WO2016121795A1

WO2016121795A1 - Lubricant solution and method for manufacturing article with lubricant coating film

Info

Publication number: WO2016121795A1
Application number: PCT/JP2016/052278
Authority: WO
Inventors: 宏明光岡; 花田　毅
Original assignee: 旭硝子株式会社
Priority date: 2015-01-27
Filing date: 2016-01-27
Publication date: 2016-08-04
Also published as: JPWO2016121795A1; CN107207981A; CN107207981B; JP6686911B2

Abstract

A lubricant solution: comprising a lubricant (A) containing a diamine-modified silicone oil and a solvent (B) containing trans-1,2-dichloroethylene (tDCE) and 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy) ethane (HFE-347pc-f); containing 40-70 mass% of tDCE in 100 mass% total of tDCE and HFE-347pc-f; and containing 30-60 mass% of HFE-347pc-f in 100 mass% total of tDCE and HFE-347pc-f.

Description

Lubricant solution and method for producing article with lubricant coating

The present invention relates to a lubricant solution and a method for producing an article with a lubricant coating.

For example, an article having a coating film containing a lubricant (hereinafter, also referred to as a lubricant coating film) is obtained by applying a lubricant solution in which a lubricant is dissolved in a solvent to the surface of an object to be coated and then evaporating the solvent. Manufactured by forming a lubricant coating on the surface of an object to be coated.

As the solvent, chlorofluorocarbons (hereinafter referred to as CFCs) and hydrochlorofluorocarbons (hereinafter referred to as HCFCs) are used because they are nonflammable and excellent in chemical and thermal stability. It is done. However, since CFCs and HCFCs adversely affect the ozone layer, the production of CFCs and HCFCs will be abolished in 2020 in developed countries.

Examples of solvents that do not adversely affect the ozone layer include perfluorocarbons (hereinafter referred to as PFCs), hydrofluorocarbons (hereinafter referred to as HFCs), and hydrofluoroethers (hereinafter referred to as HFEs). Etc. are known. However, PFCs and HFCs are substances subject to the Kyoto Protocol because of their large global warming potential. Moreover, PFCs, HFCs, and HFEs have a low solubility as a lubricant, and therefore have a narrow range of application as solvents for lubricants.

A trans-1,2-dichloroethylene (trans-CHCl = CHCl, hereinafter also referred to as tDCE) is known as a solvent that does not adversely affect the global environment and is excellent in the solubility of the lubricant. However, tDCE is difficult to use alone because it has a flash point.

Various solvents in which tDCE and a fluorine-based solvent are mixed have been proposed as solvents having excellent solubility for lubricants having no flash point. For example, Patent Document 1 discloses a solvent composed of tDCE and methyl perfluorobutyl ether (CH ₃ OCF ₂ CF ₂ CF ₂ CF ₃ , hereinafter also referred to as HFE-449s1). The solvent disclosed in Patent Document 1 is useful as a solvent for silicone lubricants. Patent Document 2 discloses a solvent containing tDCE and methyl perfluoroheptene ether (hereinafter also referred to as MPHE). The solvent disclosed in Patent Document 2 is effective as a solvent for removing the silicone fluid on the substrate surface.

When the object to be coated with the lubricant coating is a metal such as an injection needle, a modified silicone oil, particularly a diamine-modified silicone oil is used as the lubricant because it has excellent adhesion to the metal. Although the solvents of Patent Documents 1 and 2 dissolve diamine-modified silicone oil, the stability of a solution stored for several days (hereinafter referred to as storage stability) is insufficient. Therefore, the lubricant solution containing the diamine-modified silicone oil and the solvent of Patent Document 1 or 2 has a problem that the cloudiness or the lubricant is separated during storage. And when using the lubricant solution from which white turbidity or the lubricant isolate | separated, a uniform lubricant film may not be formed on the surface of a to-be-coated object.

Also, the diamine-modified silicone oil may be used in combination with a diamine group-containing alkoxysilane that is a crosslinking agent.

Further, as a solvent in which tDCE and a fluorine-based solvent are mixed, Patent Document 3 discloses that tDCE and 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane (CF ₃ CH ₂ OCF ₂ CF ₂ H (hereinafter also referred to as HFE-347pc-f), and Patent Document 4 disclose a solvent containing tDCE, HFE-347pc-f, and methanol, respectively. However, Patent Documents 3 and 4 do not describe the use of these disclosed solvents as lubricant solvents. Furthermore, it is unclear whether the solvents of Patent Documents 3 and 4 have the solubility of diamine-modified silicone oil.

