WO2019078350A1 - Solvent composition for applying silicone compound onto article surface - Google Patents

Abstract

Provided is a silicone solution which contains a solvent and a silicone compound, and which is used for the purpose of forming a coating film of the silicone compound on an article surface, while being configured such that the solvent contains 1,2-dichloro-3, 3, 3-trifluoropropene. Also provided is a method for forming a coating film of a silicone compound on an article surface, which comprises a step wherein a silicone solution containing a silicone compound and a solvent that contains 1,2-dichloro-3, 3, 3-trifluoropropene is applied onto an article surface and the solvent is subsequently removed from the silicone solution, thereby forming a coating film of the silicone compound on the article surface.

Description

Solvent composition for applying silicone compound to article surface

The present invention relates to a silicone solution containing a solvent and a silicone compound, for forming a coating of the silicone compound on the surface of an article. The present invention also relates to a method of forming a coating of a silicone compound on the surface of an article.

Conventionally, fluorine solvents have been used as dilution solvents for silicone compounds, and as such fluorine solvents, hydrochlorofluorocarbons (hereinafter also referred to as "HCFC"), hydrofluorocarbons (hereinafter referred to as "HFC") Also known are hydrofluoroethers (hereinafter also referred to as "HFE") and the like. In recent years, it is desirable to use a fluorinated solvent that has less influence on the global environment, so hydrochlorofluoroolefins (hereinafter also referred to as "HCFO") having a double bond in the molecule and hydrofluoroolefins (hereinafter referred to as Development of "HFO" is being promoted. HCFOs and HFOs have excellent environmental performance that their lifetime in the air is short due to their high reactivity with OH radicals, and their ozone depletion potential (ODP) and global warming potential (GWP) are extremely small. ing.

In HCFOs and HFOs, for example, in Patent Document 1, 1,1-dichloro-2,3,3,3-tetrafluoropropene (hereinafter also referred to as “1214 ya”) is used for applying a silicone-based lubricant. It is disclosed that it can be used as a solvent.

In Patent Document 2, 1-chloro-3,3,3-trifluoropropene (hereinafter, cis form is also referred to as “1233zd (Z)”, trans form is also referred to as “1233zd (E)”, and cis form and trans form are described. Solvent compositions for silicone compounds have been reported where no distinction is made and mixtures are also referred to as "1233 zd".

Patent Document 3 discloses a solvent composition containing 1,2-dichloro-3,3,3-trifluoropropene (hereinafter also referred to as "1223xd"), and further, 1223xd is a mineral oil and silicone oil. It is disclosed to mix with. Patent Document 4 discloses a method of manufacturing 1223xd.

However, although 1,1-dichloro-2,3,3,3-tetrafluoropropene (1214 ya) disclosed in Patent Document 1 is a solvent having excellent solubility in a silicone compound, it is stable in air. When used in air, there is a problem that the solvent decomposes and becomes acidic during use (see Examples described later).

In addition, although 1-chloro-3,3,3-trifluoropropene (1233zd) disclosed in Patent Document 2 is a solvent excellent in silicone dissolution ability, when used alone as 1233zd, an article to which a silicone compound is applied Depending on the type, the article may be damaged (see Examples below).

Patent Document 3 merely discloses that 1223xd is miscible with mineral oil and silicone oil, and Patent Document 4 only discloses a method of producing 1223xd. In any case, the specific data on the solubility of the silicone compound in 1223xd and the stability of the silicone solvent containing 1223xd and the silicone compound were unknown.

Thus, even if the fluorinated solvent has less influence on the global environment, the preferred solvent for the silicone solution for forming the coating of the silicone compound on the article surface is still insufficient and the silicone on the article surface There is a need for new silicone solutions suitable for forming coatings of compounds.

International Publication No. 2014/073372 JP 2011-46688 A WO 2005/044969 WO 2014/046251

The present invention provides a silicone solution containing a solvent and a silicone compound, which is a new silicone solution for forming a coating of a silicone compound on the surface of an article, and a method of forming a coating of a silicone compound on the surface of an article. To be an issue.

The present inventors diligently studied to solve the above problems. As a result, a silicone solution using 1,2-dichloro-3,3,3-trifluoropropene (1223xd) as a solvent for the silicone compound is suitable for forming a coating of the silicone compound on the surface of the article. The present invention has been completed.

