the function as a lubricating oil of a compressor can be sufficiently exhibited.
The kinematic viscosity of the hydrocarbon oil conforms to JIS K 2283 and is measured at a measurement temperature of 40 ° C.

炭化水素油の数平均分子量は、２００～５０００が好ましく、３００～４０００がより好ましく、５００～３０００がさらに好ましい。
炭化水素油の数平均分子量は、蒸気圧浸透圧法（ＶＰＯ法）に準拠して測定される。 The number average molecular weight of the hydrocarbon oil is preferably 200 to 5000, more preferably 300 to 4000, and even more preferably 500 to 3000.
The number average molecular weight of the hydrocarbon oil is measured according to the vapor pressure osmotic pressure method (VPO method).

冷凍機油用グリースの総質量に対する炭化水素油の含有量は、４０℃における動粘度が２００００ｍｍ２／ｓ以上の場合は、９０～９６質量％が好ましく、９３～９６質量％がより好ましく、４０℃における動粘度が２００００ｍｍ２／ｓ未満の場合は、８５～９５質量％が好ましく、９０～９５質量％がより好ましい。
炭化水素油の含有量が上記範囲内であれば、適度な粘性を発現できる。特に、炭化水素油の含有量が上記下限値以上であれば、冷凍機油用グリースが硬くなりすぎず、圧縮機の潤滑油としての機能を充分に発現できる。加えて、摺動性を良好に維持できる。炭化水素油の含有量が上記上限値以下であれば、冷凍機油用グリースが柔らかくなりすぎず、冷媒により流されにくくなる。 The content of the hydrocarbon oil with respect to the total mass of the grease for refrigerating machine oil is preferably 90 to 96% by mass, more preferably 93 to 96% by mass, and 40 ° C. when the kinematic viscosity at 40 ° C. is 20000 mm 2 / s or more. When the kinematic viscosity in the above is less than 20000 mm 2 / s, 85 to 95% by mass is preferable, and 90 to 95% by mass is more preferable.
When the content of the hydrocarbon oil is within the above range, an appropriate viscosity can be developed. In particular, when the content of the hydrocarbon oil is at least the above lower limit value, the grease for refrigerating machine oil does not become too hard, and the function as a lubricating oil of the compressor can be sufficiently exhibited. In addition, slidability can be maintained well. When the content of the hydrocarbon oil is not more than the above upper limit value, the grease for refrigerating machine oil does not become too soft and is difficult to be washed away by the refrigerant.

＜樹脂（Ａ）＞
樹脂（Ａ）は、増ちょう材としての役割を果たす。
冷凍機油用グリースが樹脂（Ａ）を含むことで、炭化水素油との相互作用により、冷媒に相溶しにくくなると共に、冷媒に流されにくくなる。加えて、冷凍機油用グリースに適度な粘性を付与できる。 <Resin (A)>
The resin (A) serves as a thickener.
When the grease for refrigerating machine oil contains the resin (A), it becomes difficult to be compatible with the refrigerant due to the interaction with the hydrocarbon oil, and it becomes difficult for the grease to flow into the refrigerant. In addition, it is possible to impart an appropriate viscosity to the grease for refrigerating machine oil.

樹脂（Ａ）の融点は２７０℃以下であり、２００℃以下が好ましく、１５０℃以下がより好ましく、１２０℃以下がさらに好ましい。
冷凍機油用グリースは、通常、炭化水素油と樹脂（Ａ）とを混合した後に樹脂（Ａ）を溶融したり、樹脂（Ａ）を溶融した後に炭化水素油と混合したりして、製造される。樹脂（Ａ）の融点が２７０℃以下であれば、樹脂（Ａ）の溶融時に炭化水素油が劣化しにくい。樹脂（Ａ）の融点の下限値については特に制限されないが、通常は１００℃程度である。 The melting point of the resin (A) is 270 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower, still more preferably 120 ° C. or lower.
Grease for refrigerating machine oil is usually produced by mixing a hydrocarbon oil and a resin (A) and then melting the resin (A), or melting the resin (A) and then mixing it with a hydrocarbon oil. Ru. When the melting point of the resin (A) is 270 ° C. or lower, the hydrocarbon oil is less likely to deteriorate when the resin (A) is melted. The lower limit of the melting point of the resin (A) is not particularly limited, but is usually about 100 ° C.

樹脂（Ａ）としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリフッ化ビニリデン樹脂などが挙げられる。これらの中でも、炭化水素油との親和性に優れ、離油度を低くできる観点から、ポリエチレン樹脂、ポリプロピレン樹脂が好ましい。
これら樹脂（Ａ）は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the resin (A) include polyethylene resin, polypropylene resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyvinylidene fluoride resin and the like. Among these, polyethylene resin and polypropylene resin are preferable from the viewpoint of having excellent affinity with hydrocarbon oil and reducing the degree of oil release.
These resins (A) may be used alone or in combination of two or more.

