JP6597956B2 - Solvent composition - Google Patents

Description

  The present invention may be referred to as Z-1-chloro-3,3,3-trifluoropropene (hereinafter, “1233zd (Z)”) having extremely low global warming potential (GWP) and ozone depletion potential (ODP). .), And a method for cleaning an article using the solvent composition.

  Fluorine-containing saturated compounds such as chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs) are used as cleaning agents to remove dirt on the surface of an article, and for application to form a coating film on the surface of an article. It has been used as a draining agent for drying the surface of an article wet with a solvent or water. Among the fluorine-containing saturated compounds, 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113), 3,3-dichloro-1,1,1,2,2-pentafluoropropane ( HCFC-225ca) and 1,3-dichloro-1,1,2,2,3-pentafluoropropane (HCFC-225cb) have characteristics such as excellent solubility, drying property, nonflammability and stability. Have been widely used.

  Since CFCs have a chemically stable structure, they have a long atmospheric lifetime and reach the stratosphere when diffused into the atmosphere. CFCs that have reached the stratosphere are decomposed by ultraviolet rays, generate chlorine radicals, and destroy the ozone layer. HCFCs, like CFCs, have chlorine atoms in their molecules and have an impact on the ozone layer, so production will be abolished in developed countries in 2020.

  Hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs) that do not contain chlorine in the molecule have been developed as solvents that replace HCFCs. HFCs and HFEs have advantages such as zero ozone depletion coefficient and excellent chemical stability, but they have a large global warming potential (GWP) and the problem of global warming remains. . Therefore, an alternative solvent having a small influence on the global environment is desired.

  Fluoroolefins having a double bond in the molecule have been developed as an alternative to HCFCs, HFCs and HFEs. Since fluoroolefins have high reactivity with OH radicals, they have excellent environmental performance such as a short lifetime in the atmosphere and extremely low ozone depletion potential and global warming potential.

  It is known that fluoroolefins are less stable than fluorine-containing saturated compounds such as HFCs. When fluoroolefins are decomposed during use as a solvent, there is a problem that the solvent is acidified (pH is lowered) and the cleaning article or the cleaning machine member is damaged. For this reason, stabilizers for stabilizing fluoroolefins have been developed.

  In Patent Document 1, 1,2-epoxybutane, glycidyl methyl ether and the like are added as stabilizers to HFOs such as 1,3,3,3-tetrafluoropropene (HFO-1234ze), Disclosed are compositions that are stable during use, handling, and storage.

  It is known that fluoroolefins have low stability in the presence of air (oxygen). Patent Document 2 discloses that the number of carbon atoms is 1 with respect to HFOs such as 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,3,3,3-tetrafluoropropene (HFO-1234ze). A refrigerant composition that is stable in the presence of air is disclosed by adding an aliphatic alcohol having an alcohol number of 1 to 4 as a stabilizer.

  Some fluoroolefins are known to have low stability in air at room temperature. In Patent Document 3, 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) decomposes and acidifies in a few days when stored in air at room temperature. It discloses the stabilization by adding ethers, epoxides, amines and the like as stabilizers.

  Fluorine-containing saturated compounds such as HCFCs and HFCs have been widely used as dry cleaning solvents for clothing. Various surfactants and additives are used for the dry cleaning solvent in order to improve the cleaning performance and the texture of clothing. For example, Patent Document 3 discloses at least one selected from the group consisting of 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) and phenols, epoxides and amines. It discloses that wool fabric garments can be washed using a solvent composition containing a stabilizer as a dry cleaning solvent.

  Patent Document 3 describes that since the stabilization technique varies depending on the type of fluoroolefin, even if the technique described in the prior art document is applied, the stabilization effect on a specific fluoroolefin cannot be predicted. On the other hand, Patent Documents 1 to 3 do not have a specific description regarding the stability of Z-1-chloro-3,3,3-trifluoropropene and the stabilizing effect under the condition where a stabilizer is added.

Special table 2010-531924 International Publication No. 2010/098447 International Publication No. 2014/073372

  The present invention relates to a solvent composition comprising at least a Z-1-chloro-3,3,3-trifluoropropene having a very low global warming potential (GWP) and ozone depletion potential (ODP) and a predetermined stabilizer. It is an object of the present invention to provide a solvent composition that is stable even in the presence of air and a method for cleaning an article using the solvent composition.

  As a result of intensive studies by the present inventors, at least one stabilizer selected from the group consisting of an amine having a hydroxyl group and an amide having a hydroxyl group, and Z-1-chloro-3,3,3-tri The present inventors have found that a solvent composition containing at least fluoropropene is stable even in the presence of air and has completed the present invention.

（一般式［１］中、Ｒ^１、Ｒ^２およびＲ^４はそれぞれ独立に水素原子、炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基、（ＣＲ^６ｂ _２ＣＲ^７ｂ _２Ｏ）_ｂＲ^８、（ＣＲ^６ｃ _２ＣＲ^７ｃ _２Ｏ）_ｃＲ^９または（ＣＲ^６ｄ _２ＣＲ^７ｄ _２Ｏ）_ｄＲ^１０を表す。Ｒ^３は水素原子、炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基またはＣＯＲ^１１を表す。Ｒ^５は炭素数１〜６のアルキレン基を表し、該アルキレン基中の炭素原子の一部または全部が芳香族環に置換されていてもよい。Ｒ^６ａ〜Ｒ^６ｄおよびＲ^７ａ〜Ｒ^７ｄはそれぞれ独立に水素原子、炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。Ｒ^８〜Ｒ^１０はそれぞれ独立に水素原子、炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。Ｒ^１１は炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。ｎは０〜９の整数を表す。ａは１〜５０の整数を表し、ｂ〜ｄはそれぞれ独立に０〜５０の整数を表し、ａ＋ｂ＋ｃ＋ｄ＝５０を満たす。Ｒ^３およびＲ^８〜Ｒ^１０のうち少なくとも一つは水素原子を表す。Ｒ^４が複数存在する場合、互いに同じまたは異なる種類であってもよく、Ｒ^５、Ｒ^６ａ〜Ｒ^６ｄ、Ｒ^７ａ〜Ｒ^７ｄおよびＲ^８〜Ｒ^１０についても同様である。
一般式［２］中、Ｒ^２およびＲ^４はそれぞれ独立に水素原子、炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基、（ＣＲ^６ｂ _２ＣＲ^７ｂ _２Ｏ）_ｂＲ^８または（ＣＲ^６ｃ _２ＣＲ^７ｃ _２Ｏ）_ｃＲ^９を表す。Ｒ^３は水素原子、炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基またはＣＯＲ^１１を表す。Ｒ^５は炭素数１〜６のアルキレン基を表し、該アルキレン基中の炭素原子の一部または全部が芳香族環に置換されていてもよい。Ｒ^６ａ〜Ｒ^６ｃおよびＲ^７ａ〜Ｒ^７ｃはそれぞれ独立に水素原子、炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。Ｒ^８〜Ｒ^９はそれぞれ独立に水素原子、炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。Ｒ^１１およびＲ^１２はそれぞれ独立に炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。ｎは０〜９の整数を表す。ａは１〜５０の整数を表し、ｂ〜ｃはそれぞれ独立に０〜５０の整数を表し、ａ＋ｂ＋ｃ＝５０を満たす。Ｒ^３およびＲ^８〜Ｒ^９のうち少なくとも一つは水素原子を表す。Ｒ^４が複数存在する場合、互いに同じまたは異なる種類であってもよく、Ｒ^５、Ｒ^６ａ〜Ｒ^６ｃ、Ｒ^７ａ〜Ｒ^７ｃおよびＲ^８〜Ｒ^９についても同様である。）
［発明３］
安定化剤が、下記式（Ａ）〜（Ｎ）で表される化合物より選ばれる少なくとも１種である、発明１に記載の溶剤組成物。