That is, the present invention includes the following inventions.
[Invention 1]
A silicone solution comprising a solvent and a silicone compound,
The solvent comprises 1,2-dichloro-3,3,3-trifluoropropene,
A silicone solution for forming a coating of the silicone compound on the surface of an article.

[Invention 2]
1,2-dichloro-3,3,3-trifluoropropene is exemplified by Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trione The silicone solution according to the invention 1, which is fluoropropene or a mixture thereof.

[Invention 3]
The silicone solution according to invention 1 or 2, wherein the solvent consists essentially of 1,2-dichloro-3,3,3-trifluoropropene.

[Invention 4]
The invention wherein the solvent further comprises at least one selected from the group consisting of hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, hydrofluorocarbons, hydrofluoroethers and hydrofluoroolefins. The silicone solution according to 1 or 2.

[Invention 5]
The silicone solution according to any one of Inventions 1 to 4, wherein the mass ratio of the solvent to the silicone compound is: solvent / the silicone compound composition = 70 to 99/1 to 30.

[Invention 6]
The silicone solution according to any one of inventions 1 to 5, wherein the article is an article composed of at least one member selected from the group consisting of a metal member, a resin member, a ceramic member and a glass member.

[Invention 7]
The silicone solution according to any one of inventions 1 to 6, wherein the article is an article composed of at least a metal member and a resin member.

[Invention 8]
In any of Inventions 1 to 7, the article is an injection needle including a needle portion and a joint portion, wherein the needle portion is formed of a metal member, and the joint portion is formed of a resin member. Silicone solution as described.

[Invention 9]
The silicone solution according to any one of Inventions 1 to 8, wherein the application is performed at low temperature.

[Invention 10]
A method of forming a coating of a silicone compound on the surface of an article, comprising the steps of:
(1) applying a silicone solution containing a solvent and a silicone compound to the surface of the article, wherein the solvent is a silicone solution containing 1,2-dichloro-3,3,3-trifluoropropene;
(2) removing the solvent from the silicone solution to form a coating of a silicone compound on the surface of the article.

[Invention 11]
1,2-dichloro-3,3,3-trifluoropropene is exemplified by Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trione The method according to invention 10, which is fluoropropene or a mixture thereof.

[Invention 12]
The method according to invention 10, wherein said solvent consists essentially of 1,2-dichloro-3,3,3-trifluoropropene.

[Invention 13]
The invention wherein the solvent further comprises at least one selected from the group consisting of hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, hydrofluorocarbons, hydrofluoroethers and hydrofluoroolefins. The method according to 10 or 11.

[Invention 14]
The method according to any of inventions 10 to 13, wherein the mass ratio of the solvent to the silicone compound is: solvent / the silicone compound composition = 70 to 99/1 to 30.

[Invention 15]
The method according to any one of inventions 10 to 14, wherein the article is an article composed of at least one member selected from the group consisting of metal members, resin members, ceramic members and glass members.

[Invention 16]
The method according to any one of claims 10 to 15, wherein the article is an article composed of at least a metal member and a resin member.

[Invention 17]
The article according to any of inventions 10 to 16, wherein the article is an injection needle having a needle portion and a joint portion, wherein the needle portion is a metal member, and the joint portion is a resin member. Method described.

[Invention 18]
The method according to any of inventions 10 to 17, wherein the application is performed at low temperature.

[Invention 19]
(C) recovering the removed solvent, the method according to any of inventions 10-18.

[Invention 20]
(D) reusing the removed solvent, the method according to any of the tenth to nineteenth aspects of the present invention.

According to the present invention, a silicone solution containing a solvent and a silicone compound, which is a new silicone solution suitable for forming a coating of a silicone compound on the surface of an article, and a coating of a silicone compound on the surface of an article We can provide a way.

Hereinafter, the present invention will be described in detail, but the present invention should not be construed as being limited to the following embodiments and the description of the examples.

According to one aspect of the present invention, there is provided a silicone solution comprising a solvent and a silicone compound. This solvent includes 1,2-dichloro-3,3,3-trifluoropropene (1223xd). This silicone solution is suitably used to form a coating of a silicone compound on the surface of an article.