Japanese Patent No. 2908033 Special table 2014-511428 gazette Japanese Patent No. 2879847 Japanese Patent No. 4556669

An object of the present invention is to provide a lubricant solution that does not adversely affect the global environment, has excellent storage stability and does not have a flash point, and a method for producing an article with a lubricant coating using the lubricant solution. And

The present invention provides a lubricant solution and an article with a lubricant coating having the following constitution.
[1] A lubricant (A) containing a diamine-modified silicone oil and a solvent (B) containing tDCE and HFE-347pc-f, wherein tDCE is a total of 100% by mass of tDCE and HFE-347pc-f. A lubricant solution comprising 40 to 70% by mass of HFE-347pc-f and 30 to 60% by mass of 100% by mass of tDCE and HFE-347pc-f in total.
[2] The lubricant solution according to [1], wherein the lubricant (A) is contained in an amount of 0.01 to 50% by mass in 100% by mass of the lubricant solution.
[3] The lubricant solution according to [1] or [2], wherein the solvent (B) is contained in an amount of 50 to 99.99% by mass in 100% by mass of the lubricant solution.
[4] The lubricant solution according to any one of [1] to [3], wherein the solvent (B) further includes an organic solvent (B1) soluble in tDCE.
[5] The lubricant solution according to [4], wherein the organic solvent (B1) is an alcohol having 1 to 3 carbon atoms.
[6] The lubricant solution according to [4] or [5], wherein the organic solvent (B1) is contained in an amount of 0.1 to 50% by mass in 100% by mass of the solvent (B).
[7] The solvent (B) is trans-1,2-dichloroethylene, 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane, The lubricant solution according to any one of [1] to [6], comprising 3 alcohols.
[8] The lubricant solution according to any one of [1] to [7], further comprising any one of a diamine group-containing alkoxysilane and a partial condensate thereof.
[9] A step of applying the lubricant solution according to any one of [1] to [8] to the surface of the object to be coated, and the solvent (B) in the lubricant solution applied to the surface of the object to be coated And a step of forming a coating film containing the lubricant (A) on the surface of the object to be coated.
[10] The method for producing an article with a lubricant coating according to [9], wherein the article to be coated is an injection needle.

According to the present invention, it is possible to provide a lubricant solution that does not adversely affect the global environment, has excellent storage stability, and does not have a flash point. Furthermore, it is possible to provide a method for producing an article with a lubricant coating, which can safely produce an article having a uniform lubricant coating without adversely affecting the global environment.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiment. Various modifications and substitutions can be made to the following embodiments without departing from the scope of the present invention.

The following definitions of terms apply throughout this specification and the claims. “Lubricant” means a material used to reduce friction on a contact surface and prevent generation of heat and wear damage when two members move with the surfaces in contact with each other. “Fluorine-based lubricant” means a lubricant having a fluorine atom in the molecule. “Silicone-based lubricant” means a lubricant containing silicone. “Silicone oil” is a polymer of an organosilicon compound having a siloxane bond (Si—O—Si) as the main skeleton and an organic group such as a methyl group bonded to a silicon atom, so-called silicone, which has a relatively high degree of polymerization. It means low and oily at room temperature (25 ° C.). The “diamine-modified silicone oil” means one having a diamine group (—RNHR′NH ₂ , where R and R ′ are each a divalent organic group) as part of the organic group of the silicone oil. To do. "Solvent" means that diamine-modified silicone oil can be dissolved by itself or in combination with other solvents, can evaporate at the temperature at which a lubricant film is formed, and does not react with lubricants and additives. Means a liquid compound at room temperature (25 ° C.). “Organic solvent that is soluble in tDCE” means that the solvent is mixed with tDCE so as to have a desired concentration and stirred at room temperature (25 ° C.) to dissolve evenly without causing two-layer separation or turbidity. An organic solvent that can be produced. “No flash point” means having no flash point between 23 ° C. and boiling point. “Diamine group-containing alkoxysilane” means a compound having a diamine group and an alkoxy group bonded to a silicon atom.

<Lubricant solution>
The lubricant solution of the present invention contains a lubricant (A) and a solvent (B). The lubricant solution may contain an additive (C) in addition to the lubricant (A) and the solvent (B) as required, within a range not impairing the effects of the present invention.

(Lubricant (A))
The lubricant (A) contains a diamine-modified silicone oil. If necessary, the lubricant (A) may contain other lubricants in a range not impairing the effects of the present invention, in addition to the diamine-modified silicone oil.

[Diamine-modified silicone oil]
Specific examples of the diamine-modified silicone oil or the lubricant (A) containing the diamine-modified silicone oil include the following. A main component is a copolymer of a diamine group-containing alkylsiloxane and dimethylsiloxane described in JP-B-46-3627. The reaction product of a diamine group-containing silane and an epoxy group-containing silane and a silanol group-containing diorganopolysiloxane described in JP-B 61-35870 or JP-B 62-52796 Things to do. A mixture of silicone and diorganopolysiloxane having a diamine group at the side chain and / or terminal described in JP-A-7-178159. A mixture of a non-reactive silicone and a silicone obtained by reacting a diamine group-containing alkoxysilane, an epoxy group-containing alkoxysilane and a silicone having silanol groups at both ends as described in JP-A-10-309316.

As a diamine-modified silicone oil, dimethylpolysiloxane side chain or a part of the methyl group at the end is substituted with a diamine group because it is easily available, adsorbs to the metal surface, and is excellent in lubricity. The compound represented by Formula (1) is preferable.