（式（Ａ）中、ｘ、ｙおよびｚはそれぞれ独立に１以上の整数を表し、ｘ＋ｙ＋ｚ＝１３を満たす。
式（Ｋ）中、Ｒ^１３は炭素数８〜１８の脂肪族炭化水素基を表す。
式（Ｌ）中、ｖおよびｗはそれぞれ独立に０〜５の整数を表し、ｖ＋ｗ＝５を満たす。
式（Ｎ）中、Ｒ^１４は炭素数１２〜１８の脂肪族炭化水素基を表す。）
［発明４］
安定化剤が、アミンまたはアミドと、アルキレンオキシドとを反応させて得られる生成物であって、
反応温度が０〜２００℃であり、アミンおよびアミドの総量１モルに対してアルキレンオキシドを１〜５０モル用いて反応させる、発明１に記載の溶剤組成物。
［発明５］
アミンが、アンモニア、Ｃ_１〜２０第一級アミン、Ｃ_１〜２０第二級アミン、ポリアルキレンポリアミン、芳香族アミン、複素環式アミン、尿素およびグリシンからなる群より選ばれる少なくとも１種であり、
アミドが、カルボン酸アミド、カルボン酸Ｃ_２〜２０一級アミド、カルボン酸Ｃ_２〜２０二級アミド、およびラクタム類からなる群より選ばれる少なくとも１種であり、
アルキレンオキシドが、エチレンオキシド、プロピレンオキシド、１，２−ブチレンオキシドおよび２，３−ブチレンオキシドからなる群より選ばれる少なくとも１種である、
発明４に記載の溶剤組成物。
［発明６］
Ｚ−１−クロロ−３，３，３−トリフルオロプロペンおよび安定化剤の総量に対して５００ｐｐｍ〜１質量％の水をさらに含む、発明１〜５の何れかに記載の溶剤組成物。
［発明７］
安定化剤の含有量が、Ｚ−１−クロロ−３，３，３−トリフルオロプロペンに対して０．０１〜１０質量％である、発明１〜６の何れかに記載の溶剤組成物。
［発明８］
発明１〜７の何れかに記載の溶剤組成物を用いる、物品を洗浄する方法。
［発明９］
発明１〜７の何れかに記載の溶剤組成物を用いる、衣類をドライクリーニングする方法。
［発明１０］
発明１〜７の何れかに記載の溶剤組成物を用いる、衣類の帯電を防止する方法。
［発明１１］
Ｚ−１−クロロ−３，３，３−トリフルオロプロペンを安定化する方法であって、
Ｚ−１−クロロ−３，３，３−トリフルオロプロペンと安定化剤とを配合し、
該安定化剤が、ヒドロキシル基を有するアミン化合物または、ヒドロキシル基を有するアミド化合物である、方法。
［発明１２］
安定化剤が、下記一般式［１］で表される化合物または下記一般式［２］で表される化合物である、発明１１に記載の方法。

（一般式［１］中、Ｒ^１、Ｒ^２およびＲ^４はそれぞれ独立に水素原子、炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基、（ＣＲ^６ｂ _２ＣＲ^７ｂ _２Ｏ）_ｂＲ^８、（ＣＲ^６ｃ _２ＣＲ^７ｃ _２Ｏ）_ｃＲ^９または（ＣＲ^６ｄ _２ＣＲ^７ｄ _２Ｏ）_ｄＲ^１０を表す。Ｒ^３は水素原子、炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基またはＣＯＲ^１１を表す。Ｒ^５は炭素数１〜６のアルキレン基を表し、該アルキレン基中の炭素原子の一部または全部が芳香族環に置換されていてもよい。Ｒ^６ａ〜Ｒ^６ｄおよびＲ^７ａ〜Ｒ^７ｄはそれぞれ独立に水素原子、炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。Ｒ^８〜Ｒ^１０はそれぞれ独立に水素原子、炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。Ｒ^１１は炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。ｎは０〜９の整数を表す。ａは１〜５０の整数を表し、ｂ〜ｄはそれぞれ独立に０〜５０の整数を表し、ａ＋ｂ＋ｃ＋ｄ＝５０を満たす。Ｒ^３およびＲ^８〜Ｒ^１０のうち少なくとも一つは水素原子を表す。Ｒ^４が複数存在する場合、互いに同じまたは異なる種類であってもよく、Ｒ^５、Ｒ^６ａ〜Ｒ^６ｄ、Ｒ^７ａ〜Ｒ^７ｄおよびＲ^８〜Ｒ^１０についても同様である。
一般式［２］中、Ｒ^２およびＲ^４はそれぞれ独立に水素原子、炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基、（ＣＲ^６ｂ _２ＣＲ^７ｂ _２Ｏ）_ｂＲ^８または（ＣＲ^６ｃ _２ＣＲ^７ｃ _２Ｏ）_ｃＲ^９を表す。Ｒ^３は水素原子、炭素数１〜３０のアルキル基、炭素数２〜３０のアルケニル基またはＣＯＲ^１１を表す。Ｒ^５は炭素数１〜６のアルキレン基を表し、該アルキレン基中の炭素原子の一部または全部が芳香族環に置換されていてもよい。Ｒ^６ａ〜Ｒ^６ｃおよびＲ^７ａ〜Ｒ^７ｃはそれぞれ独立に水素原子、炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。Ｒ^８〜Ｒ^９はそれぞれ独立に水素原子、炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。Ｒ^１１およびＲ^１２はそれぞれ独立に炭素数１〜３０のアルキル基または炭素数２〜３０のアルケニル基を表す。ｎは０〜９の整数を表す。ａは１〜５０の整数を表し、ｂ〜ｃはそれぞれ独立に０〜５０の整数を表し、ａ＋ｂ＋ｃ＝５０を満たす。Ｒ^３およびＲ^８〜Ｒ^９のうち少なくとも一つは水素原子を表す。Ｒ^４が複数存在する場合、互いに同じまたは異なる種類であってもよく、Ｒ^５、Ｒ^６ａ〜Ｒ^６ｃ、Ｒ^７ａ〜Ｒ^７ｃおよびＲ^８〜Ｒ^９についても同様である。）
［発明１３］
安定化剤が、下記式（Ａ）〜（Ｎ）で表される化合物より選ばれる少なくとも１種である、発明１１に記載の方法。

（式（Ａ）中、ｘ、ｙおよびｚはそれぞれ独立に１以上の整数を表し、ｘ＋ｙ＋ｚ＝１３を満たす。
式（Ｋ）中、Ｒ^１３は炭素数８〜１８の脂肪族炭化水素基を表す。
式（Ｌ）中、ｖおよびｗはそれぞれ独立に０〜５の整数を表し、ｖ＋ｗ＝５を満たす。
式（Ｎ）中、Ｒ^１４は炭素数１２〜１８の脂肪族炭化水素基を表す。）
［発明１４］
安定化剤が、アミンまたはアミドと、アルキレンオキシドとを反応させて得られる生成物であって、
反応温度が０〜２００℃であり、アミンおよびアミドの総量１モルに対してアルキレンオキシドを１〜５０モル用いて反応させる、発明１１に記載の方法。
［発明１５］
アミンが、アンモニア、Ｃ_１〜２０第一級アミン、Ｃ_１〜２０第二級アミン、ポリアルキレンポリアミン、芳香族アミン、複素環式アミン、尿素およびグリシンからなる群より選ばれる少なくとも１種であり、
アミドが、カルボン酸アミド、カルボン酸Ｃ_２〜２０一級アミド、カルボン酸Ｃ_２〜２０二級アミドおよびラクタム類からなる群より選ばれる少なくとも１種であり、
アルキレンオキシドが、エチレンオキシド、プロピレンオキシド、１，２−ブチレンオキシドおよび２，３−ブチレンオキシドからなる群より選ばれる少なくとも１種である、
発明１４に記載の方法。
［発明１６］
Ｚ−１−クロロ−３，３，３−トリフルオロプロペンおよび安定化剤の総量に対して５００ｐｐｍ〜１質量％の水をさらに配合する、発明１１〜１５の何れか一項に記載の方法。
［発明１７］
安定化剤の配合量が、Ｚ−１−クロロ−３，３，３−トリフルオロプロペンに対して０．０１〜１０質量％である、発明１１〜１６の何れか一項に記載の方法。 That is, the present invention includes the following inventions.
[Invention 1]
A solvent composition comprising at least Z-1-chloro-3,3,3-trifluoropropene and a stabilizer,
A solvent composition, wherein the stabilizer is an amine compound having a hydroxyl group or an amide compound having a hydroxyl group.
[Invention 2]
The solvent composition according to claim 1, wherein the stabilizer is a compound represented by the following general formula [1] or a compound represented by the following general formula [2].

(In the general formula [1], R ¹ , R ² and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O). _b R ^{8 represents} (CR ^6c ₂ CR ^7c ₂ O) _c R ⁹ or (CR ^6d ₂ CR ^7d ₂ O) _d R ^10. R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or 2 carbon atoms. Represents an alkenyl group having ˜30 or COR ^11. R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring. ^{6a to} R ^6d and R ^{7a to} R ^7d each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, and R ^{8 to} R ¹⁰ each independently represent a hydrogen atom or carbon. Number 1-30 Alky Represents a group or an alkenyl group having 2 to 30 carbon atoms ^{.R 11} is .a is 1 represents an integer of .n is 0-9 for an alkenyl group of alkyl or C2-30 C1-30 Represents an integer of 50, and b to d each independently represents an integer of 0 to 50, and satisfy a + b + c + d = 50, at least one of R ³ and R ^{8 to} R ¹⁰ represents a hydrogen atom, and R ⁴ represents a plurality. when present, may be the same or different types from each other ^is the same for ^{R 5, R 6a ~R 6d,} R 7a ~R 7d and ^R 8 ^{to R 10.}
In general formula [2], R ² and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O) _b R ⁸ or It represents a _{^{(CR 6c 2 CR 7c 2 O}} ) c R 9. R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or COR ¹¹ . R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring. R ^{6a to} R ^6c and R ^{7a to} R ^7c each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. R ^{8 to} R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms. n represents an integer of 0 to 9. a represents an integer of 1 to 50, b to c each independently represents an integer of 0 to 50, and a + b + c = 50 is satisfied. At least one of R ³ and R ^{8 to} R ⁹ represents a hydrogen atom. When a plurality of R ⁴ are present, they may be the same or different from each other, and the same applies to R ⁵ , R ^{6a to} R ^6c , R ^{7a to} R ^7c, and R ^{8 to} R ⁹ . )
[Invention 3]
The solvent composition according to Invention 1, wherein the stabilizer is at least one selected from compounds represented by the following formulas (A) to (N).