Since 1,2-dichloro-3,3,3-trifluoropropene (1223xd) contains two chlorine atoms in its molecule, it is assumed that its polarity is higher than 1233zd and its dissolution ability is higher. Surprisingly, it has been found that damage to the article can be suppressed while exhibiting high solubility in silicone compounds, as disclosed in the document. As disclosed herein, a silicone solvent using 1,2-dichloro-3,3,3-trifluoropropene (1223xd) as a solvent for the silicone compound forms a coating of the silicone compound on the surface of the article It turned out that it is suitable for

Also, according to another aspect of the present invention, there is provided a method of forming a coating of a silicone compound on an article surface. In this method, the above-mentioned silicone solution is suitably used.

1. Silicone Solution Hereinafter, the silicone solution will be described.

<Solvent>
In the present invention, at least 1223 x d is used as a solvent.

The solvent may consist essentially of 1223xd. Here, "consisting essentially of 1223xd" means that the content of 1223xd in the solvent is 90% by mass or more, and the component other than 1223xd is 10% by mass or less, preferably the content of 1223xd is 95 It means that it is mass% or more, and components other than 1223xd are 5 mass% or less. The types of components other than this 1223xd are not particularly limited. Examples thereof include, but are not limited to, raw materials and by-products used in the synthesis process of 1223xd, impurities that may be contained in 1223xd of recycled products, stabilizers, and the like.

(1,2-dichloro-3,3,3-trifluoropropene (1223xd))
1223xd is a known compound and can be produced, for example, by the method described in Patent Document 3.

In the present invention, 1223xd may be either a cis form (hereinafter also referred to as "1223xd (Z)") or a trans form (hereinafter also referred to as "1223xd (E)"), or a mixture of both. Good. In one aspect of the present invention, 1223 x d (Z) is preferably employed. Moreover, in another aspect of the present invention, a mixture of 1223xd (Z) and 1223xd (E) is preferably employed. When a mixture of 1223xd (Z) and 1223xd (E) is used as a solvent, the thermodynamically stable isomer 1223zd (Z) is preferred, and 1223xd (Z) and 1223xd (E) are preferred. It is more preferable that the mass ratio thereof is 1223 × d (Z) / 1223 × d (E) = 80/20 to 99.99 / 0.01, and 1223 × d (Z) / 1223 × d (E) = 90/10 to 99.99 / 0 .01 is particularly preferred.

(Other solvents)
In the present invention, the solvent may use other solvent (A) in combination with 1223xd. As such solvent (A), hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, hydrofluorocarbons (HFCs), hydrofluoroethers (HFE), hydrofluoroolefins (HFO) And the like. The solvent (A) may be of one type or of two or more types.

Among commercially available silicone compounds, there are those which contain not only silicone compounds but also solvents such as hydrocarbons and alcohols (for example, MDX4-4159, manufactured by Dow Corning). In the present invention, the other solvent (A) may be a solvent contained in such a silicone compound.

In the present invention, the content of the solvent (A) in the solvent may be 100% by mass or less with respect to 1223xd. In one aspect of the present invention, the content of the solvent (A) in the solvent is preferably less than 100% by mass, more preferably 50% by mass or less, and more preferably 20% by mass or less with respect to 1223xd. Being particularly preferred. In another aspect of the present invention, the content of the solvent (A) in the solvent is preferably 10% by mass or less, more preferably 5% by mass or less, with respect to 1223 × d, and 1% by mass It is particularly preferred that

<Silicone compound>
In the present invention, as the silicone compound, for example, various silicones used for coating the surface of an article can be used, but the invention is not limited thereto. Specific examples of such silicones include straight silicones, and modified silicones such as reactive silicones and non-reactive silicones. More specifically, examples of straight silicones include methyl silicones, phenyl silicones, dimethyl silicones bonded with hydrogen atoms as substituents, methyl phenyl silicones, methyl hydrogen silicones and the like. The reactive silicone includes amino-modified, epoxy-modified, carboxy-modified, carbinol-modified, methacryl-modified, phenol-modified, heterofunctional-group modified and the like. Non-reactive silicones include polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, hydrophilic special-modified, fluorine-modified and the like. These silicones may be one or a mixture of two or more. The silicone compound may also be a nitrogen-containing modified silicone.