In formula (1), each A is independently a methyl group, a hydroxy group, an epoxy group, an alkoxy group (—OR ″), or a diamine group (—RNHR′NH ₂ ), provided that at least one of A One is a diamine group, R and R ′ are each a divalent organic group, and R ″ is a monovalent organic group. m and n are each an integer of 1 or more. R is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms, and particularly preferably an alkylene group having 3 carbon atoms. R ′ is preferably an alkylene group, more preferably an alkylene group having 1 to 5 carbon atoms, and particularly preferably an alkylene group having 2 carbon atoms. R ″ is preferably an alkyl group, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

Examples of commercially available diamine-modified silicone oil or lubricant (A) containing diamine-modified silicone oil include the following. “TSF 4702”, “TSF 4703”, “TSF 4704”, “TSF 4705”, “TSF 4706”, “TSF 4707”, “TSF 4708” manufactured by Momentive Performance Materials Japan. “SF8417”, “BY16-849”, “BY16-205”, “FZ-3760”, “BY16-892”, “FZ-3785”, “BY16-872”, “BY16-” manufactured by Toray Dow Corning 893 "," FZ-3789 "," MDX4-4159 ". “L653”, “L655”, “L656”, “L662”, “WR210”, “WR301”, “WR1100”, “WR1200”, “WR1300”, “WR1250”, “WT1650”, manufactured by Asahi Kasei Wacker Silicone “65000VP”. “KF-859”, “KF-393”, “KF-860”, “KF-880”, “KF-8004”, “KF-8002”, “KF-8005”, “KF” manufactured by Shin-Etsu Chemical Co., Ltd. -867 "," KF-8021 "," KF-896 "," KF-861 ". A diamine modified silicone oil may be used individually by 1 type, and may use 2 or more types together.

[Other lubricants]
Other lubricants are preferably silicone-based lubricants or fluorine-based lubricants other than diamine-modified silicone oils because of their excellent solubility in tDCE. Other lubricants are appropriately selected according to the required lubrication performance. The other lubricant may be in any form of liquid (oil), semi-solid (grease), and solid.

As the silicone oil, dimethyl silicone oil, which is an unmodified silicone oil, or modified silicone oil (excluding diamine-modified silicone oil) is preferable. As the modified silicone oil, hydrogen-modified silicone oil, methylphenyl silicone oil, and cyclic dimethyl silicone oil are preferable. Examples of commercially available silicone oils include the following. “KF-96”, “KF-965”, “KF-968”, “KF-99”, “KF-50”, “KF-54”, “HIVAC F-4”, “ "HIVAC F-5", "KF-56A", "KF-995". “SH200” manufactured by Toray Dow Corning.

As the silicone grease, silicone oil is preferably used as a base oil and a thickener such as metal soap and various additives are blended. Examples of commercially available silicone greases include the following. “G-30 Series”, “G-40 Series”, “FG-720 Series”, “G-411”, “G-501”, “G-6500”, “G-330” manufactured by Shin-Etsu Chemical Co., Ltd. , “G-340”, “G-350”, “G-630”. “MORICOAT (registered trademark) SH33L”, “MORICOAT (registered trademark) 41”, “MORICOAT (registered trademark) 44”, “MORICOAT (registered trademark) 822M”, “MORICOAT (registered trademark) 111” manufactured by Toray Dow Corning "Molicoat (registered trademark) high vacuum grease", "Molicoat (registered trademark) thermal diffusion compound".

Examples of the fluorine-based lubricant include fluorine oil, fluorine grease, and fluorine-based solid lubricant (polytetrafluoroethylene powder and the like). Examples of the silicone-based lubricant include silicone oil and silicone grease. Examples of the fluorine-based lubricant and the silicone-based lubricant include fluorosilicone oil which is a modified silicone oil in which a terminal or a side chain is substituted with a fluoroalkyl group.

Fluorine oil is preferably a low polymer of perfluoropolyether or chlorotrifluoroethylene. Examples of commercially available fluorine oils include the following. "Crytox (registered trademark) GPL102" manufactured by DuPont. "Daifloil (registered trademark) # 1", "Daiflooil (registered trademark) # 3", "Daiflooil (registered trademark) # 10", "Daiflooil (registered trademark) # 20", "Daiflooil (registered trademark)" manufactured by Daikin Industries, Ltd. ) # 50 "," Daifloil (registered trademark) # 100 "," Demnam (registered trademark) S-65 ". "Fomblin (registered trademark) M03", "Fomblin (registered trademark) M15", "Fomblin (registered trademark) M30", "Fomblin (registered trademark) M60", "Fomblin" manufactured by Solvay Specialty Polymers (Registered trademark) M100 ”,“ fomblin (registered trademark) Y04 ”,“ fomblin (registered trademark) Y06 ”,“ fomblin (registered trademark) Y25 ”,“ fomblin (registered trademark) Y45 ”,“ fomblin ” (Registered trademark) YR "," fomblin (registered trademark) YPL1500 "," fomblin (registered trademark) YPL1800 "," fomblin (registered trademark) YLVAC06 / 6 "," fomblin (registered trademark) YLVAC14 / 6 " , “Fomblin® YLVAC 16/6”, “Fomblin® YLVA” 25/6 ”,“ fomblin® YHVAC 18/8 ”,“ fomblin® YHVAC 25/9 ”,“ fomblin® YHVAC 40/11 ”,“ fomblin® YHVAC140 / 13 "," Fomblin (registered trademark) W150 "," Fomblin (registered trademark) W500 "," Fomblin (registered trademark) W800 "," Fomblin (registered trademark) Z03 "," Fomblin (registered trademark) " Z15 "," Fomblin (registered trademark) Z25 "," Fomblin (registered trademark) Z60 ".