炭化水素油の４０℃における動粘度が２００００ｍｍ２／ｓ以上の場合、冷凍機油用グリースの総質量に対する樹脂（Ａ）の含有量は、４～１０質量％が好ましく、４～７質量％がより好ましい。
炭化水素油の４０℃における動粘度が２００００ｍｍ２／ｓ未満の場合、冷凍機油用グリースの総質量に対する樹脂（Ａ）の含有量は、５～１５質量％が好ましく、５～１０質量％がより好ましい。
樹脂（Ａ）の含有量が上記範囲内であれば、適度な粘性を発現できる。特に、樹脂（Ａ）の含有量が上記下限値以上であれば、冷凍機油用グリースが柔らかくなりすぎず、冷媒により流されにくくなる。樹脂（Ａ）の含有量が上記上限値以下であれば、冷凍機油用グリースが硬くなりすぎず、圧縮機の潤滑油としての機能を充分に発現できる。加えて、摺動性を良好に維持できる。 When the kinematic viscosity of the hydrocarbon oil at 40 ° C. is 20000 mm 2 / s or more, the content of the resin (A) with respect to the total mass of the grease for refrigerating machine oil is preferably 4 to 10% by mass, more preferably 4 to 7% by mass. preferable.
When the kinematic viscosity of the hydrocarbon oil at 40 ° C. is less than 20000 mm 2 / s, the content of the resin (A) with respect to the total mass of the grease for refrigerating machine oil is preferably 5 to 15% by mass, more preferably 5 to 10% by mass. preferable.
When the content of the resin (A) is within the above range, an appropriate viscosity can be developed. In particular, when the content of the resin (A) is at least the above lower limit value, the grease for refrigerating machine oil does not become too soft and is difficult to be washed away by the refrigerant. When the content of the resin (A) is not more than the above upper limit value, the grease for refrigerating machine oil does not become too hard, and the function as a lubricating oil of the compressor can be sufficiently exhibited. In addition, slidability can be maintained well.

＜任意成分＞
本発明の冷凍機油用グリースは、炭化水素油および樹脂（Ａ）からなるものでもよいし、炭化水素油および樹脂（Ａ）以外の成分（任意成分）を含んでいてもよい。
任意成分としては、潤滑剤、酸化防止剤、酸捕捉剤、金属不活性剤などの各種添加剤が挙げられる。 <Arbitrary ingredient>
The grease for refrigerating machine oil of the present invention may be composed of a hydrocarbon oil and a resin (A), or may contain a component (arbitrary component) other than the hydrocarbon oil and the resin (A).
Optional components include various additives such as lubricants, antioxidants, acid scavengers, and metal deactivators.

潤滑剤としては、例えば、モノ－ｍまたはｐ－トルイル－ジフェニルホスフェート、ジ－ｍまたはｐ－トルイル－モノフェニルホスフェート、トリ－ｍまたはｐ－トルイルホスフェート（トリクレジルホスフェート（ＴＣＰ））、モノ－ｍまたはｐ－トルイル－ジキシレニルホスフェート、ジ－ｍまたはｐ－トルイル－モノキシレニルホスフェート、モノ－ｍまたはｐ－トルイル－ジキシレニルホスフェート、ジ－ｍまたはｐ－トルイル－モノキシレニルホスフェート、トリス（ｍまたはｐ－ｔｅｒｔ－ブチルフェニル）－ホスフェート、ビス－（ｍまたはｐ－ｔｅｒｔ－ブチルフェニル）－モノ－フェニルホスフェート、モノ－（ｍまたはｐ－ｔｅｒｔ－ブチルフェニル）－ジフェニルホスフェート、トリフェニルホスフェート（ＴＰＰ））、トリキシレニルホスフェート、モノフェニル－ジキシレニルホスフェート、ジフェニル－モノキシレニルホスフェート、モノブチルチオフェート、ジブチルチオフェートまたはトリブチルチオフェート(これらを「モノ／ジ／トリブチルチオフェート」と略記する。以下同様）、モノ／ジ／トリヘキシルチオホスフェート、モノ／ジ／トリオクチルチオホスフェート、モノ／ジ／トリ（２－エチルヘキシル）チオホスフェート、モノ／ジ／トリノニルチオホスフェート、モノ／ジ／トリデシルチオホスフェート、モノ／ジ／トリラウリルチオホスフェート、モノ／ジ／トリミリスチルチオホスフェート、モノ／ジ／トリパルミチルチオホスフェート、モノ／ジ／トリステアリルチオホスフェート、モノ／ジ／トリオレイルチオホスフェート等のリン酸エステル化合物などが挙げられる。
これら潤滑剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the lubricant include mono-m or p-toluyl-diphenyl phosphate, di-m or p-toluyl-monophenyl phosphate, trim or p-toluyl phosphate (tricresyl phosphate (TCP)), and mono-. m or p-toluyl-dixylenyl phosphate, dim or p-toluyl-monoxylenyl phosphate, mono-m or p-toluyl-dixylenyl phosphate, dim or p-toluyl-monoxylenyl Phosphate, Tris (m or p-tert-butylphenyl) -phosphate, Bis- (m or p-tert-butylphenyl) -mono-phenyl phosphate, mono- (m or p-tert-butylphenyl) -diphenyl phosphate, Triphenyl Phosphate (TPP)), Trixylenyl Phosphate, Monophenyl-Dixylenyl Phosphate, Diphenyl-Monoxylenyl Phosphate, Monobutyl Thiophate, Dibutyl Thiophate or Tributyl Thiophate (these are "mono / di / tributyl"). Abbreviated as "thiofate". The same shall apply hereinafter), mono / di / trihexylthiophosphate, mono / di / trioctylthiophosphate, mono / di / tri (2-ethylhexyl) thiophosphate, mono / di / trinonylthiophosphate. , Mono / di / tridecylthiophosphate, mono / di / trilaurylthiophosphate, mono / di / trimilistilthiophosphate, mono / di / trypalmitylthiophosphate, mono / di / tristearylthiophosphate, mono / di / Examples thereof include phosphate ester compounds such as trioleylthiophosphate.
These lubricants may be used alone or in combination of two or more.

酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチルヒドロキシトルエン（ＢＨＴ）、４，４’－メチレンビス（２，６－ジ－ｔｅｒｔ－ブチルヒドロキシトルエン）、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオン酸－２－エチルヘキシルエステル、３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニルプロピオン酸－２－エチルヘキシルエステル、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオン酸トリデシルエステル、３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニルプロピオン酸トリデシルエステル、３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオン酸ステアリルエステル、３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニルプロピオン酸ステアリルエステル、ビス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニルプロピオン酸）－トリグリコールエステル、ビス（３－ｔｅｒｔ－ブチル－４－ヒドロキシ－５－メチルフェニルプロピオン酸）－トリグリコールエステル、２，５－ｔｅｒｔ－アミルヒドロキノン等のフェノール系酸化防止剤などが挙げられる。
これら酸化防止剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the antioxidant include 2,6-di-tert-butylhydroxytoluene (BHT), 4,4'-methylenebis (2,6-di-tert-butylhydroxytoluene), and 2,2'-methylenebis (2,2-di-tert-butylhydroxytoluene). 4-Methyl-6-tert-butylphenol), 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid-2-ethylhexyl ester, 3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid- 2-Ethylhexyl ester, 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid tridecyl ester, 3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid tridecyl ester, 3,5-di -Tert-Butyl-4-hydroxyphenylpropionic acid stearyl ester, 3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid stearyl ester, bis (3,5-di-tert-butyl-4-hydroxyphenylpropion) Examples thereof include phenolic antioxidants such as acid) -triglycol ester, bis (3-tert-butyl-4-hydroxy-5-methylphenylpropionic acid) -triglycol ester, and 2,5-tert-amylhydroquinone. ..
These antioxidants may be used alone or in combination of two or more.

酸捕捉剤としては、例えば、ブチルグリシジルエーテル、酪酸グリシジルエステル、ヘキシルグリシジルエーテル、ヘキサン酸グリシジルエステル、２－エチルヘキシルグリシジルエーテル、２－エチルヘキサン酸グリシジルエステル、ネオペンチルグリシジルエーテル、ピバル酸グリシジルエステル、デシルグリシジルエーテル、デカン酸グリシジルエステル、ステアリルグリシジルエーテル、ステアリン酸グリシジルエステル、オレイルグリシジルエーテル、オレイン酸グリシジルエステル、フェニルグリシジルエーテル、安息香酸グリシジルエステル、トルイルグリシジルエーテル、キシレニルグリシジルエーテル、ｔｅｒｔ－ブチルフェニルグリシジルエーテル、フタル酸グリシジルエステル、オキサシクロヘキシルメチルオキサシクロヘキシルカルボン酸エステル等のグリシジル系エステル化合物またはグリシジル系エーテル化合物（以下、これらを総称して「エポキシ系酸捕捉剤」ともいう。）などが挙げられる。
これら酸捕捉剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the acid trapping agent include butyl glycidyl ether, butyric acid glycidyl ester, hexyl glycidyl ester, hexane acid glycidyl ester, 2-ethylhexyl glycidyl ester, 2-ethylhexanoic acid glycidyl ester, neopentyl glycidyl ether, pivalic acid glycidyl ester, and decyl. Glycyzyl ether, decanoic acid glycidyl ester, stearyl glycidyl ether, stealic acid glycidyl ester, oleyl glycidyl ether, oleic acid glycidyl ester, phenyl glycidyl ether, benzoic acid glycidyl ester, toluyl glycidyl ether, xylenyl glycidyl ether, tert-butylphenyl glycidyl Examples thereof include glycidyl-based ester compounds such as ether, phthalic acid glycidyl ester, and oxacyclohexylmethyloxacyclohexylcarboxylic acid ester, or glycidyl-based ether compounds (hereinafter, these are collectively referred to as “epoxy-based acid trapping agent”).
These acid scavengers may be used alone or in combination of two or more.