<Silicone solution>
In the silicone solution of the present invention, the content of the solvent and the silicone compound is not particularly limited. In one aspect of the present invention, the content of the solvent and the silicone compound in the silicone solution is preferably 100% by mass or less of the silicone compound with respect to the solvent. In another aspect of the present invention, the content of the solvent and the silicone compound in the silicone solution is preferably 70/30 to 99/1 in terms of the mass ratio of the solvent to the silicone compound. For example, solvent / silicone compound = 99/1, 98/2, 97/3, 95/5, 90/10, 85/15, 80/20, 75/25, 70/30). Within this range, a film having a sufficient film thickness is easily formed, and a film having a uniform film thickness is easily obtained.

The silicone solution of the present invention may contain other components in addition to the solvent and the silicone compound, as long as the effects of the present invention are not adversely affected, but it is preferable that the silicone solution substantially consists of the solvent and the silicone compound. . Here, "consists essentially of a solvent and a silicone compound" means that the total content of the solvent and the silicone compound in the silicone solution of the present invention is 90% by mass or more, preferably 95% by mass or more, and more preferably It means that it is 98% by mass or more, particularly preferably 99% by mass or more.

(Other ingredients)
Other components can be appropriately selected by those skilled in the art according to the application. Other components include, for example, pH adjusters, leveling agents, thickeners, pigments, dyes, silica fine particles, metal oxide fine particles, metal powders, antioxidants, ultraviolet light stabilizers, heat ray reflection, absorption imparting agents, Examples thereof include a flexibility imparting agent, an antistatic agent, an antifouling agent, and a water repellency imparting agent. In addition, the other components may be impurities derived from the solvent used or the silicone compound. Examples of such impurities include, but are not limited to, raw materials and by-products used in the synthesis process of 1223xd and silicone compounds, and impurities that may be contained in 1223xd of recycled products.

The other components may be moisture, but depending on the type of silicone compound, the moisture may cause the silicone compound to become cloudy. Therefore, the lower the content of water in the silicone solution, the better, and the weight ratio to the silicone solution is preferably 50 ppm or less, particularly preferably 20 ppm or less. The other components may be an acid component, but the acid component may adversely affect the product itself or the use environment of the product depending on the article to be applied and the use of the product. Therefore, the smaller the acid content, the better, and the weight ratio to the silicone solution is preferably less than 1 ppm. In one aspect of the present invention, the silicone solution preferably contains no water or acid. The acid component can be removed by washing the solvent and the like with water, and the water content can be removed by drying with a desiccant such as molecular sieve.

<Articles>
The silicone solution of the present invention is suitably used to form a coating of a silicone compound on the surface of an article. Such articles include, but are not limited to, articles of various materials such as metals, resins, ceramics, glasses or composites thereof. In addition, such an article may be an article provided with a metal member, a resin member, a ceramic member, a glass member, or a composite member thereof. Here, as the metal, stainless steel, aluminum, an aluminum alloy and the like can be mentioned, but it is not limited thereto. Examples of the resin include acrylonitrile butadiene styrene copolymer synthetic resin (ABS resin), polyethylene, acrylic resin, polyvinyl chloride (hard), polypropylene, chloroprene, acrylonitrile butadiene rubber, fluororubber, silicone rubber, butyl rubber, natural rubber, ethylene Examples thereof include propylene rubber, Teflon (registered trademark), nylon 66, polyester glass, phenol resin, polycarbonate, polyacetal, chlorosulfonated polyethylene rubber, hydrogenated acrylonitrile butadiene rubber, polyfluorinated vicinidine, nylon, styrene butadiene rubber and the like. Among such articles, an article composed of at least a metal member or a resin member or both is preferable. Examples of such articles include puncture needles such as injection needles, winged needles and indwelling needles, blades such as cutting blades, and springs and spring portions of dispensers (liquid quantitative ejection devices), etc. It is not limited to these. In particular, an article comprising at least a metal member and a resin member is preferable, and an injection needle comprising a needle portion and a joint portion, wherein the needle portion is made of a metal member, and the joint portion is made of a resin member Injection needles are particularly preferred.