Fluorine grease preferably contains fluorine oil as a base oil and is blended with polytetrafluoroethylene powder or other thickener. Examples of commercially available fluorine greases include the following. "Crytox (registered trademark) Grease 240AC" manufactured by DuPont. "Daifloil (registered trademark) Grease DG-203", "Demnam (registered trademark) L65", "Demnam (registered trademark) L100", "Demnam (registered trademark) L200" manufactured by Daikin Industries, Ltd. “Sumitec F936” manufactured by Sumiko Lubricant Co., Ltd. "Molicoat (registered trademark) HP-300", "Molicoat (registered trademark) HP-500", "Molicoat (registered trademark) HP-870", and "Molicoat (registered trademark) 6169" manufactured by Toray Dow Corning. "Fomblin (registered trademark) OT-20", "Fomblin (registered trademark) RT-15", "Fomblin (registered trademark) YVAC2", "Fomblin (registered trademark) YVAC3" manufactured by Solvay Specialty Polymers .

Examples of commercially available fluorosilicone oils include the following. "Unidyne (registered trademark) TG-5601" manufactured by Daikin Industries, Ltd. "Moricoat (registered trademark) 3451" and "Moricoat (registered trademark) 3452" manufactured by Toray Dow Corning. “FL-5”, “X-22-821”, “X-22-822”, “FL-100” manufactured by Shin-Etsu Chemical Co., Ltd.

1 type may be sufficient as the other lubricant contained in a lubricant (A), and 2 or more types may be sufficient as it. The silicone-based lubricant and the fluorine-based lubricant may be used alone or in combination.

(Solvent (B))
The solvent (B) contains tDCE and HFE-347pc-f. If necessary, the solvent (B) may contain an organic solvent (B1) soluble in tDCE in addition to tDCE and HFE-347pc-f as long as the effects of the present invention are not impaired. The solvent (B) preferably does not contain any other solvent other than tDCE, HFE-347pc-f, and the organic solvent (B1).

[TDCE]
Since tDCE is an olefin having a double bond between carbon atoms, it has a short lifetime in the atmosphere and does not adversely affect the global environment. Since tDCE has a boiling point of about 49 ° C., it has excellent drying properties. In addition, since the boiling point is about 49 ° C. even when the liquid is boiled, tDCE is less likely to adversely affect parts that are easily affected by heat such as resin parts. tDCE has a low surface tension and low viscosity and easily evaporates even at room temperature. tDCE is excellent in the solubility of other lubricants. As described above, tDCE has sufficient performance as a solvent in a lubricant solution, except that it has a flash point.

Examples of commercially available tDCE include the following. “Trans-LC (registered trademark)” manufactured by Daido Air Products Electronics. “Trans-1,2-dichloroethylene” manufactured by PPG INDUSTRIES INC.

[HFE-347pc-f]
HFE-347pc-f has a zero ozone depletion coefficient and a low global warming coefficient. HFE-347pc-f has an excellent drying property because it has a boiling point of about 56 ° C. In addition, even if boiled and vaporized, the boiling point is about 56 ° C., so HFE-347pc-f is less likely to adversely affect parts that are easily affected by heat such as resin parts. HFE-347pc-f has no flash point. HFE-347pc-f has low surface tension and low viscosity and easily evaporates even at room temperature. As described above, HFE-347pc-f has sufficient performance as a solvent in a lubricant solution, except that the solubility of the diamine-modified silicone oil is low.

HFE-347pc-f is prepared in the presence of an aprotic polar solvent and a catalyst (alkali metal alkoxide or alkali metal hydroxide) described in WO 2004/108644, for example. It can be produced by a method of reacting fluoroethanol and tetrafluoroethylene.

Examples of commercially available HFE-347pc-f include the following. “Asahiklin (registered trademark) AE-3000” manufactured by Asahi Glass Co., Ltd.

[Organic solvent (B1)]
The organic solvent (B1) is an organic solvent soluble in tDCE. The organic solvent (B1) is appropriately selected according to various purposes such as increasing the solubility and adjusting the volatilization rate.

Examples of the organic solvent (B1) include hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons (excluding tDCE), HFCs, HFEs (HFE-347pc-f) soluble in tDCE. ), Hydrofluoroolefins (hereinafter also referred to as HFOs), chlorofluoroolefins (hereinafter also referred to as CFOs), hydrochlorofluoroolefins (HCFOs), and the like.

As hydrocarbons soluble in tDCE, hydrocarbons having 5 or more carbon atoms are preferable. The hydrocarbons may be chain hydrocarbons, cyclic hydrocarbons, saturated hydrocarbons, or unsaturated hydrocarbons. . As hydrocarbons soluble in tDCE, n-pentane, 2-methylbutane, n-hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, n-heptane, 2-methylhexane , 3-methylhexane, 2,4-dimethylpentane, n-octane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 2,2-dimethylhexane, 2,5-dimethylhexane, 3,3- Dimethylhexane, 2-methyl-3-ethylpentane, 3-methyl-3-ethylpentane, 2,3,3-trimethylpentane, 2,3,4-trimethylpentane, 2,2,3-trimethylpentane, 2- Methylheptane, 2,2,4-trimethylpentane, n-nonane, 2,2,5-trimethylhexane, n-decane, n-dodecane, 2 Methyl-2-butene, 1-pentene, 2-pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, bicyclohexane, cyclohexene, α-pinene, dipentene, decalin, tetralin, amylnaphthalene and the like are included. Of these, n-pentane, cyclopentane, n-hexane, cyclohexane and n-heptane are preferred.