金属不活性剤としては、例えば、１Ｈ－ベンゾトリアゾール、４－メチルベンゾトリアゾール、５－メチルベンゾトリアゾール、ベンゾトリアゾール－１－メチルアミン、４－メチルベンゾトリアゾール－１－メチルアミン、５－メチルベンゾトリアゾール－１－メチルアミン、Ｎ－メチルベンゾトリアゾール－１－メチルアミン、Ｎ－エチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジメチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジエチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジプロピルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジブチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジヘキシルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジオクチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ビス（２－エチルヘキシル）－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジメチル－４－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジメチル－５－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジエチル－４－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジエチル－５－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジプロピル－４－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジプロピル－５－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジブチル－４－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジブチル－５－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジヘキシル－４－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジヘキシル－５－ベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ビス（２－エチルヘキシル）－４－メチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ビス（２－エチルヘキシル）－５－メチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジオレイル－４－メチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジオレイル－５－メチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジステアリル－４－メチルベンゾトリアゾール－１－メチルアミン、Ｎ，Ｎ－ジステアリル－５－メチルベンゾトリアゾール－１－メチルアミン等のベンゾトリアゾール系化合物またはその誘導体あるいはそれらの混合物などが挙げられる。
これら金属不活性剤は、１種単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 Examples of the metal deactivator include 1H-benzotriazole, 4-methylbenzotriazole, 5-methylbenzotriazole, benzotriazole-1-methylamine, 4-methylbenzotriazole-1-methylamine, and 5-methylbenzotriazole. -1-Methylamine, N-Methylbenzotriazole-1-methylamine, N-ethylbenzotriazole-1-methylamine, N, N-dimethylbenzotriazole-1-methylamine, N, N-diethylbenzotriazole-1 -Methylamine, N, N-dipropylbenzotriazole-1-methylamine, N, N-dibutylbenzotriazole-1-methylamine, N, N-dihexylbenzotriazole-1-methylamine, N, N-dioctylbenzo Triazole-1-methylamine, N, N-bis (2-ethylhexyl) -benzotriazole-1-methylamine, N, N-dimethyl-4-benzotriazole-1-methylamine, N, N-dimethyl-5- Benzotriazole-1-methylamine, N, N-diethyl-4-benzotriazole-1-methylamine, N, N-diethyl-5-benzotriazole-1-methylamine, N, N-dipropyl-4-benzotriazole -1-Methylamine, N, N-dipropyl-5-benzotriazole-1-methylamine, N, N-dibutyl-4-benzotriazole-1-methylamine, N, N-dibutyl-5-benzotriazole-1 -Methylamine, N, N-dihexyl-4-benzotriazole-1-methylamine, N, N-dihexyl-5-benzotriazole-1-methylamine, N, N-bis (2-ethylhexyl) -4-methyl Benzotriazole-1-methylamine, N, N-bis (2-ethylhexyl) -5-methylbenzotriazole-1-methylamine, N, N-diorail-4-methylbenzotriazole-1-methylamine, N, N -Diorail-5-Methylbenzotriazole-1-methylamine, N, N-distearyl-4-methylbenzotriazole-1-methylamine, N, N-distearyl-5-methylbenzotriazole-1-methylamine, etc. Examples thereof include benzotriazole-based compounds or derivatives thereof or mixtures thereof.
These metal deactivating agents may be used alone or in combination of two or more.

冷凍機油用グリースの総質量に対する任意成分の含有量は、１０質量％以下が好ましく、７質量％以下がより好ましい。任意成分の含有量が１０質量％以下であれば、冷凍機油用グリースから析出しにくい。 The content of the optional component with respect to the total mass of the grease for refrigerating machine oil is preferably 10% by mass or less, more preferably 7% by mass or less. When the content of the optional component is 10% by mass or less, it is difficult to precipitate from the grease for refrigerating machine oil.

＜物性＞
冷凍機油用グリースの２５℃における不混和ちょう度は、１００～３４０である。冷凍機油用グリースの不混和ちょう度が１００以上であれば、冷凍機油用グリースが硬くなりすぎず、圧縮機の潤滑油としての機能を充分に発現できる。加えて、摺動性を良好に維持できる。冷凍機油用グリースの不混和ちょう度が３４０以下であれば、冷凍機油用グリースが柔らかくなりすぎず、冷媒により流されにくくなる。冷凍機油用グリースの不混和ちょう度は、１５０以上が好ましく、２００以上がより好ましく、２５０以上がさらに好ましい。
冷凍機油用グリースの不混和ちょう度は、炭化水素油の物性（特に動粘度）や、樹脂（Ａ）の含有量によって調整できる。具体的には、炭化水素油の動粘度が高くなるに連れて、不混和ちょう度は低くなる傾向にある。また、樹脂（Ａ）の含有量が多くなるに連れて、不混和ちょう度は低くなる傾向にある。
冷凍機油用グリースの不混和ちょう度は、ＪＩＳ Ｋ ２２２０に準拠し、測定温度２５℃にて測定される。 <Physical characteristics>
The immiscible consistency of the grease for refrigerating machine oil at 25 ° C. is 100 to 340. When the immiscible consistency of the grease for refrigerating machine oil is 100 or more, the grease for refrigerating machine oil does not become too hard, and the function as a lubricating oil of a compressor can be sufficiently exhibited. In addition, slidability can be maintained well. When the immiscible consistency of the grease for refrigerating machine oil is 340 or less, the grease for refrigerating machine oil does not become too soft and is difficult to be washed away by the refrigerant. The immiscible consistency of the grease for refrigerating machine oil is preferably 150 or more, more preferably 200 or more, still more preferably 250 or more.
The immiscible consistency of the grease for refrigerating machine oil can be adjusted by adjusting the physical characteristics (particularly kinematic viscosity) of the hydrocarbon oil and the content of the resin (A). Specifically, as the kinematic viscosity of the hydrocarbon oil increases, the immiscibility tends to decrease. Further, as the content of the resin (A) increases, the immiscible consistency tends to decrease.
The immiscible consistency of the grease for refrigerating machine oil is measured at a measurement temperature of 25 ° C. in accordance with JIS K 2220.