(In the formula (A), x, y and z each independently represent an integer of 1 or more and satisfy x + y + z = 13.
In the formula (K), R ¹³ represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms.
In the formula (L), v and w each independently represent an integer of 0 to 5 and satisfy v + w = 5.
In the formula (N), R ¹⁴ represents an aliphatic hydrocarbon group having 12 to 18 carbon atoms. )
[Invention 4]
A stabilizer is a product obtained by reacting an amine or amide with an alkylene oxide,
The solvent composition according to Invention 1, wherein the reaction temperature is 0 to 200 ° C., and the reaction is carried out using 1 to 50 mol of alkylene oxide per 1 mol of the total amount of amine and amide.
[Invention 5]
The amine is at least one selected from the group consisting of ammonia, _C1-20 primary amine, _C1-20 secondary amine, polyalkylene polyamine, aromatic amine, heterocyclic amine, urea and glycine. ,
The amide is at least one selected from the group consisting of a carboxylic acid amide, a carboxylic acid C _2-20 primary amide, a carboxylic acid C _2-20 secondary amide, and lactams;
The alkylene oxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide,
The solvent composition as described in invention 4.
[Invention 6]
The solvent composition according to any one of Inventions 1 to 5, further comprising 500 ppm to 1% by mass of water based on the total amount of Z-1-chloro-3,3,3-trifluoropropene and the stabilizer.
[Invention 7]
The solvent composition according to any one of Inventions 1 to 6, wherein the content of the stabilizer is 0.01 to 10 mass% with respect to Z-1-chloro-3,3,3-trifluoropropene.
[Invention 8]
A method for washing an article using the solvent composition according to any one of inventions 1 to 7.
[Invention 9]
A method for dry-cleaning clothing using the solvent composition according to any one of inventions 1 to 7.
[Invention 10]
A method of preventing clothing from being charged, using the solvent composition according to any one of inventions 1 to 7.
[Invention 11]
A method for stabilizing Z-1-chloro-3,3,3-trifluoropropene comprising the steps of:
Blending Z-1-chloro-3,3,3-trifluoropropene and a stabilizer,
The method in which the stabilizer is an amine compound having a hydroxyl group or an amide compound having a hydroxyl group.
[Invention 12]
The method according to invention 11, wherein the stabilizer is a compound represented by the following general formula [1] or a compound represented by the following general formula [2].

(In the general formula [1], R ¹ , R ² and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O). _b R ^{8 represents} (CR ^6c ₂ CR ^7c ₂ O) _c R ⁹ or (CR ^6d ₂ CR ^7d ₂ O) _d R ^10. R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or 2 carbon atoms. Represents an alkenyl group having ˜30 or COR ^11. R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring. ^{6a to} R ^6d and R ^{7a to} R ^7d each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, and R ^{8 to} R ¹⁰ each independently represent a hydrogen atom or carbon. Number 1-30 Alky Represents a group or an alkenyl group having 2 to 30 carbon atoms ^{.R 11} is .a is 1 represents an integer of .n is 0-9 for an alkenyl group of alkyl or C2-30 C1-30 Represents an integer of 50, and b to d each independently represents an integer of 0 to 50, and satisfy a + b + c + d = 50, at least one of R ³ and R ^{8 to} R ¹⁰ represents a hydrogen atom, and R ⁴ represents a plurality. when present, may be the same or different types from each other ^is the same for ^{R 5, R 6a ~R 6d,} R 7a ~R 7d and ^R 8 ^{to R 10.}
In general formula [2], R ² and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O) _b R ⁸ or It represents a _{^{(CR 6c 2 CR 7c 2 O}} ) c R 9. R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or COR ¹¹ . R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring. R ^{6a to} R ^6c and R ^{7a to} R ^7c each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. R ^{8 to} R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms. n represents an integer of 0 to 9. a represents an integer of 1 to 50, b to c each independently represents an integer of 0 to 50, and a + b + c = 50 is satisfied. At least one of R ³ and R ^{8 to} R ⁹ represents a hydrogen atom. When a plurality of R ⁴ are present, they may be the same or different from each other, and the same applies to R ⁵ , R ^{6a to} R ^6c , R ^{7a to} R ^7c, and R ^{8 to} R ⁹ . )
[Invention 13]
The method according to Invention 11, wherein the stabilizer is at least one selected from compounds represented by the following formulas (A) to (N).

(In the formula (A), x, y and z each independently represent an integer of 1 or more and satisfy x + y + z = 13.
In the formula (K), R ¹³ represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms.
In the formula (L), v and w each independently represent an integer of 0 to 5 and satisfy v + w = 5.
In the formula (N), R ¹⁴ represents an aliphatic hydrocarbon group having 12 to 18 carbon atoms. )
[Invention 14]
A stabilizer is a product obtained by reacting an amine or amide with an alkylene oxide,
The process according to invention 11, wherein the reaction temperature is 0 to 200 ° C., and the reaction is carried out using 1 to 50 mol of alkylene oxide per 1 mol of the total amount of amine and amide.
[Invention 15]
The amine is at least one selected from the group consisting of ammonia, _C1-20 primary amine, _C1-20 secondary amine, polyalkylene polyamine, aromatic amine, heterocyclic amine, urea and glycine. ,
The amide is at least one selected from the group consisting of a carboxylic acid amide, a carboxylic acid C _2-20 primary amide, a carboxylic acid C _2-20 secondary amide, and lactams;
The alkylene oxide is at least one selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide,
The method according to invention 14.
[Invention 16]
The method according to any one of Inventions 11 to 15, further comprising 500 ppm to 1% by mass of water based on the total amount of Z-1-chloro-3,3,3-trifluoropropene and a stabilizer.
[Invention 17]
The method as described in any one of invention 11-16 whose compounding quantity of a stabilizer is 0.01-10 mass% with respect to Z-1-chloro-3,3,3- trifluoropropene.

In the present specification, among the alkyl groups having 1 to 30 carbon atoms, the alkyl group having 4 to 30 carbon atoms may have a linear, branched or cyclic carbon chain, and the carbon chain is Any carbon atom formed may be substituted with an aromatic ring.
Among the alkenyl groups having 2 to 30 carbon atoms, the alkenyl groups having 4 to 30 carbon atoms may have a linear, branched or cyclic carbon chain, and form the carbon chain. Any carbon atom may be substituted with an aromatic ring. The position and number of multiple bonds in the alkenyl group having 2 to 30 carbon atoms are not particularly limited.
The aliphatic hydrocarbon group may have a linear, branched or cyclic carbon chain, and may have multiple bonds between carbon atoms forming the carbon chain. Well, its location and number are not limited.

  As shown in Reference Examples described later, Z-1-chloro-3,3,3-trifluoropropene is substantially decomposed even when left at 110 ° C. for 3 days under the condition that it does not come into contact with air and water. Is not recognized and is a very stable compound. However, as shown in the examples and comparative examples described below, when water is added to Z-1-chloro-3,3,3-trifluoropropene and heated under air conditions, acid content is generated and pH is increased. Decreases. In general, lowering the pH of the solvent is an undesirable phenomenon because it can cause corrosion of cleaning equipment and metal articles, inactivation of soap, embrittlement of articles (especially clothing such as cotton, pulp, and rayon). Those skilled in the art may actively add water in order to remove inorganic or organic solvent-insoluble stains. Moisture may enter the cleaning tank. Thus, the technique for preventing the pH drop of Z-1-chloro-3,3,3-trifluoropropene due to the inclusion of moisture is very important.

  Similar to the stabilizer selection in Patent Document 3, the stabilizing effect expected for various stabilizers is also exhibited in the blending with Z-1-chloro-3,3,3-trifluoropropene. Whether it is very difficult to predict on a desk. As disclosed in the present invention, the present inventors have found a compound having a stabilizing effect for preventing a decrease in pH with respect to Z-1-chloro-3,3,3-trifluoropropene.

  In Patent Document 3, there is no specific description of the effects obtained when the solvent composition of the present invention is used for washing clothes, for example, the influence on the texture of the finish or the antistatic effect.