As alcohols soluble in tDCE, alcohols having 1 to 16 carbon atoms are preferable, and alcohols having 1 to 3 carbon atoms are more preferable because they have an azeotropic composition with tDCE and HFE-347pc-f. The alcohol may be a chain alcohol, may be a cyclic alcohol, may be a saturated alcohol, or may be an unsaturated alcohol. Examples of alcohols soluble in tDCE include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-ethyl-1-propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 4 -Methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, 1-nonanol, 3, 5,5-trimethyl-1-hexanol, -Decanol, 1-undecanol, 1-dodecanol, allyl alcohol, propargyl alcohol, benzyl alcohol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 4-methylcyclohexanol, α-terpineol 2,6-dimethyl-4-heptanol, nonyl alcohol, tetradecyl alcohol and the like. Among these, methanol, ethanol, and isopropyl alcohol are preferable.

As ketones soluble in tDCE, ketones having 3 to 9 carbon atoms are preferable. The ketones may be chain ketones, cyclic ketones, saturated ketones, or unsaturated ketones. Ketones soluble in tDCE include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, diisobutyl ketone, mesityl oxide, phorone. 2-octanone, cyclohexanone, methylcyclohexanone, isophorone, 2,4-pentanedione, 2,5-hexanedione, diacetone alcohol, acetophenone, and the like. Among these, acetone and methyl ethyl ketone are preferable.

As ethers soluble in tDCE, ethers having 2 to 8 carbon atoms are preferable. The ethers may be chain ethers, cyclic ethers, saturated ethers, or unsaturated ethers. Examples of ethers soluble in tDCE include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetol, methylanisole, furan, methylfuran, tetrahydrofuran and the like. Among these, diethyl ether, diisopropyl ether, and tetrahydrofuran are preferable.

As the esters soluble in tDCE, esters having 2 to 19 carbon atoms are preferable. The esters may be chain esters, may be cyclic esters, may be saturated esters, or may be unsaturated esters. Esters soluble in tDCE include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate , Pentyl acetate, methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, ethyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, Isobutyl isobutyrate, ethyl 2-hydroxy-2-methylpropionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, benzyl benzoate, γ-butyrolactone, diethyl oxalate, dibutyl oxalate, oxalic acid Pentyl, diethyl malonate, dimethyl maleate, diethyl maleate, dibutyl maleate, dibutyl tartrate, tributyl citrate, dibutyl sebacate, dimethyl phthalate, diethyl phthalate, include dibutyl phthalate and the like. Among these, methyl acetate and ethyl acetate are preferable.

As chlorocarbons soluble in tDCE, chlorocarbons having 1 to 3 carbon atoms are preferable. The chlorocarbons may be chain chlorocarbons, cyclic chlorocarbons, saturated chlorocarbons, or unsaturated chlorocarbons. . Examples of chlorocarbons soluble in tDCE include methylene chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2, 2,2-tetrachloroethane, pentachloroethane, 1,1-dichloroethylene, cis-1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, 1,2-dichloropropane and the like. Of these, methylene chloride is preferred.

As the HFCs soluble in tDCE, chain or cyclic HFCs having 4 to 8 carbon atoms are preferable, and HFCs having one or more fluorine atoms in one molecule are more than hydrogen atoms. Examples of HFCs soluble in tDCE include 1,1,1,3,3-pentafluorobutane, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,2,2,3,3,4-heptafluorocyclopentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,1,2,2,3 , 3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorooctane Etc. are included. Among them, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3,4,4-nonafluorohexane, 1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane is preferred.

HFEs soluble in tDCE include HFE-449s1, ethyl perfluorobutyl ether, and the like. Among these, HFE-449s1 is preferable. Examples of HFOs soluble in tDCE include MPHE, 1,1,1,4,4,4-hexafluoro-2-butene and the like. Examples of CFOs soluble in tDCE include 1,1-dichloro-2,3,3,3-tetrafluoro-1-propene (CFO-1214ya). HCFOs soluble in tDCE include cis and trans isomers of 1-chloro-3,3,3-trifluoropropene, 1,1-dichloro-3,3,3-trifluoropropene and the like.

The organic solvent (B1) contained in the solvent (B) may be one type or two or more types. When two or more organic solvents (B1) are included in the solvent (B), the combination of the organic solvents (B1) may be a combination of the same category or a combination of different categories of solvents. Also good. For example, the organic solvent (B1) may be a combination of two kinds of hydrocarbons or a combination of one kind of hydrocarbon and one kind of alcohol.

The organic solvent (B1) is more preferably a solvent having no flash point. As the organic solvent (B1) having no flash point, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1,1,1,2,2,3,3 , 4,4-nonafluorohexane, HFCs such as 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, HFE-449s1, etc. HFEs etc. are mentioned. Even when a solvent having a flash point is used as the organic solvent (B1), the solvent (B) is preferably mixed with tDCE and HFE-347pc-f within a range not having a flash point. In addition, when tDCE and HFE-347pc-f and the organic solvent (B1) form an azeotropic composition, they can be used in the azeotropic composition.