＜製造方法＞
冷凍機油用グリースは、例えば以下のようにして製造できる。
まず、炭化水素油と、樹脂（Ａ）と、必要に応じて任意成分とを混合する。次いで、混合物を樹脂（Ａ）の融点以上に加熱して混合物中の樹脂（Ａ）を溶融し、冷凍機油用グリースを得る。
任意成分は樹脂（Ａ）を溶融した後に混合物に添加してもよい。また、予め樹脂（Ａ）を溶融しておき、この溶融した樹脂（Ａ）と、炭化水素油と、必要に応じて任意成分とを混合してもよい。
樹脂（Ａ）を溶融する際の温度は、樹脂（Ａ）の融点以上であれば特に制限されないが、炭化水素油の劣化を抑制する観点から、上限は樹脂（Ａ）の融点＋１０℃が好ましい。 <Manufacturing method>
The grease for refrigerating machine oil can be produced, for example, as follows.
First, the hydrocarbon oil, the resin (A), and if necessary, an arbitrary component are mixed. Next, the mixture is heated to a temperature equal to or higher than the melting point of the resin (A) to melt the resin (A) in the mixture to obtain grease for refrigerating machine oil.
The optional component may be added to the mixture after melting the resin (A). Further, the resin (A) may be melted in advance, and the melted resin (A), the hydrocarbon oil, and an arbitrary component may be mixed if necessary.
The temperature at which the resin (A) is melted is not particularly limited as long as it is equal to or higher than the melting point of the resin (A), but the upper limit is preferably the melting point of the resin (A) + 10 ° C. from the viewpoint of suppressing deterioration of the hydrocarbon oil. ..

＜作用効果＞
以上説明した本実施形態の冷凍機油用グリースによれば、炭化水素油と樹脂（Ａ）とを含み、２５℃における不混和ちょう度が１００～３４０であるため、冷媒に相溶しにくく、かつ、冷媒に流されにくくなる。よって、本実施形態の冷凍機油用グリースは圧縮機から吐出されにくく、冷凍サイクル内の管壁や熱交換機等に付着して油膜を形成することを防止でき、熱伝導率を良好に維持でき、熱交換能力の低下を抑制できる。 <Action effect>
According to the grease for refrigerating machine oil of the present embodiment described above, since the grease contains the hydrocarbon oil and the resin (A) and has an immiscible consistency of 100 to 340 at 25 ° C., it is difficult to be compatible with the refrigerant and is not compatible with the refrigerant. , It becomes difficult to be washed away by the refrigerant. Therefore, the grease for refrigerating machine oil of the present embodiment is difficult to be discharged from the compressor, can be prevented from adhering to the pipe wall or the heat exchanger in the refrigerating cycle to form an oil film, and can maintain good thermal conductivity. It is possible to suppress a decrease in heat exchange capacity.

しかも、本実施形態の冷凍機油用グリースは、圧縮機から吐出されにくいので、冷凍サイクル内に油分離器を設ける必要がない。よって、冷凍サイクルの大型化や部品点数の増加を抑制できる。
加えて、本実施形態の冷凍機油用グリースを用いた圧縮機は、冷凍機油用グリースが吐出されにくいので、あたかもオイルレス圧縮機のように見える。 Moreover, since the grease for refrigerating machine oil of the present embodiment is difficult to be discharged from the compressor, it is not necessary to provide an oil separator in the refrigerating cycle. Therefore, it is possible to suppress an increase in the size of the refrigeration cycle and an increase in the number of parts.
In addition, the compressor using the grease for refrigerating machine oil of the present embodiment looks like an oilless compressor because the grease for refrigerating machine oil is difficult to be discharged.

また、炭化水素油の４０℃における動粘度が２００００ｍｍ２／ｓ以上の場合、樹脂（Ａ）の含有量が４～１０質量％であれば、冷凍機油としての適度な粘度を維持しつつ、冷媒により流されにくくなる。 When the kinematic viscosity of the hydrocarbon oil at 40 ° C. is 20000 mm 2 / s or more and the content of the resin (A) is 4 to 10% by mass, the refrigerant maintains an appropriate viscosity as a refrigerating machine oil. Makes it harder to be washed away.

また、炭化水素油の４０℃における動粘度が２００００ｍｍ２／ｓ未満の場合、樹脂（Ａ）の含有量が５～１５質量％であれば、冷凍機油としての適度な粘度を維持しつつ、冷媒により流されにくくなる。 Further, when the kinematic viscosity of the hydrocarbon oil at 40 ° C. is less than 20000 mm 2 / s and the content of the resin (A) is 5 to 15% by mass, the refrigerant maintains an appropriate viscosity as a refrigerating machine oil. Makes it harder to be washed away.

＜用途＞
本発明の冷凍機油用グリースは、圧縮機の冷凍機油として好適である。 <Use>
The grease for refrigerating machine oil of the present invention is suitable as a refrigerating machine oil for a compressor.