  According to the present invention, a solvent containing at least a Z-1-chloro-3,3,3-trifluoropropene having a very low global warming potential (GWP) and ozone depletion potential (ODP) and a predetermined stabilizer. It is a composition, and can provide a solvent composition that is stable even in the presence of air, and a method for cleaning an article using the solvent composition.

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

(Solvent composition)
The solvent composition of the present invention contains at least Z-1-chloro-3,3,3-trifluoropropene and a stabilizer. The content of the stabilizer in the solvent composition of the present invention is not particularly limited as long as the pH decrease of Z-1-chloro-3,3,3-trifluoropropene can be suppressed, and Z-1-chloro-3,3 , 3-trifluoropropene may be 0.01-10 mass%. Among these, in addition to preventing the pH of Z-1-chloro-3,3,3-trifluoropropene from being lowered, various effects such as excellent detergency and good finish of cleaning are obtained. % Is preferred.

Z-1-chloro-3,3,3-trifluoropropene is a fluoroolefin having a very low global warming potential (GWP) and ozone depletion potential (ODP), and can be easily synthesized by a known method.
In addition, the global warming potential (GWP) of Z-1-chloro-3,3,3-trifluoropropene is less than 1, and the ozone depletion potential (ODP) is less than 0.00034 (Chemosphere 2015, vol. 129, pp.135-141).

  As the stabilizer, an amine compound having at least a hydroxyl group in the molecule or an amide compound having at least a hydroxyl group in the molecule is used. Hereinafter, these amine compounds and amide compounds may be collectively referred to as “nitrogen-containing alcohol compounds according to the present invention”. The nitrogen-containing alcohol compound according to the present invention may be various isomers. The nitrogen-containing alcohol compound according to the present invention may be used alone or in combination of two or more. By containing the nitrogen-containing alcohol compound according to the present invention in the solvent composition of the present invention, the pH decrease of Z-1-chloro-3,3,3-trifluoropropene is suppressed. This is particularly effective in systems where moisture is present under air conditions.

  The molecular weight of the nitrogen-containing alcohol compound according to the present invention is not particularly limited. The nitrogen-containing alcohol compound according to the present invention may have a molecular weight of 100 to 2000, preferably 160 to 1600. Within this range, the pH drop of Z-1-chloro-3,3,3-trifluoropropene can be satisfactorily suppressed, and Z-1-chloro-3,3,3-trifluoro Good solubility in propene.

  The nitrogen-containing alcohol compound according to the present invention has a hydroxyl group in the molecule and an amine having 1 to 10 nitrogen atoms, or a hydroxyl group in the molecule and has 1 to 1 nitrogen atoms. 10 amides are preferred, an amine having a hydroxyl group in the molecule and having 1 to 4 nitrogen atoms, or an amide having a hydroxyl group in the molecule and having 1 to 4 nitrogen atoms. Particularly preferred.

The nitrogen-containing alcohol compound according to the present invention may be a compound represented by the following general formula [1] or a compound represented by the following general formula [2].

In general formula [1], R ¹ , R ² and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O) _b R ^{8 represents} (CR ^6c ₂ CR ^7c ₂ O) _c R ⁹ or (CR ^6d ₂ CR ^7d ₂ O) _d R ¹⁰ .
R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or COR ¹¹ .
R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring.
R ^{6a to} R ^6d and R ^{7a to} R ^7d each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms.
R ^{8 to} R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms.
R ¹¹ represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms.
n represents an integer of 0 to 9.
a represents an integer of 1 to 50, b to d each independently represents an integer of 0 to 50, and a + b + c + d = 50 is satisfied.
At least one of R ³ and R ^{8 to} R ¹⁰ represents a hydrogen atom.
When a plurality of R ⁴ are present, they may be the same or different from each other, and the same applies to R ⁵ , R ^6a to R ^6d , R ^{7a to} R ^7d, and R ^{8 to} R ¹⁰ .

In general formula [2], R ² and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O) _b R ⁸ or It represents a _{^{(CR 6c 2 CR 7c 2 O}} ) c R 9.
R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or COR ¹¹ .
R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring.
R ^{6a to} R ^6c and R ^{7a to} R ^7c each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms.
R ^{8 to} R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms.
R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms.
n represents an integer of 0 to 9.
a represents an integer of 1 to 50, b to c each independently represents an integer of 0 to 50, and a + b + c = 50 is satisfied.
At least one of R ³ and R ^{8 to} R ⁹ represents a hydrogen atom.
When a plurality of R ⁴ are present, they may be the same or different from each other, and the same applies to R ⁵ , R ^{6a to} R ^6c , R ^{7a to} R ^7c, and R ^{8 to} R ⁹ .

The alkyl group having 1 to 30 carbon atoms and the alkenyl group having 2 to 30 carbon atoms are preferably those having 12 to 20 carbon atoms.
R ⁵ is preferably an alkylene group having 1 to 3 carbon atoms, particularly preferably an alkylene group having 2 to 3 carbon atoms.

（式（Ａ）中、ｘ、ｙおよびｚはそれぞれ独立に１以上の整数を表し、ｘ＋ｙ＋ｚ＝１３を満たす。）
（Ｂ） エチレンジアミン−Ｎ，Ｎ’−ジエタノール、

（Ｃ） エチレンジアミン−Ｎ，Ｎ，Ｎ’，Ｎ’−テトラ−２−プロパノール、

（Ｄ） トリエチレンテトラミン−Ｎ−２−プロパノール、

（Ｅ） キシレンジアミン−Ｎ−２−プロパノール、

（Ｆ） アルキロールアマイド、

（Ｇ） オレイン酸トリエタノールアミンエステル、

（Ｈ） ラウリルアミン−Ｎ，Ｎ−ジエタノール、

（Ｉ） ステアリルアミン−Ｎ，Ｎ−ジエタノール、

（Ｊ） オレイルアミン−Ｎ，Ｎ−ジエタノール、

（Ｋ） ビス（２−ヒドロキシエチル）大豆アミン、

（式（Ｋ）中、Ｒ^１３は炭素数８〜１８の脂肪族炭化水素基を表す。）
（Ｌ） オレイン酸ジアルコールアミド、

（式（Ｌ）中、ｖおよびｗはそれぞれ独立に０〜５の整数を表し、ｖ＋ｗ＝５を満たす。）
（Ｍ） ステアリルアミノプロピルアミノエタノール、

（Ｎ） １，３−プロピレンジアミン−Ｎ−Ｃ_{１２−１８}−アルキル−Ｎ’−エタノール。

（式（Ｎ）中、Ｒ^１４は炭素数１２〜１８の脂肪族炭化水素基を表す。） The nitrogen-containing alcohol compound according to the present invention may be a compound represented by the following formulas (A) to (N), and these are exemplified as particularly preferred compounds:
(A) N-stearyl-N, N ′, N′-tris (polyoxyethylene) -1,3-diaminopropane,

(In the formula (A), x, y and z each independently represent an integer of 1 or more and satisfy x + y + z = 13.)
(B) ethylenediamine-N, N′-diethanol,

(C) ethylenediamine-N, N, N ′, N′-tetra-2-propanol,

(D) triethylenetetramine-N-2-propanol,

(E) xylenediamine-N-2-propanol,

(F) alkylol amide,

(G) oleic acid triethanolamine ester,

(H) Laurylamine-N, N-diethanol,

(I) stearylamine-N, N-diethanol,

(J) oleylamine-N, N-diethanol,

(K) bis (2-hydroxyethyl) soyamine,

(In the formula (K), R ¹³ represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms.)
(L) oleic acid dialcoholamide,

(In formula (L), v and w each independently represent an integer of 0 to 5 and satisfy v + w = 5.)
(M) stearylaminopropylaminoethanol,

(N) 1,3-propylenediamine-N—C _12-18 -alkyl-N′-ethanol.

(In the formula (N), R ¹⁴ represents an aliphatic hydrocarbon group having 12 to 18 carbon atoms.)

  These compounds may be used alone or in combination of two or more.

  The nitrogen-containing alcohol compound according to the present invention may be a product obtained by reacting an amine or amide with an alkylene oxide.

The amine is at least one selected from the group consisting of ammonia, _C1-20 primary amine, _C1-20 secondary amine, polyalkylene polyamine, aromatic amine, heterocyclic amine, urea and glycine. Can be mentioned.
As _C1-20 primary amines, methylamine, ethylamine, propylamine, isopropylamine, allylamine, butylamine, isobutylamine, pentylamine, hexylamine, 2-ethylhexylamine, laurylamine, stearylamine, oleylamine, soybean amine Examples thereof include, but are not limited to, primary amines having a C1-C20 aliphatic hydrocarbon group.
As _C1-20 secondary amines, dimethylamine, diethylamine, dipropylamine, diisopropylamine, diallylamine, dibutylamine, diisobutylamine, dipentylamine, dihexylamine, bis (2-ethylhexyl) amine, dioleylamine, distearyl Although primary amine which has C1-C20 aliphatic hydrocarbon groups, such as an amine and dilauryl amine, is mentioned, it is not limited to these.
Examples of the polyalkylene polyamine include, but are not limited to, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, stearyl-1,3-propanediamine, metaxylenediamine, and propylenediamine.
Aromatic amines include aniline, N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline, toluidine, anisidine, benzidine, catecholamine, benzylamine, α-methylbenzylamine, phenethylamine, xylenediamine, diphenylamine However, it is not limited to these.
Heterocyclic amines include, but are not limited to, morpholine, N-methylmorpholine, pyridine, piperazine, piperidine, pyrrolidine, pyrrole, pyrazole, imidazoline, imidazole and the like.