Injection needles for medical use and the like are often disposable in view of hygiene, and such an injection needle generally uses metal as the material of the needle portion and resin as the material of the joint portion. As such a resin, general purpose resins such as PP (polypropylene resin), ABS (acrylonitrile-butadiene-styrene copolymer synthetic resin), PC (polycarbonate resin), PA (polyacrylic resin) and the like are generally used. In one step of a general manufacturing method of such an injection needle, after joining a metal cylinder (needle portion) and a resin member (joint portion), the silicone solution of the present invention is applied to the needle portion by a method such as immersion. Apply When using a silicone solution containing a solvent that is highly polymer-erodible, if the solution adheres to the joint, the joint may be damaged. Therefore, it is preferable to use a solvent with low polymer attack as a solvent of the silicone solution. In this respect, the solvent in the silicone solution has low polymer attack. Therefore, in forming a coating of a silicone compound on such an injection needle, a silicone solution using the present solvent can be particularly suitably adopted.

2. Method of Forming a Coating of a Silicone Compound on an Article Hereinafter, a method of forming a coating of a silicone compound will be described.

The method of the present invention comprises the following steps (1) and (2).
(1) A step of applying a silicone solution containing a solvent and a silicone compound, wherein the solvent is a silicone solution containing 1,2-dichloro-3,3,3-trifluoropropene, to an article.
(2) removing the solvent from the silicone solution to form a coating of a silicone compound on the surface of the article.

In a preferred embodiment of the present invention, a silicone solution can be applied to an article and a solvent can be removed from the applied silicone solution to form a coating of a silicone compound on the article.

The method for applying the silicone solution to the article is not particularly limited, and those skilled in the art can appropriately adopt conventionally known methods. Examples include, but are not limited to, a method of immersing the article in a silicone solution, a method of spray coating, and the like. The temperature upon application may be lower than the boiling point of the solvent contained in the silicone solution. In addition, as also shown in the examples, a mixture of 1223xd and a silicone compound is uniform even at a low temperature, for example, in a cold place (generally, at a temperature of 1 to 15 ° C. The same applies hereinafter). Since it is a layer liquid, the method of the present invention can be suitably adopted even in such a working environment.

The method for removing the solvent from the applied silicone solution is not particularly limited, and those skilled in the art can appropriately adopt conventionally known methods. For example, a method of volatilizing components such as a solvent by leaving at room temperature or under heating may be mentioned, but it is not limited thereto.

The removed solvent may be recovered and can be reused as the solvent of the present invention. Alternatively, it can be reused for other applications. The recovered solvent may be purified and then reused. That is, the method of the present invention may include the following step (c), step (d) or both of them.
(C) recovering the removed solvent.
(D) Reusing the removed solvent.

1. Stability Test of Silicone Solution Hereinafter, a test for examining the stability of the silicone solution will be described.

[Examples 1 to 4 and Comparative Examples 1 to 2 and Reference Example 1]
According to the following method, a silicone compound was dissolved in a solvent to prepare a silicone solution, and its stability test was conducted.

The solvents (9.5 mL) and silicone compound (0.5 mL) shown in Table 1 were placed in a 20 mL glass sample bottle and mixed to obtain a uniform solution. The solution was stored in a dark place at a temperature controlled at 23 ° C., and the state of the solution was visually observed after 0 days (immediately after mixing the silicone compound and the solvent), 3 days, and 7 days. The solution was evaluated as colorless and clear (no turbidity) as "○" and as slightly colored and cloudy as "評 価", and clearly colored and gelated as "×" It evaluated as ". The results are shown in Table 1.

In Table 1, KF-96 is a straight silicone manufactured by Shin-Etsu Silicone Co., Ltd., and MDX4-4159 is a modified silicone (nitrogen-containing silicone) manufactured by Dow Corning. 1223xd (Z form: 96%, E form: 4%) and 1223xd (Z) were subjected to water washing and zeolite drying, and used one having an acid content of less than 1 ppm and a water content of 10 ppm. 1214ya (1,1-dichloro-2,3,3,3-tetrafluoropropene), 1233zd (Z) and Asahi Klin (registered trademark) AK-225 (manufactured by Asahi Glass Co., Ltd.) were washed with water, separated in two phases, Dehydrated with Sieve (registered trademark) 3 Å was used. Asahiculin (registered trademark) AK-225 is 1,1-dichloro-2,2,3,3,3-pentafluoropropane (HCFC-225ca) and 1,3-dichloro-1,2,2,3, respectively. It is a mixture of 3,3-pentafluoropropane (HCFC-225 cb).