以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

「測定・評価」
＜不混和ちょう度の測定＞
冷凍機油用グリースの不混和ちょう度は、ＪＩＳ Ｋ ２２２０に準拠し、測定温度２５℃にて測定した。 "Measurement / evaluation"
<Measurement of immiscible consistency>
The immiscible consistency of the grease for refrigerating machine oil was measured at a measurement temperature of 25 ° C. in accordance with JIS K 2220.

＜粘度の測定＞
冷凍機油用グリースの粘度は、ＪＩＳ Ｚ ８８０３に準拠し、Ｂ型粘度計を用いて測定温度２５℃にて測定した。 <Measurement of viscosity>
The viscosity of the grease for refrigerating machine oil was measured at a measurement temperature of 25 ° C. using a B-type viscometer in accordance with JIS Z 8803.

＜非相溶性の評価＞
冷凍機油用グリースの非相溶性は、ＪＩＳ Ｋ ２２１１に準拠し、以下のようにして評価した。
ハイパーグラスシリンダ（観察窓が設けられた耐圧容器）を用い、該容器の内側に冷凍機油用グリースを塊状に塗布した。塗布する箇所は、容器の片側かつ観察窓のない部分とした。
次いで、容器に冷媒としてハイドロフルオロカーボンを容器の半分の高さまで投入した後、容器を密閉した。
容器を１分間振った後、冷凍機油用グリースの塊が冷媒に溶解しているか否かを観察窓から目視にて確認し、以下の評価基準にて非相溶性を評価した。○を合格とする。
○：冷凍機油用グリースの塊が冷媒に溶解していない。
×：冷凍機油用グリースの塊が冷媒に溶解している。 <Evaluation of incompatibility>
The incompatibility of the grease for refrigerating machine oil was evaluated according to JIS K 2211 as follows.
Using a hyperglass cylinder (a pressure-resistant container provided with an observation window), grease for refrigerating machine oil was applied in a lump on the inside of the container. The place to apply was one side of the container and the part without the observation window.
Next, hydrofluorocarbon as a refrigerant was charged into the container to half the height of the container, and then the container was sealed.
After shaking the container for 1 minute, it was visually confirmed from the observation window whether or not the lump of grease for refrigerating machine oil was dissolved in the refrigerant, and the incompatibility was evaluated according to the following evaluation criteria. ○ is passed.
◯: A lump of grease for refrigerating machine oil is not dissolved in the refrigerant.
X: A lump of grease for refrigerating machine oil is dissolved in the refrigerant.

＜流れにくさの評価＞
非相溶性の評価と同様にして、容器内に冷凍機油用グリースを塊状に塗布し、さらに冷媒を投入した後に容器を密閉した。
容器を１分間振った後、容器を手に持って回転させて冷媒を流動させたときに、冷凍機油用グリースの塊が冷媒と共に流動するか否かを観察窓から目視にて確認し、以下の評価基準にて冷凍機油用グリースの流れにくさ（非流動性）を評価した。また、冷凍機油用グリースの柔らかさは、指で触って確認した。○を合格とする。
○：冷凍機油用グリースの塊が冷媒と共に流動せず、かつ冷凍機油用グリースが適度な柔らかさを有している。
×１：冷凍機油用グリースの塊が冷媒と共に流動する。
×２：冷凍機油用グリースの塊が冷媒と共に流動しないが、冷凍機油用グリースが硬く、ワックス状を呈している。 <Evaluation of difficulty in flow>
In the same manner as in the evaluation of incompatibility, grease for refrigerating machine oil was applied in a lump in the container, and after further adding the refrigerant, the container was sealed.
After shaking the container for 1 minute, visually check from the observation window whether or not the lump of grease for refrigerating machine oil flows with the refrigerant when the container is held in the hand and rotated to flow the refrigerant. The flow resistance (non-fluidity) of the grease for refrigerating machine oil was evaluated according to the evaluation criteria of. The softness of the grease for refrigerating machine oil was confirmed by touching it with a finger. ○ is passed.
◯: The lump of the grease for refrigerating machine oil does not flow together with the refrigerant, and the grease for refrigerating machine oil has appropriate softness.
× 1: A lump of grease for refrigerating machine oil flows together with the refrigerant.
× 2: The lump of grease for refrigerating machine oil does not flow together with the refrigerant, but the grease for refrigerating machine oil is hard and waxy.

＜摺動性の評価＞
ガラス板に冷凍機油用グリースを塊状に塗布し、塗布した冷凍機油用グリースを指で擦ったときの感触で、以下の評価基準にて摺動性を評価した。○を合格とし、△を実用上問題なしと判断した。
○：抵抗を感じない。
△：抵抗をやや感じる。
×：抵抗を感じる。 <Evaluation of slidability>
The grease for refrigerating machine oil was applied in a lump on a glass plate, and the slidability was evaluated according to the following evaluation criteria based on the feeling when the applied grease for refrigerating machine oil was rubbed with a finger. ○ was judged to be acceptable, and △ was judged to have no practical problem.
○: I do not feel any resistance.
Δ: I feel some resistance.
×: I feel resistance.