Examples of the amide include at least one selected from the group consisting of a carboxylic acid amide, a carboxylic acid C _2-20 primary amide, a carboxylic acid C _2-20 secondary amide, and lactams.
Examples of the carboxylic acid amide include compounds represented by C _1-20 CONH ₂ (C _1-20 represents an aliphatic hydrocarbon group having 1 _{to 20} carbon atoms) such as acetamide, but are not limited thereto. .
The carboxylic acid _{C 2 to 20} primary _{amides, C 1~20 CONHC} 2~20 _{(C 1~20} represents an aliphatic hydrocarbon group having 1 to 20 carbon _{atoms, C 2 to 20} is from 1 to 20 carbon atoms Represents an aliphatic hydrocarbon group), but is not limited thereto.
The carboxylic acid _{C 2 to 20} primary _{amides, C 1~20 CON (C 2~20)} 2 (C 1~20 represents an aliphatic hydrocarbon group having 1 to 20 carbon _{atoms, C 2 to 20} carbon number 1 to 20 aliphatic hydrocarbon groups, and the two C _2-20 may be the same or different from each other), but are not limited thereto.
Examples of the lactam include, but are not limited to, α-lactam, β-lactam, γ-lactam, and δ-lactam.

  Examples of the alkylene oxide include at least one selected from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, and 2,3-butylene oxide. Of these, ethylene oxide and propylene oxide are preferable.

  The reaction temperature between the amine or amide and the alkylene oxide depends on the type of substrate, the presence or absence of a catalyst, etc., but may be 0 to 200 ° C, preferably 120 to 180 ° C, particularly preferably 150 to 180 ° C. . If it is less than 0 ° C, the reaction is very slow and unproductive, and if it exceeds 200 ° C, the product tends to be colored yellow, which is not preferable.

  In this reaction, a catalyst may be used. The catalyst may be a basic one, preferably an inorganic base, and particularly preferably a metal hydroxide, specifically sodium hydroxide or potassium hydroxide. The amount of the catalyst used is preferably 0.01 to 5% by mass, more preferably 0.1 to 1% by mass, based on the amine. If it is less than this, the catalytic effect is substantially small, and if it is more than this, the material may be wasted. After the reaction, neutralization may be performed using an acid such as acetic acid, or it may be used as it is for the solvent composition of the present invention.

  In this reaction, a solvent is not particularly required, but can be used as desired. In this case, aromatic hydrocarbon solvents such as benzene, toluene and xylene are preferred. A solvent having a hydroxyl group, an amino group or the like is not preferable because it may react as a substrate. Similarly, water is not preferable, and it is preferable to remove water that can be contained in the solvent by performing a dehydration treatment or the like.

  The material of the reactor is not particularly limited as long as it can withstand this reaction. Stainless steel is preferred. Moreover, the reactor may be equipped with a blowing tube, a stirrer, a cooler, and the like. The reactor is preferably a stainless steel autoclave equipped with a blowing tube, a stirrer and a cooler. In order to prevent the side reaction from proceeding and the raw materials and products from being oxidized and colored, it is preferable that the inside of the reactor is sufficiently replaced with an inert gas such as nitrogen or argon in advance.

  The reaction pressure is not particularly limited, but is preferably from normal pressure to 0.3 MPa, particularly preferably from 0.15 to 0.2 MPa. If the pressure suddenly increases due to reaction heat or abnormal side reactions, the safety valve should be degassed and operated safely.

  Since this reaction is an exothermic reaction, it is preferable to charge amine or amide or a catalyst first and blow alkylene oxide while observing the reaction state. The blowing speed is not particularly limited. However, if the blowing speed is too high, the reaction temperature is remarkably increased and the product may be colored, which is not preferable. Needless to say, if the blowing speed is too slow, the productivity deteriorates. Usually, it is preferable to adjust the rate so that the reaction temperature falls within a preferred range. After completion of the preparation of the alkylene oxide, aging may be performed by continuing the stirring while maintaining the temperature as desired.

  In this reaction, the charging ratio of amine or amide and alkylene oxide is not particularly limited. The alkylene oxide is preferably 1 to 50 mol, particularly preferably 1 to 30 mol, based on 1 mol of the total amount of amine and amide.

  The product after completion of the reaction may be subjected to operations such as distillation, sublimation, washing, etc. to purify the nitrogen-containing alcohol compound according to the present invention, but it should be used as it is for the solvent composition of the present invention without purification. You can also. Moreover, the alkylene oxide which may be contained in the product after completion | finish of reaction may be removed from a product, and you may use for the solvent composition of this invention as it is. As will be described later, since alkylene oxide can be used as an acid acceptor, an antioxidant, etc., when it is desired to add alkylene oxide to the solvent composition of the present invention, an excess amount of alkylene oxide is contained in the above reaction. You may charge.

  The solvent composition of the present invention can be used, for example, as a cleaning agent for removing flux, processing oil, dust, etc. adhering to an article in a washing process of the article in a washing machine opened to the air. It is a stable solvent composition in which each component contained in the solvent composition is difficult to decompose. Even if the solvent composition of the present invention contains water, the stability of each component contained in the solvent composition is unlikely to decrease, and can be suitably used for cleaning articles.

(Other ingredients)
The solvent composition of the present invention may further contain an acid acceptor, an antioxidant and the like. Examples of the acid acceptor and antioxidant include nitro compounds, epoxy compounds, phenols, imidazoles, hydroxyl group-free amines, hydrocarbons, and the like. Examples of the nitro compound include aliphatic and / or aromatic derivatives. Examples of the aliphatic nitro compound include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane and the like. As aromatic nitro compounds, for example, nitrobenzene, o-, m- or p-dinitrobenzene, trinitrobenzene, o-, m- or p-nitrotoluene, o-, m- or p-ethylnitrobenzene, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylnitrobenzene, o-, m- or p-nitroacetophenone, o-, m- or p-nitrophenol, o -, M- or p-nitroanisole and the like can be mentioned.

  Examples of the epoxy compound include ethylene oxide, 1,2-butylene oxide, propylene oxide, styrene oxide, cyclohexene oxide, glycidol, epichlorohydrin, glycidyl methacrylate, phenyl glycidyl ether, allyl glycidyl ether, methyl glycidyl ether, butyl glycidyl ether, Monoepoxy compounds such as 2-ethylhexyl glycidyl ether, diepoxybutane, vinylcyclohexene dioxide, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane tolglycidyl ether, etc. Compounds and the like. It is also possible to add the unreacted epoxy compound during the production of the nitrogen-containing alcohol without separating it.

  Examples of the phenols include phenols containing various substituents such as alkyl groups, alkenyl groups, alkoxy groups, carboxyl groups, carbonyl groups, and halogens in addition to the hydroxyl groups. For example, 2,6-di-t-butyl-p-cresol, o-cresol, m-cresol, p-cresol, thymol, pt-butylphenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol , Eugenol, isoeugenol, butylhydroxyanisole, monovalent phenols such as phenol and xylenol, or divalent tert-butylcatechol, 2,5-di-t-aminohydroquinone, 2,5-di-t-butylhydroquinone, etc. Phenol and the like.

  Examples of the imidazoles include 1-methylimidazole having an alkyl group, a cycloalkyl group, or an aryl group having a straight chain having 1 to 18 carbon atoms or a branched chain having 3 to 18 carbon atoms as an N-position substituent, 1-n-butylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1- (β-oxyethyl) imidazole, 1-methyl-2-propylimidazole, 1-methyl-2-isobutylimidazole, 1-n-butyl- 2-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethylimidazole, 1,5-dimethylimidazole, 1,2,5-trimethylimidazole, 1,4,5-trimethylimidazole, 1-ethyl-2- And methyl imidazole. These compounds may be used alone, or two or more compounds may be used in combination.

  Examples of amines containing no hydroxyl group include pentylamine, hexylamine, diisopropylamine, diisobutylamine, di-n-propylamine, diallylamine, triethylamine, N-methylaniline, pyridine, morpholine, N-methylmorpholine, triallylamine, Allylamine, α-methylbenzylamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, propylamine, isopropylamine, dipropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, diventylamine, triventylamine, 2 -Ethylhexylamine, aniline, N, N-dimethylaniline, N, N-diethylaniline, ethylenediamine, propylenediamine, diethylene Riamin, tetraethylenepentamine, benzylamine, dibenzylamine, diphenylamine, and the like. These may be used alone, or two or more compounds may be used in combination.