As shown in Table 1, when using 1223xd, 1223xd (cis: 96%, trans: 4%), 1233zd (Z) and AK-225 as solvents, the solution after 3 and 7 days All states were colorless and transparent. However, although 1214ya is a compound having a chlorine atom, a fluorine atom and a double bond in the molecule, like 1223xd and 1233zd, the solution becomes pale yellowish after 3 days when it is used. After 7 days, it became yellowish and clear gelation was confirmed.

In addition, when the solution after completion of the test of Comparative Example 1 (after 7 days) was extracted with ultrapure water and measured with pH test paper, the pH value was 4.1, and generation of an acid component was confirmed.

2. Article Compatibility Test Hereinafter, a test for examining the compatibility of the silicone solution with an article will be described.

[Examples 5 to 6 and Comparative Examples 4 to 5 and Reference Example 2]
The solvent (95 mL) and silicone compound (5 mL) shown in Table 2 were placed in a 500 mL glass beaker and mixed to prepare a clear and uniform silicone solution. The test piece made of PP resin, test piece made of PC resin, test piece made of PA resin, test piece made of PA resin, and test piece made of ABS resin are each immersed for 5 minutes in a silicone solution cooled to 5 ° C., and then the test piece is recovered and naturally dried. I did. The condition of the test piece after drying was visually observed. Those with no change in the dimensions and surface of the test piece before and after immersion were evaluated as "o", and those with significant erosion and dimensional change were evaluated as "x". The results are shown in Table 2.

As shown in Table 2, no change was observed in the test pieces before and after immersion in Example 5, Example 6, Comparative Example 4 and Reference Example 1, but in Comparative Example 5, the test pieces after immersion (PC, PA) And each of the ABS test pieces showed significant erosion and dimensional change. Thus, it has been found that even if the solvent used is a compound having a chlorine atom, a fluorine atom and a double bond in the molecule, the compound has a different article compatibility.

3. Drying Evaluation Test Hereinafter, a test for measuring the drying property of the solvent in the silicone solution will be described.

[Example 7]
A mixed solution of 1223 × d (Z) (95 mL) and MDX 4-4159 (5 mL) was prepared. After immersion in this solution for 10 seconds while moving the needle part of Terumo disposable injection needle (23G × 1 ′ ′, NN-2325R) up and down, it was pulled out of the solution and shaken three times to remove the solution. Dry air was blown for 10 seconds from the joint side to the disposable injection needle to obtain a silicone-coated needle in a similar manner to obtain a total of 5 silicone-coated needles: these 5 silicone-coated needles The needle was put in a 150 mL glass sample bottle, sealed tightly, and allowed to stand for 2 hours at 60 ° C. After standing, 1 mL of the gas in the sample bottle was sampled and analyzed by a FID type gas chromatograph. The peak derived from the silicone compound was detected, but the peak derived from 1223xd (Z) was not detected. Corn coating preformed needle means that the volatilized before sealed put in a glass sample bottle. That, 1223xd (Z) is found to have a superior drying property as a solvent.

4. Coating Evaluation Test, Drying Evaluation Test, and Solvent Solubility Evaluation Test at Low Temperature Hereinafter, tests in which the coating property, drying property and solubility of the silicone solution on articles are examined will be described.

[Examples 8 to 15]
Using the silicone solution which is in the category of the present invention, a coating property evaluation test, a drying property evaluation test and a solvent solubility evaluation test of the silicone compound were conducted.

A clear, uniform silicone solution was prepared by mixing the solvents listed in Table 3 with a silicone compound and cooled to 5 ° C. A metal plate made of SUS304 was immersed in this silicone solution, and then naturally dried to obtain a metal plate made of SUS304 on which a silicone film was formed. The silicone film-formed SUS304 metal plate was visually observed. The coating property of the coating film of the metal plate was evaluated as "good" when no unevenness was observed, and the coating property was evaluated as "poor" when the unevenness was observed.