＜総合評価＞
非相溶性の評価、流れにくさの評価および摺動性の評価の結果に基づき、以下の評価基準にて評価した。○を合格とし、△を実用上問題なしと判断した。
○：全ての評価が○である。
△：非相溶性の評価および流れにくさの評価が○であり、摺動性の評価が△である。
×：各評価のうち、×が１つ以上ある。 <Comprehensive evaluation>
Based on the results of incompatibility evaluation, flow resistance evaluation, and slidability evaluation, evaluation was performed according to the following evaluation criteria. ○ was judged to be acceptable, and △ was judged to have no practical problem.
◯: All evaluations are ◯.
Δ: The evaluation of incompatibility and the evaluation of flow resistance are ◯, and the evaluation of slidability is Δ.
×: Of each evaluation, there is one or more ×.

「実施例１」
炭化水素油として、上記一般式（１）で表される単位を有するポリマー（ａ１）（日油社製、商品名「日油ポリブテン・エマウエット（登録商標） ３０Ｎ」、動粘度（４０℃）：２４０００ｍｍ２／ｓ、数平均分子量（Ｍｎ）：１３５０）を用いた。
樹脂（Ａ）として、長径が約２ｍｍのビーズ状のポリエチレン樹脂（ＰＥ）（融点：９２～１２７℃、比重：０．８８～０．９７）を用いた。
表１に示す配合組成に従い、炭化水素油と樹脂（Ａ）とを混合した後、得られた混合物を１３０℃に加熱して混合物中の樹脂（Ａ）を溶融し、冷凍機油用グリースを得た。
得られた冷凍機油用グリースについて、不混和ちょう度および粘度を測定し、非相溶性、流れにくさ（非流動性）および摺動性を評価した。結果を表１に示す。 "Example 1"
As the hydrocarbon oil, a polymer (a1) having a unit represented by the above general formula (1) (manufactured by NOF CORPORATION, trade name "NOF Polybutene Emmawet (registered trademark) 30N", kinematic viscosity (40 ° C.): 24000 mm 2 / s, number average molecular weight (Mn): 1350) was used.
As the resin (A), a bead-shaped polyethylene resin (PE) having a major axis of about 2 mm (melting point: 92 to 127 ° C., specific gravity: 0.88 to 0.97) was used.
After mixing the hydrocarbon oil and the resin (A) according to the compounding composition shown in Table 1, the obtained mixture is heated to 130 ° C. to melt the resin (A) in the mixture to obtain grease for refrigerating machine oil. rice field.
The immiscible consistency and viscosity of the obtained grease for refrigerating machine oil were measured, and incompatibility, flow resistance (non-fluidity) and slidability were evaluated. The results are shown in Table 1.

「実施例２～７」
表１に示す配合組成となるように変更した以外は、実施例１と同様にして冷凍機油用グリースを製造し、各種測定および評価を行った。結果を表１に示す。 "Examples 2 to 7"
Grease for refrigerating machine oil was produced in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1, and various measurements and evaluations were performed. The results are shown in Table 1.

「実施例８～１０」
炭化水素油として、上記一般式（１）で表される単位を有するポリマー（ａ２）（日油社製、商品名「日油ポリブテン・エマウエット（登録商標） ３Ｎ」、動粘度（４０℃）：２１００ｍｍ２／ｓ、数平均分子量：７２０）を用い、表２に示す配合組成となるように変更した以外は、実施例１と同様にして冷凍機油用グリースを製造し、各種測定および評価を行った。結果を表２に示す。 "Examples 8 to 10"
As the hydrocarbon oil, a polymer (a2) having a unit represented by the above general formula (1) (manufactured by NOF Corporation, trade name "NOF Polybutene Emmawet (registered trademark) 3N", kinematic viscosity (40 ° C.): Using 2100 mm 2 / s, number average molecular weight: 720), grease for refrigerating machine oil was produced in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 2, and various measurements and evaluations were performed. rice field. The results are shown in Table 2.

「比較例１～３」
表３に示す配合組成となるように変更した以外は、実施例１と同様にして冷凍機油用グリースを製造し、各種測定および評価を行った。結果を表３に示す。 "Comparative Examples 1 to 3"
Grease for refrigerating machine oil was produced in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 3, and various measurements and evaluations were performed. The results are shown in Table 3.