  Examples of the hydrocarbons include α-methylstyrene, p-isopropenyltoluene, isoprenes, propadiene, terpenes and the like.

  Although content, such as an acid acceptor in a solvent composition of this invention, antioxidant, is not specifically limited, It is 0. with respect to the total amount of Z-1-chloro-3,3,3-trifluoropropene and a stabilizer. The range of 01-20 mass% is preferable.

  In order to improve the performance of the solvent composition, the solvent composition of the present invention may further contain a surfactant. Examples of the surfactant include sorbitan aliphatic esters such as sorbitan monooleate and sorbitan trioleate; polyoxyethylene sorbite fatty acid esters such as sorbit tetraoleate of polyoxyethylene; polyethylene such as polyoxyethylene monolaurate Glycol fatty acid esters; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene alkylamine fatty acid amides such as polyoxyethylene oleic acid amide Nonionic surfactants such as the like. These surfactants may be used alone or in combination of two or more.

  In order to improve the performance of the solvent composition, in addition to the nonionic surfactant, a cationic surfactant and / or an anionic surfactant may be contained in the solvent composition of the present invention.

  The content of the surfactant in the solvent composition of the present invention is not particularly limited, but is 0.01 to 20% by mass with respect to the total amount of Z-1-chloro-3,3,3-trifluoropropene and the stabilizer. The range of is preferable.

The solvent composition of the present invention may further contain water. When water is contained, it is effective for removing water-soluble soils in the use for washing articles and the use for dry cleaning of clothes, which will be described later. Of course, this does not prevent water from being included in the solvent composition of the present invention for other uses and purposes.
The water content is not particularly limited. The lower limit is not particularly limited with respect to the total amount of Z-1-chloro-3,3,3-trifluoropropene and the stabilizing agent, and may be more than 0 ppm (mass ratio). Is more preferably 500 ppm or more. The upper limit is not particularly limited, and is preferably 1% by mass or less because animal fiber felting during clothing washing is suppressed. This does not prevent the inclusion of more than 1% by weight of water.

(How to clean articles)
The method for cleaning an article (object to be cleaned) using the solvent composition of the present invention is not particularly limited in terms of conditions other than using the solvent composition of the present invention. For example, hand-wiping cleaning, spray cleaning, immersion cleaning, rocking cleaning, ultrasonic cleaning, steam cleaning, and a combination thereof may be employed. These methods may be performed while heating. Further, another cleaning method may be adopted after the cleaning by any of the cleaning methods, and the order is not particularly limited. There are no particular limitations on the cleaning device, cleaning conditions, and the like, and they can be selected as appropriate. The solvent composition of the present invention can be used repeatedly over a long period of time without substantially lowering the pH.

  Cleaning applications using the solvent composition of the present invention include flux, processing oil, wax, mold release, etc., attached to various articles (objects to be cleaned) such as ICs, electronic parts, precision machine parts, optical parts, and aircraft parts. Examples include cleaning and removal of agents, dust, dust, and shavings. Further, the solvent composition of the present invention can be applied to cleaning articles (objects to be cleaned) of various materials such as metals, resins, glasses, ceramics, elastomers, rubbers, fibers, plated products, and composite materials thereof. Furthermore, the solvent composition of the present invention can be used for washing for removing stains on various clothes from fabrics made of natural fibers or synthetic fibers.

(Dry cleaning method for clothing)
The solvent composition of the present invention is a garment woven with natural fibers exemplified by wool, silk, cotton, hemp, etc., and chemical fibers such as rayon, acetate, nylon, acrylic, polyester (backs, shirts, sweaters, jackets) Skirts, trousers, jumpers, gloves, mufflers, stalls, etc.) are excellent for removing dirt and stains, and therefore suitable for dry cleaning of clothing.
As shown also in the below-mentioned Example, the washing | cleaning test of the wet artificial contamination cloth (5 cm x 5 cm) by the Laundry Science Association was used for the washing | cleaning test of JIS L 0860 (dye | dye with respect to dry cleaning) using the solvent composition of this invention. When using the solvent composition of the present invention, the whiteness (L ^* value (white: 100, black: 0) measured with a diffraction grating double monochromator) is Z -1-Chloro-3,3,3-trifluoropropene is improved over the case where it is used alone. Although Z-1-chloro-3,3,3-trifluoropropene alone has good detergency, the solvent composition of the present invention has further excellent detergency. Moreover, since whiteness can be further improved by mix | blending a nonionic surfactant, a solubilizer, and water with the solvent composition of this invention, it is preferable to mix | blend these.

The solvent composition of the present invention has not only the basic performance required for a dry cleaning detergent (solvent) for clothes such as the removal of dirt and stains described above, but also the texture of the clothes after dry cleaning is good. It also has an excellent feature.
This texture is often evaluated quantitatively in addition to subjective evaluations such as appearance and feel by those skilled in the art. In particular, the evaluation result of the pure bending test in the KES system is emphasized. Using the KES system, the bending back property (2HB / B) is derived by measuring the bending hardness (B) and the recovery property (2HB) of the test cloth (Saito, Tsutsumi, Harada; Japan Textile Products Consumer Science Journal) 30: 7 pp.289-292 (1989)). Those skilled in the art determine that the “set property” is better as the bend return property (2HB / B) is larger. Good setability means that the clothes (clothing) after cleaning are finished as if they were new without being out of shape. If the value of the bending back property (2HB / B) changes by 5% or more, those skilled in the art can feel a clear change in the texture. Therefore, the test result of the test cloth prepared by adhering the nitrogen-containing alcohol compound according to the present invention to an untreated raw cloth was compared with the test result of the untreated raw cloth, and 2HB / B (bending back property) It is preferable to use a nitrogen-containing alcohol compound according to the present invention that increases by 5% or more, and more preferably a detergent (solvent) that increases by 10% or more. Further, since the nitrogen-containing alcohol compound according to the present invention having a large increase rate can be said to have a high effect per unit amount, the bendability desired by those skilled in the art can be reduced by reducing the amount of the nitrogen-containing alcohol compound according to the present invention. Can also be given. Here, when the bending hardness (B) fluctuates significantly, the original texture of the dough changes, so that the nitrogen-containing alcohol compound according to the present invention has a large bending hardness fluctuation and a high recovery (2HB). Is preferred.
In addition, since fabrics generally have different properties depending on the warp direction (longitudinal direction) and the weft direction (lateral direction), the change in bending hardness (B) is small and the recoverability (2HB) is large in both directions. It is particularly preferable to use a detergent (solvent).
In the pure bending test in the KES system, the solvent composition of the present invention is used as a detergent (solvent), the base fabric is immersed in the solvent composition of the present invention, and the nitrogen-containing alcohol compound according to the present invention is the base fabric. A test cloth is prepared by squeezing to adhere 0.2% by mass with respect to the mass and drying. When a pure bending test is performed on this test cloth, the bending hardness (B) hardly changes and the effect of significantly increasing the recoverability (2HB) can be obtained. In particular, it is judged that the setability is clearly improved because the bending back property increases by 5% or more with respect to the raw fabric. Good results are also obtained in sensory tests by those skilled in the art. This is also shown in the examples described later.
From the above, the solvent composition of the present invention is suitable for use in dry cleaning of clothes (clothing).

(Method to prevent clothes from charging)
The method for preventing the garment from being charged using the solvent composition of the present invention is to use the solvent composition of the present invention, and other conditions are not particularly limited. In general, it is preferable that the surface electrical resistance of the cloth is reduced after the clothing is cleaned. As the surface electrical resistance is smaller, electrostatic charging is prevented, and various adverse effects (discharge shock, clothing clinging, dust adhesion) due to electrostatic charging are suppressed. Those whose surface electrical resistance decreases after the treatment are preferable as compared with the raw fabric. When the test cloth similar to the above is prepared using the solvent composition of the present invention and the surface electric resistance is measured, the surface electric resistance is lower than the measurement result of the raw cloth, which indicates that it is difficult to be charged. This is also shown in the examples described later. Thus, the use of the solvent composition of the present invention can prevent clothing from being charged.

(Method for stabilizing Z-1-chloro-3,3,3-trifluoropropene)
The method for stabilizing Z-1-chloro-3,3,3-trifluoropropene of the present invention is to use the solvent composition of the present invention, and other conditions are not particularly limited. As described above, under air conditions, when Z-1-chloro-3,3,3-trifluoropropene is heated in the presence of water, an acid content may be generated and the pH may be lowered. By using the nitrogen-containing alcohol compound according to the present invention as the agent, the pH drop of Z-1-chloro-3,3,3-trifluoropropene is suppressed.

[Preparation Example]
Stabilizers A to N were prepared as shown below.