(Additive (C))
The additive (C) is a component other than the lubricant (A) and the solvent (B) in the lubricant solution. Examples of the additive (C) include a crosslinking agent, a solvent other than tDCE, HFE-347pc-f, and the organic solvent (B1); other additives than these.

Examples of the crosslinking agent include alkoxysilanes or partial condensates (oligomers) thereof. Alkoxysilanes include so-called silane coupling agents such as tetraalkoxysilanes, mono, di, or trialkoxysilanes having alkyl or aryl groups, mono, di, or trialkoxysilanes having reactive functional groups. . As the alkoxysilanes, diamine group-containing alkoxysilanes are preferable from the viewpoint of excellent adsorbability with metals.

Examples of the diamine group-containing alkoxysilane include 3- (2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propylmethyldimethoxysilane, and the like. Examples of commercially available diamine group-containing alkoxysilanes include the following. “KBM-602” and “KBM-603” manufactured by Shin-Etsu Chemical Co., Ltd. “TSL8340” and “TSL8345” manufactured by Momentive Performance Materials Japan.

Examples of other solvents other than tDCE, HFE-347pc-f and organic solvent (B1), or other additives include nitromethane, nitroethane, nitropropane, nitrobenzene, diethylamine, triethylamine, isopropylamine, diisopropylamine, butylamine , Isobutylamine, tert-butylamine, α-picoline, N-methylbenzylamine, diallylamine, N-methylmorpholine, phenol, o-cresol, m-cresol, p-cresol, thymol, p-tert-butylphenol, tert-butyl Catechol, catechol, isoeugenol, o-methoxyphenol, 4,4'-dihydroxyphenyl-2,2-propane, isoamyl salicylate, benzyl salicylate, methyl salicylate 2,6-di-t-butyl-p-cresol, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'- Methylphenyl) -5-chlorobenzotriazole, 1,2,3-benzotriazole, 1-[(N, N-bis-2-ethylhexyl) aminomethyl] benzotriazole, 1,2-propylene oxide, 1,2- Examples include butylene oxide, 1,4-dioxane, butyl glycidyl ether, and phenyl glycidyl ether.

(Ratio of each component)
The proportion of the lubricant (A) is preferably 0.01 to 50% by mass, more preferably 0.05 to 30% by mass, and further preferably 0.1 to 20% by mass, out of 100% by mass of the lubricant solution. . When the ratio of the lubricant (A) is within the above range, it is easy to adjust the thickness of the coating film when the lubricant solution is applied and the thickness of the lubricant coating after drying to an appropriate range.

Lubricant (A) may consist of diamine-modified silicone oil alone or may contain other lubricants. When the lubricant (A) contains another lubricant in addition to the diamine-modified silicone oil, the proportion of the diamine-modified silicone oil is preferably 1 to 99% by mass in 100% by mass of the lubricant (A). More preferably, it is -95 mass%, and further preferably 20-90 mass%. The proportion of the other lubricant is preferably 1 to 99% by mass, more preferably 5 to 90% by mass, and still more preferably 10 to 80% by mass, out of 100% by mass of the lubricant (A).

The ratio of the solvent (B) is preferably 50 to 99.99% by mass, more preferably 70 to 99.95% by mass, and further preferably 80 to 99.9% by mass, out of 100% by mass of the lubricant solution. If the ratio of the solvent (B) is within the above range, it is easy to adjust the thickness of the coating film when the lubricant solution is applied and the thickness of the lubricant coating after drying to an appropriate range.

The proportion of tDCE is 40 to 70% by mass, preferably 45 to 60% by mass, more preferably 50 to 55% by mass, out of the total 100% by mass of tDCE and HFE-347pc-f. The ratio of HFE-347pc-f is 30 to 60% by mass, preferably 40 to 55% by mass, and more preferably 45 to 50% by mass, out of the total 100% by mass of tDCE and HFE-347pc-f. When the ratio of tDCE and the ratio of HFE-347pc-f are within the above ranges, the solubility of the diamine-modified silicone oil is excellent, and the lubricant solution does not have a flash point.

The total ratio of tDCE and HFE-347pc-f is preferably 50 to 100% by mass, more preferably 75 to 100% by mass, and further preferably 80 to 100% by mass, out of 100% by mass of the solvent (B). When the solvent (B) contains the organic solvent (B1), it is preferable that the solvent (B) contains the organic solvent (B1) as long as it does not have a flash point. When the solvent (B) contains the organic solvent (B1), the total proportion of tDCE and HFE-347pc-f is preferably 50 to 99.9% by mass, out of 100% by mass of the solvent (B), and 75 to 99.9% by mass is more preferable, and 80 to 99.9% by mass is more preferable. The proportion of the organic solvent (B1) needs to be adjusted as appropriate within the range where the solvent (B) does not have a flash point according to the flammability characteristics of the organic solvent (B1). 0.1 to 50% by mass is preferable, 0.1 to 25% by mass is more preferable, and 0.1 to 20% by mass is further preferable. If the ratio of the total of tDCE and HFE-347pc-f and the ratio of the organic solvent (B1) are within the above ranges, the effects of the present invention are sufficiently exhibited.

The proportion of the additive (C) is preferably 5% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less, out of 100% by mass of the lubricant solution. If the ratio of the additive (C) is within the above range, the effects of the present invention are sufficiently exhibited.