Further, a metal plate made of SUS304 and coated with a silicone film was put in a glass sample bottle, sealed up, and allowed to stand at 60 ° C. for 2 hours. After standing, 1 mL of the gas in the sample bottle was sampled and analyzed by a FID-type gas chromatograph. The thing which the peak derived from a solvent was not detected evaluated that dryness was "good", and the thing from which the peak derived from a solvent was detected evaluated that dryness was "defect."

In addition, as a solvent solubility test of the silicone compound under a low temperature, the state of the silicone solution when the prepared silicone solution was cooled to 5 ° C. was visually observed. The solubility was evaluated as "good" when the silicone solution was a transparent and uniform layer at 5 ° C, and the solubility was evaluated as "poor" when the silicone solution was an uneven layer. .

The results of these evaluation tests are shown in Table 3. In Table 3, 1223 x d represents a mixture of Z form (96% by mass) and E form (4% by mass), and the mass ratio represents the mass ratio of solvent to silicone compound (solvent / silicone compound).

Claims (20)

1. A silicone solution comprising a solvent and a silicone compound,
   The solvent comprises 1,2-dichloro-3,3,3-trifluoropropene,
   A silicone solution for forming a coating of the silicone compound on the surface of an article.
2. 1,2-dichloro-3,3,3-trifluoropropene is exemplified by Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trione The silicone solution according to claim 1, which is fluoropropene or a mixture thereof.
3. The silicone solution according to claim 1 or 2, wherein the solvent consists essentially of 1,2-dichloro-3,3,3-trifluoropropene.
4. The solvent further comprises at least one selected from the group consisting of hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, hydrofluorocarbons, hydrofluoroethers and hydrofluoroolefins. The silicone solution according to item 1 or 2.
5. The silicone solution according to claim 1, wherein the mass ratio of the solvent to the silicone compound is: solvent / the silicone compound composition = 70 to 99/1 to 30.
6. The silicone solution according to claim 1, wherein the article is an article composed of at least one member selected from the group consisting of a metal member, a resin member, a ceramic member and a glass member.
7. The silicone solution according to claim 6, wherein the article is an article composed of at least a metal member and a resin member.
8. The silicone according to claim 7, wherein the article is an injection needle including a needle portion and a joint portion, the needle portion being made of a metal member, and the joint portion being made of a resin member. solution.
9. The silicone solution according to claim 1, wherein the application is performed at low temperature.
10. (1) applying a silicone solution containing a solvent containing 1,2-dichloro-3,3,3-trifluoropropene and a silicone compound on the surface of the article,
    (2) removing the solvent from the silicone solution to form a coating of a silicone compound on the surface of the article;
    A method of forming a coating of a silicone compound on the surface of an article, comprising:
11. 1,2-dichloro-3,3,3-trifluoropropene is exemplified by Z-1,2-dichloro-3,3,3-trifluoropropene, E-1,2-dichloro-3,3,3-trione The method according to claim 10, which is fluoropropene or a mixture thereof.
12. 11. The method of claim 10, wherein the solvent consists essentially of 1,2-dichloro-3,3,3-trifluoropropene.
13. The solvent further comprises at least one selected from the group consisting of hydrocarbons, alcohols, ketones, ethers, esters, chlorocarbons, hydrofluorocarbons, hydrofluoroethers and hydrofluoroolefins. Item 12. The method according to Item 10 or 11.
14. The method according to claim 10, wherein the mass ratio of the solvent to the silicone compound is: solvent / the silicone compound composition = 70 to 99/1 to 30.
15. The method according to claim 10, wherein the article is an article composed of at least one member selected from the group consisting of metal members, resin members, ceramic members and glass members.
16. The method according to claim 15, wherein the article is an article composed of at least a metal member and a resin member.
17. The method according to claim 16, wherein the article is an injection needle having a needle portion and a joint portion, the needle portion being made of a metal member, and the joint portion being made of a resin member.
18. 11. The method of claim 10, wherein the application is performed at low temperature.
19. 11. The method of claim 10, further comprising: (c) recovering the removed solvent.
20. 11. The method of claim 10, further comprising: (d) recycling the removed solvent.