（式（Ａ）中、ｘ、ｙおよびｚはそれぞれ独立に１以上の整数を表し、ｘ＋ｙ＋ｚ＝１３を満たす。） (Stabilizer A)
424 g of N-stearyl-1,3-propanediamine (product name: Lipomin DAHT flake, manufactured by Lion Corporation, molecular weight: 326) was charged into a 2 L stirring and addition pressure reaction kettle, and 2.0 g of potassium hydroxide was added as a catalyst. After replacing the air in the reaction vessel with nitrogen, it was sealed, and while maintaining the temperature in the reaction vessel at 170 to 180 ° C., 744 g of ethylene oxide was gradually injected over 2 hours to cause a reaction. The compound represented was obtained. After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer A” without separation and purification.

(In the formula (A), x, y and z each independently represent an integer of 1 or more and satisfy x + y + z = 13.)

(Stabilizer B)
500 g of ethylenediamine (molecular weight: 60) was placed in a 2 L stirring and addition pressure reaction kettle, the air in the reaction vessel was replaced with nitrogen, and then sealed, and 733 g of ethylene oxide was added while maintaining the reaction vessel temperature at 60 to 80 ° C. The reaction was carried out over 2 hours to obtain a compound represented by the formula (B). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer B” without separation and purification.

(Stabilizer C)
240 g of ethylenediamine (molecular weight: 60) was placed in a 2 L stirred addition pressure reaction kettle, the air in the reaction vessel was replaced with nitrogen, and then sealed, and 928 g of propylene oxide was maintained while maintaining the reaction vessel temperature at 60-80 ° C. Was allowed to react for 4 hours to obtain a compound represented by the formula (C). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer C” without separation and purification.

(Stabilizer D)
730 g of triethylenetetramine (molecular weight: 146) was placed in a 2 L stirring and addition pressure reaction vessel, the air in the reaction vessel was replaced with nitrogen, and then sealed, while maintaining the temperature in the reaction vessel at 60 to 80 ° C., propylene oxide 290 g was injected over 1 hour and reacted to obtain a compound represented by the formula (D). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer D” without separation and purification.

(Stabilizer E)
After adding 680 g of meta-xylenediamine (molecular weight: 136) to a 2 L stirred pressure reactor, 4 g of sodium hydroxide was added as a catalyst, and the air in the reaction vessel was replaced with nitrogen, then sealed and sealed in the reaction vessel. While maintaining the temperature at 170 to 180 ° C., 290 g of propylene oxide was injected and reacted for 1 hour to obtain a compound represented by the formula (E). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer E” without separation and purification.

(Stabilizer F)
Lauric acid (molecular weight: 200) 400 g and diethanolamine (molecular weight: 105) 420 g are put into a 2 L dehydration kettle with a stirrer, and dehydration reaction is performed at 170 ° C. for 3 hours under a nitrogen stream. The compound obtained was obtained. After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer F” without separation and purification.

(Stabilizer G)
423 g of oleic acid (molecular weight: 283) and 224 g of triethanolamine (molecular weight: 149) are placed in a 2 liter dehydration kettle with a stirrer, heated in a nitrogen stream and dehydrated at a temperature of 170 ° C. for 2 hours. A compound represented by (G) was obtained. After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer G” without separation and purification.

(Stabilizer H)
After adding 724 g of laurylamine (product name: Lipomin 12D, manufactured by Lion Co., Ltd., molecular weight: 185) to a 2 L stirring addition pressure reaction kettle, the air in the reaction vessel was replaced with nitrogen, sealed and heated, and then reacted. While maintaining the internal temperature at 160 to 170 ° C., 345 g of ethylene oxide was injected, and the mixture was allowed to react at a temperature of 160 to 170 ° C. for 2 hours while cooling to obtain a compound represented by the formula (H). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer H” without separation and purification.

(Stabilizer I)
807 g of stearylamine (product name: Lipomin 18D, manufactured by Lion Corporation, molecular weight: 270) is placed in a 2 L stirring and addition pressure reaction kettle, the air in the reaction vessel is replaced with nitrogen, and after sealing, the mixture is heated and heated. While maintaining the temperature at 160 to 170 ° C., 264 g of ethylene oxide was injected and reacted for 2 hours to obtain a compound represented by the formula (I). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer I” without separation and purification.

(Stabilizer J)
801 g of oleylamine (product name: Lipomin O, manufactured by Lion Corporation, molecular weight: 268) is placed in a 2 L stirring addition pressure reaction kettle, the air in the reaction vessel is replaced with nitrogen, and after sealing, heated, the temperature in the reaction vessel Was maintained at 160 to 170 ° C., and 264 g of ethylene oxide was injected over 2 hours for reaction to obtain a compound represented by the formula (J). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer J” without separation and purification.

(Stabilizer K)
Put 828 g of soybean amine (Product name: Nissan Amine SB, NOF Corporation, molecular weight: about 270) in a 2 L autoclave with a stirrer, replace the air in the autoclave with nitrogen, heat it after sealing, and heat in the reaction vessel While maintaining the temperature at 160 to 170 ° C., 352 g of ethylene oxide was injected and reacted for 2 hours to obtain bis (2-hydroxyethyl) soyamine. After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer K” without separation and purification.

（式（Ｌ）中、ｖおよびｗはそれぞれ独立に０〜５の整数を表し、ｖ＋ｗ＝５を満たす。） (Stabilizer L)
In a 2 L autoclave with a stirrer, 562 g of oleic acid amide (product name: Armoslip HT powder, manufactured by Lion Corporation, molecular weight: 281) and 2.3 g of sodium hydroxide as a catalyst were placed, and the air in the autoclave was filled with nitrogen. Substitution, sealing and heating were performed, and while maintaining the temperature in the reaction vessel at 160 to 170 ° C., 440 g of ethylene oxide was injected and reacted for 2 hours to obtain a compound represented by the formula (L). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer L” without separation and purification.

(In formula (L), v and w each independently represent an integer of 0 to 5 and satisfy v + w = 5.)

(Stabilizer M)
978 g of N-stearyl-1,3-propanediamine (product name: Lipomin DAHT Flakes, manufactured by Lion Corporation, molecular weight: 326) is placed in a 2 L autoclave with a stirrer, and the air in the autoclave is replaced with nitrogen, and after sealing While heating and maintaining the temperature in the reaction vessel at 160 to 170 ° C., 132 g of ethylene oxide was injected and reacted for 2 hours to obtain a compound represented by the formula (M). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer M” without separation and purification.

（式（Ｎ）中、Ｒ^１４は炭素数１２〜１８のアルキル基を表す。） (Stabilizer N)
887 g of N—C _12-18 -alkyl-1,3-propanediamine (product name: Lipomin DAT, manufactured by Lion Corporation, molecular weight: about 275) is placed in a 2 L stirred autoclave, and the air in the autoclave is filled with nitrogen. Substitution, sealing and heating were performed, and while maintaining the temperature in the reaction vessel at 160 to 170 ° C., 359 g of ethylene oxide was injected over 2 hours to cause reaction, thereby obtaining a compound represented by the formula (N). After completion of the reaction, the reaction product was cooled to room temperature and designated as “Stabilizer N” without separation and purification.

(In the formula (N), R ¹⁴ represents an alkyl group having 12 to 18 carbon atoms.)

(Thermal stability test)
[Example 1]
In a 50 mL capacity stainless steel container, Z-1-chloro-3,3,3-trifluoropropene (30 g), ultrapure water (1 g), stabilizer A (Z-1-chloro-3,3,3-tri 1.0 vol%) with respect to the mixture of fluoropropene and ultrapure water. When preparing the sample, the sample and the air were in contact with each other during the test without removing the air in the stainless steel container. The stainless steel container into which the sample was introduced was left in a constant temperature air bath at 120 ° C. and heated for 48 hours. After heating, the stainless steel container was cooled to room temperature, further cooled in an ice water bath, and then opened. Table 1 shows the results obtained by analyzing the organic matter by gas chromatography (FID) and measuring the change in purity, washing the organic matter with 30 mL of ultrapure water, and measuring the pH of the aqueous phase with a pH meter.

[Example 2]
Tested in the same manner as in Example 1 except that the amount of stabilizer A added was 0.5 vol% with respect to the mixture of Z-1-chloro-3,3,3-trifluoropropene and ultrapure water. did. The results are shown in Table 1.

[Examples 3 to 8]
The test was conducted in the same manner as in Example 1 or 2 except that the stabilizer C, F or G was used instead of the stabilizer A. However, as shown in Table 1, in Examples 3, 5 and 7, the amount of stabilizer added was 1 with respect to the mixture of Z-1-chloro-3,3,3-trifluoropropene and ultrapure water. On the other hand, in Examples 4, 6 and 8, the addition amount of the stabilizer was 0. 0 with respect to the mixture of Z-1-chloro-3,3,3-trifluoropropene and ultrapure water. It is 5 vol%. The results are shown in Table 1.