「比較例４」
炭化水素油として、上記一般式（１）で表される単位を有するポリマー（ａ２）（日油社製、商品名「日油ポリブテン・エマウエット（登録商標） ３Ｎ」、動粘度（４０℃）：２１００ｍｍ２／ｓ、数平均分子量：７２０）を用いた。
樹脂（Ａ）の代わりにシリカ（粒子径：５～５０ｎｍ、比重：２．２）を用いた。
表３に示す配合組成に従い、炭化水素油とシリカとを混合し、冷凍機油用グリースを得た。得られた冷凍機油用グリースを１３０℃で６０分以上、加熱脱泡した。
加熱脱泡前後の冷凍機油用グリースの不混和ちょう度および粘度を測定した。結果を表３に示す。なお、表３中、不混和ちょう度および粘度の欄の上段に加熱脱泡前の冷凍機油用グリースの不混和ちょう度および粘度を示し、下段に加熱脱泡後の冷凍機油用グリースの不混和ちょう度および粘度を示した。
また、加熱脱泡後の冷凍機油用グリースについて、非相溶性、流れにくさ（非流動性）および摺動性を評価した。結果を表３に示す。 "Comparative Example 4"
As the hydrocarbon oil, a polymer (a2) having a unit represented by the above general formula (1) (manufactured by NOF CORPORATION, trade name "NOF Polybutene Emmawet (registered trademark) 3N", kinematic viscosity (40 ° C.): 2100 mm 2 / s, number average molecular weight: 720) was used.
Silica (particle diameter: 5 to 50 nm, specific gravity: 2.2) was used instead of the resin (A).
Hydrocarbon oil and silica were mixed according to the compounding composition shown in Table 3 to obtain grease for refrigerating machine oil. The obtained grease for refrigerating machine oil was defoamed by heating at 130 ° C. for 60 minutes or longer.
The immiscibility and viscosity of the grease for refrigerating machine oil before and after heat defoaming were measured. The results are shown in Table 3. In Table 3, the upper part of the column of immiscibility and viscosity shows the immiscibility and viscosity of the grease for refrigerating machine oil before heat defoaming, and the lower part shows the immiscibility of grease for refrigerating machine oil after heat defoaming. The consistency and viscosity were shown.
In addition, the incompatibility, flow resistance (non-fluidity), and slidability of the grease for refrigerating machine oil after defoaming by heating were evaluated. The results are shown in Table 3.

Figure 0007044514000001
Figure 0007044514000001

Figure 0007044514000002
Figure 0007044514000002

Figure 0007044514000003
Figure 0007044514000003

表１、２の結果から明らかなように、各実施例で得られた冷凍機油用グリースは、冷媒に相溶しにくく、かつ、冷媒に流されにくかった。また、摺動性にも優れていた。
対して、表３の結果から明らかなように、不混和ちょう度が３４０超である比較例１、２で得られた冷凍機油用グリースは、冷媒に流されやすかった。
不混和ちょう度が１００未満である比較例３で得られた冷凍機油用グリースは、冷媒と共に流動しないが、ワックス状を呈しており、冷凍機油として不向きであった。
樹脂（Ａ）の代わりにシリカを用いた比較例４で得られた冷凍機油用グリースは、冷媒に流されやすかった。
なお、比較例１、２、４の場合、冷凍機油用グリースが冷媒に流されやすかったため、摺動性の評価は不要と判断し、評価しなかった。 As is clear from the results in Tables 1 and 2, the grease for refrigerating machine oil obtained in each example was difficult to be compatible with the refrigerant and was not easily washed away by the refrigerant. It was also excellent in slidability.
On the other hand, as is clear from the results in Table 3, the grease for refrigerating machine oil obtained in Comparative Examples 1 and 2 having an immiscible consistency of more than 340 was easily washed away by the refrigerant.
The grease for refrigerating machine oil obtained in Comparative Example 3 having an immiscible consistency of less than 100 did not flow with the refrigerant, but was waxy and unsuitable as refrigerating machine oil.
The grease for refrigerating machine oil obtained in Comparative Example 4 in which silica was used instead of the resin (A) was easily washed away by the refrigerant.
In the cases of Comparative Examples 1, 2 and 4, since the grease for refrigerating machine oil was easily flowed into the refrigerant, it was judged that the evaluation of slidability was unnecessary and was not evaluated.

Claims (3)

炭化水素油と、融点が２７０℃以下の樹脂とを含み、
前記樹脂が、ポリエチレン樹脂、ポリプロピレン樹脂またはこれらの組み合わせであり、
２５℃における不混和ちょう度が１００～３４０である、冷凍機油用グリース。 It contains a hydrocarbon oil and a resin having a melting point of 270 ° C. or lower.
The resin is a polyethylene resin, a polypropylene resin, or a combination thereof.
A grease for refrigerating machine oil having an immiscible consistency at 25 ° C. of 100 to 340. 前記炭化水素油の４０℃における動粘度が２００００ｍｍ２／ｓ以上であり、前記樹脂の含有量が４～１０質量％である、請求項１に記載の冷凍機油用グリース。 The grease for refrigerating machine oil according to claim 1, wherein the hydrocarbon oil has a kinematic viscosity of 20000 mm 2 / s or more at 40 ° C. and a resin content of 4 to 10% by mass. 前記炭化水素油の４０℃における動粘度が２００００ｍｍ２／ｓ未満であり、前記樹脂の含有量が５～１５質量％である、請求項１に記載の冷凍機油用グリース。 The grease for refrigerating machine oil according to claim 1, wherein the hydrocarbon oil has a kinematic viscosity of less than 20000 mm 2 / s at 40 ° C. and a resin content of 5 to 15% by mass.
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JP2009144005A (en) 2007-12-12 2009-07-02 Tsubakimoto Chain Co Lubricant composition for chain and chain
JP2012251014A (en) 2011-05-31 2012-12-20 Idemitsu Kosan Co Ltd Bearing grease
JP2015229723A (en) 2014-06-05 2015-12-21 株式会社日立製作所 Wire rope for elevator apparatus and elevator apparatus using the same
JP2017105932A (en) 2015-12-10 2017-06-15 株式会社日立製作所 Grease for elevator rope, elevator rope and traction type elevator

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