When the lubricant solution contains a diamine group-containing alkoxysilane, the proportion of the diamine group-containing alkoxysilane is preferably 0.01 to 5% by mass, and 0.05 to 3% by mass in 100% by mass of the lubricant solution. More preferred is 0.1 to 1% by mass. When the ratio of the diamine group-containing alkoxysilane is equal to or higher than the lower limit, the effect as a crosslinking agent is sufficiently exhibited. If the ratio of the diamine group-containing alkoxysilane is not more than the above upper limit, the effects of the present invention are sufficiently exhibited.

The lubricant solution of the present invention uses tDCE and HFE-347pc-f, which have a small ozone depletion coefficient and a global warming coefficient, as a solvent, and thus does not adversely affect the global environment. Further, as a solvent, tDCE having excellent solubility of diamine-modified silicone oil and HFE-347pc-f having low solubility but no flash point of diamine-modified silicone oil are used at a specific ratio. The solubility of the modified silicone oil is excellent, the cloudiness or the lubricant does not separate during storage of the lubricant solution, and the lubricant solution does not have a flash point.

<Method for producing article with lubricant coating>
The manufacturing method of the articles | goods with a lubricant film of this invention has the following process (a) and process (b). In the step (a), the lubricant solution of the present invention is applied to the surface of an object to be coated. The step (b) evaporates the solvent (B) in the lubricant solution applied to the surface of the object to be coated, and forms a lubricant film that is a film containing the lubricant (A) on the surface of the object to be coated. Form.

(Process (a))
Examples of the object to be coated include various materials such as metal, plastic, elastomer, glass, and ceramic, and metal is preferable. Specific examples of the object to be coated include an injection needle and cylinder of a syringe, a medical tube component, a metal blade, a catheter, and the like, and an injection needle is preferable.

Examples of the method of applying the lubricant solution include application by brush, application by spray, application by immersing an object to be coated in the lubricant solution, and the like.

(Process (b))
As a method for evaporating the solvent (B) in the lubricant solution applied to the surface of the object to be coated, a known drying method may be mentioned. Examples of the drying method include air drying and drying by heating. The drying temperature is preferably 20 to 100 ° C. By evaporating the solvent (B) in the lubricant solution applied to the object to be coated, a lubricant coating film is formed on the surface of the object to be coated. Thus, an article with a lubricant coating provided with a lubricant coating on the surface of the object to be coated is manufactured.

The method for producing an article with a lubricant coating of the present invention uses the lubricant solution of the present invention containing tDCE and HFE-347pc-f having a low ozone depletion coefficient and a global warming coefficient as a solvent. No adverse effect. In addition, since the lubricant solution of the present invention is excellent in solubility of the diamine-modified silicone oil and does not separate from the cloudiness or lubricant during storage, a uniform lubricant coating can be formed. Moreover, since the lubricant solution of the present invention having no flash point is used, an article with a lubricant coating can be produced safely.

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. Examples 1 to 5 and 7 to 11 are reference examples, Examples 6, 12, 13, 16 to 21, 23 to 27, 30, 31, 34, and 35 are examples. Examples 14, 15, 22, and 28 29, 32 and 33 are comparative examples.

(Solubility test)
100 g of the solvent (B) prepared below was put into a heat-resistant glass bottle, and a predetermined amount of the following silicone oil as a test object was added to the solvent (B) at 23 ° C. The state of the lubricant solution immediately after the test object was added at 23 ° C. and the state of the lubricant solution stored at 23 ° C. for 5 days were observed, and the solubility was evaluated according to the following criteria.
A: Excellent, no cloudiness or separation of lubricant is observed.
B: Although it is good and thin cloudiness is seen, there is no problem in practical use.
C: Poor and clearly cloudy or lubricant separated.

(Flash point)
About the solvent before adding silicone oil, the presence or absence of the flash point from 23 degreeC to a boiling point was confirmed using the Cleveland open-type flash point measuring device (made by Yoshida Seisakusho, type 828).

(Examples 1 to 13)
[Solubility of various silicone oils in solvent (B)]
A solvent containing tDCE (manufactured by PPG INDUSTRIES INC, trans-1,2-dichloroethylene), HFE-347pc-f (manufactured by Asahi Glass Co., Ltd., ASAHIKLIN (registered trademark) AE-3000) and ethanol in the proportions shown in Table 1 ( A predetermined amount of the following silicone oil was added to B) to prepare a lubricant solution, and the solubility was evaluated. The results are shown in Table 1. In Examples 1, 2, 7, and 8, dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-96) was used. In Examples 3 and 9, epoxy-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-101) was used. In Examples 4 and 10, monoamine-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-868) was used. In Examples 5 and 11, hydrogen-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-99) was used. In Examples 6, 12, and 13, diamine-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-859) was used.

As shown in Table 1, it can be seen that the solvent (B) is highly soluble in each silicone oil.

(Examples 14 to 25)
[Solubility of diamine-modified silicone oil in solvent and flash point of solvent]
a solvent containing tDCE (manufactured by PPG INDUSTRIES INC, trans-1,2-dichloroethylene), HFE-347pc-f (manufactured by Asahi Glass Co., Ltd., ASAHIKLIN (registered trademark) AE-3000), and a ratio of ethanol shown in Table 2 Prepared. A predetermined amount of diamine-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-859) was added to each solvent to prepare a lubricant solution, and the solubility and flash point were evaluated. The results are shown in Table 2.

In Examples 14 and 15, since the ratio of tDCE was large, the solvent had a flash point. In Examples 16 to 21 and 23 to 25, since the ratio of tDCE to HFE-347pc-f is within the range of the present invention, the diamine-modified silicone oil is dissolved and the solvent (B) has no flash point. It was. In Example 22, since the ratio of HFE-347pc-f was large, the diamine-modified silicone oil did not dissolve, and the lubricant solution separated into two layers immediately after the addition of the diamine-modified silicone oil.

(Examples 26 to 33)
[Solubility of diamine-modified silicone oil in various solvents]
Table 3 shows various solvents and diamine-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-859) or a silicone oil product containing 50% by mass of diamine-modified silicone oil (manufactured by Dow Corning Toray, MDX4-4159). A lubricant solution containing a proportion was prepared and its solubility was evaluated. The results are shown in Table 3. In Examples 28 and 32, Novec (registered trademark) HFE-71DE (manufactured by 3M Japan, tDCE / HFE-449s1 = 50/50 (mass ratio)) was used. In Examples 29 and 33, Vertrel (registered trademark) Sion (manufactured by DuPont, a mixture of tDCE and HFOs) was used.

In Examples 26, 27, 30, and 31, since the ratio of tDCE to HFE-347pc-f is within the range of the present invention, no white turbidity or separation of the lubricant was observed in the lubricant solution. In Examples 28, 29, 32, and 33, since a fluorine-containing solvent other than HFE-347pc-f was contained, the cloudiness or separation of the lubricant was observed in the lubricant solution after 5 days, and the storage stability was poor.

(Example 34)
[Application test of lubricant solution]
A solvent (B) composed of 50.3% by mass of tDCE and 49.7% by mass of HFE-347pc-f was prepared. A diamine-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd., KF-859) was added to the solvent (B) so that the oil concentration in the solution was 3% by mass to prepare a lubricant solution. A lubricant solution is applied to the surface of an aluminum vapor-deposited plate obtained by vapor-depositing aluminum on an iron plate with an average thickness of about 0.4 mm, and air-dried at a temperature of 19 to 21 ° C. A lubricant coating was formed. No white turbidity was observed in the lubricant solution, and the solvent (B) quickly evaporated from the lubricant solution after application, and the state of the lubricant coating was also good.

(Example 35)
[Application test of lubricant solution]
A solvent (B) composed of 50.5% by mass of tDCE, 47.5% by mass of HFE-347pc-f, and 2% by mass of ethanol was prepared. A lubricant solution was prepared in the same manner as in Example 34 except that the solvent (B) was used, and a lubricant coating film was formed on the surface of the aluminum vapor deposition plate. No white turbidity was observed in the lubricant solution, and the solvent (B) quickly evaporated from the lubricant solution after application, and the state of the lubricant coating was also good.

The lubricant solution of the present invention is useful as a lubricant solution for forming a lubricant coating on the surface of a metal such as an injection needle.

Claims

A lubricant (A) containing a diamine-modified silicone oil;
A solvent (B) containing trans-1,2-dichloroethylene and 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane,
Of trans-1,2-dichloroethylene is 100% by mass in total of trans-1,2-dichloroethylene and 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane 40-70% by mass,
1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane is trans-1,2-dichloroethylene and 1,1,2,2-tetrafluoro-1- (2 , 2,2-trifluoroethoxy) ethane in a total amount of 100% by mass, containing 30 to 60% by mass of a lubricant solution.
The lubricant solution according to claim 1, wherein the lubricant (A) is contained in an amount of 0.01 to 50% by mass in 100% by mass of the lubricant solution.
The lubricant solution according to claim 1 or 2, wherein the solvent (B) is contained in an amount of 50 to 99.99% by mass in 100% by mass of the lubricant solution.
The lubricant solution according to any one of claims 1 to 3, wherein the solvent (B) further comprises an organic solvent (B1) soluble in trans-1,2-dichloroethylene.
The lubricant solution according to claim 4, wherein the organic solvent (B1) is an alcohol having 1 to 3 carbon atoms.
The lubricant solution according to claim 4 or 5, wherein the organic solvent (B1) is contained in an amount of 0.1 to 50% by mass in 100% by mass of the solvent (B).
The solvent (B) is trans-1,2-dichloroethylene, 1,1,2,2-tetrafluoro-1- (2,2,2-trifluoroethoxy) ethane, and an alcohol having 1 to 3 carbon atoms. The lubricant solution according to any one of claims 1 to 6, comprising
The lubricant solution according to any one of claims 1 to 7, further comprising any one of a diamine group-containing alkoxysilane and a partial condensate thereof.
Applying the lubricant solution according to any one of claims 1 to 8 to the surface of an object to be coated;
Evaporating the solvent (B) in the lubricant solution applied to the surface of the object to be coated, and forming a coating film containing the lubricant (A) on the surface of the object to be coated. A method for producing an article with a lubricant coating, characterized in that:
The method for producing an article with a lubricant coating according to claim 9, wherein the object to be coated is an injection needle.