[Comparative Example 1]
The test was performed in the same manner as in Example 1 except that Stabilizer A was not added. The results are shown in Table 1.

  As shown in Table 1, in Comparative Example 1 in which water was added in the presence of air, the pH of Z-1-chloro-3,3,3-trifluoropropene was from 5.811 to 4.457 before the test. Declined. On the other hand, in Examples 1 to 8 in which a stabilizer was added, the pH decrease of Z-1-chloro-3,3,3-trifluoropropene was suppressed.

[Reference Example 1]
A metal test piece (manufactured by SUS316) was placed in a stainless steel container (manufactured by SUS316) having a capacity of 100 mL. After removing air remaining in the stainless steel container using a vacuum pump, Z-1-chloro-3,3,3-trifluoropropene (50 g) was introduced into the stainless steel container. In the reference example, unlike Examples 1 to 8 and Comparative Example 1, ultrapure water was not introduced into the stainless steel container. The stainless steel container into which the sample was introduced was immersed in an oil bath, heated to 110 ° C., and held for 3 days. After heating, the stainless steel container was cooled to room temperature, further cooled in an ice water bath, and then opened. Organic substances were mixed with ultrapure water, acidic components were extracted, and acidic components (fluoride ions and chloride ions) were measured using an ion chromatograph. The fluoride ion and chloride ion contained in the Z-1-chloro-3,3,3-trifluoropropene after heating were both 0.1 ppm (mass ratio) or less, and no decomposition was observed.

  The result of Reference Example 1 shows that the stability of Z-1-chloro-3,3,3-trifluoropropene is good under the condition where air and water do not coexist. The test results of Comparative Example 1 and Reference Example 1 indicate that the stability of the solvent composition containing Z-1-chloro-3,3,3-trifluoropropene decreases when it comes into contact with water in the presence of air. ing. The results of Examples 1 to 8 shown in Table 1 indicate that the stability of the solvent composition containing Z-1-chloro-3,3,3-trifluoropropene is significantly improved by adding a stabilizer. It shows that.

(KES-FB2 pure bending test)
[Example 9]
Stabilizer B synthesized in Preparation Example and Z-1-chloro-3,3,3-trifluoropropene were mixed, and the content of stabilizer B was Z-1-chloro-3,3,3-tri A solvent composition that was 0.2% by mass with respect to fluoropropene was prepared. A wool surge cloth (dimensions: 22 cm × 22 cm, mass: 12.5 g) is dipped in the prepared solvent composition, taken out from the solvent composition, and drawn using a roller squeezer 100% (mass 25 g ± 0.00). The pressure was adjusted so as to be 5%). The operation of immersing and squeezing the wool surge into the solvent composition was performed twice in total (2DIP, 2NIP). The wool surge after the operation was air-dried overnight on a metal net. After drying, a test cloth was prepared by cutting a wool surge cloth left in a constant temperature and humidity room (temperature: 20 ° C., humidity: 65%) for 24 hours to 20 cm × 20 cm.

  Using the test cloth, a KES-FB2 pure bending test was performed in the constant temperature and humidity chamber. Using a KES-FB system (texture measuring system) manufactured by Kato Tech Co., Ltd. as a testing machine, the test cloth B (bending hardness), 2HB (recovery) in both the longitudinal (warp) and transverse (weft) directions of the test cloth Property) was measured, and 2HB / B (bending return property) was calculated from the measured value.

[Examples 10 to 17, Comparative Example 2]
The test was performed in the same manner as in Example 9 except that the stabilizer B was replaced with the stabilizers C, D, E, F, H, I, L, and M. Further, a test was carried out in the same manner as in Example 9 using Z-1-chloro-3,3,3-trifluoropropene to which no stabilizer was added, and Comparative Example 2 was obtained.

  The test results of Examples 9 to 17 and Comparative Example 2 are shown in Table 2 (vertical direction) and Table 3 (horizontal direction). In Tables 2 and 3, the numerical values of Comparative Examples 2 to which no stabilizer was added were used as reference values, and the numerical values of Examples 9 to 17 to which the stabilizer was added were shown as relative values.

  As shown in Tables 2 and 3, the wool surge bend-returning property was improved under the conditions in which any of the stabilizers of Examples 9 to 17 was added. This result has shown that the setting property of the wool surge was improved by adding a stabilizer.

(KES-FB4 surface test)
[Examples 18 to 26, Comparative Example 3]

  Test cloths of Examples 18 to 26 and Comparative Example 3 were prepared in the same manner as in Examples 9 to 17 and Comparative Example 2.

  Using a KES-FB system (texture measurement system) manufactured by Kato Tech Co., Ltd., MIU (average friction coefficient), MMD (fluctuation average of friction coefficient) and SMD (surface roughness) were measured as the surface properties of the test cloth. .

  The test results are shown in Table 4 (vertical direction) and Table 5 (horizontal direction). In Tables 4 and 5, the numerical values of Comparative Examples 3 to which no stabilizer was added were used as reference values, and the numerical values of Examples 18 to 26 to which stabilizers were added were shown as relative values.

  As shown in Tables 4 and 5, the friction coefficient was equal to or higher than that of the stabilizer-free condition in any of the conditions in which the stabilizers of Examples 18 to 26 were added.

(Measurement of surface electrical resistance)
[Examples 27 to 35, Comparative Example 4]
Test cloths of Examples 27 to 35 and Comparative Example 4 were prepared in the same manner as in Examples 9 to 17 and Comparative Example 2.

  Using a surface resistance measuring device (Kanebo friction band voltage measuring device EST-8), the surface electrical resistance (Ω) of the test cloth when the applied voltage was 1000 V was measured. The results are shown in Table 6. In Table 6, the numerical values of Comparative Examples 4 to which no stabilizer was added were used as reference values, and the numerical values of Examples 27 to 35 to which the stabilizer was added were shown as relative values.

  As shown in Table 6, the surface electrical resistance decreased in any condition where any stabilizer of Examples 27 to 35 was added as compared to the condition where no stabilizer was added. Stabilizers F, H and L significantly reduced the surface electrical resistance. This result shows that by adding a stabilizer, the electrical resistance of the wool surge surface is remarkably lowered and the antistatic performance is greatly improved.

  In Examples 9 to 35, the textures of the test cloths prepared under the conditions where any stabilizer was added were evaluated visually and to the touch, and all were good results.

(Cloth dry cleaning test)
[Examples 36 to 39, Reference Example 2]
In Examples 36 to 39 and Reference Example 2, the cleaning performance of the solvent composition was evaluated based on JIS L 0860 (Dye Fastness Test Method for Dry Cleaning). A wet artificially contaminated cloth (manufactured by Laundry Science Association, L ^* value: 62.136) was immersed in the solvent composition and washed for 30 minutes in the presence of a stainless steel ball at 20 ° C. The washed cloth was dried, and L ^* values (whiteness; 0 (black) to 100 (white)) were determined using a diffraction grating double monochromator (manufactured by Hitachi, Ltd., model number: C-2000S). Here, as the solvent composition, a mixture prepared by mixing Z-1-chloro-3,3,3-trifluoropropene (200 mL) and a stabilizer (5 g) was used as the stabilizer. In Example 36, Stabilizer C was used, in Example 37 Stabilizer H was used, in Example 38 Stabilizer I was used, and in Example 39 Stabilizer L was used. In Reference Example 2, only Z-1-chloro-3,3,3-trifluoropropene was used as the solvent composition. These results are shown in Table 7.

[Examples 40 to 43, Reference Example 3]
As solvent composition, Z-1-chloro-3,3,3-trifluoropropene (200 mL), stabilizer (5 g), water (0.2 mL), solubilizer (propylene glycol monomethyl, 2.5 g) The cleaning performance was evaluated in the same manner as in Examples 36 to 39 and Reference Example 1 except that a nonionic surfactant (polyoxyethylene tridecyl ether, 2.5 g) was used. Here, as the stabilizer, stabilizer C is used in Example 40, stabilizer H is used in Example 41, stabilizer I is used in Example 42, and stabilizer L is used in Example 43. It was. Reference Example 3 was prepared by mixing the above-described Z-1-chloro-3,3,3-trifluoropropene, water, a solubilizer and a nonionic surfactant without using a stabilizer. Was used as a solvent composition. The results are shown in Table 8.

As shown in Table 7 and Table 8, even when Z-1-chloro-3,3,3-trifluoropropene of Reference Example 2 was used alone, an improvement in L ^* value was confirmed. It was confirmed that in any of the solvent compositions of Examples 36 to 43 blended with L, the L ^* value was improved as compared with the case of Reference Example 2.

Claims (13)

A solvent composition comprising at least Z-1-chloro-3,3,3-trifluoropropene and a stabilizer,
The stabilizing agent is an amide compound having a human Dorokishiru group, solvent composition. A solvent composition comprising at least Z-1-chloro-3,3,3-trifluoropropene and a stabilizer,
The stabilizing agent is a compound represented by the compound represented by the following general formula [1] or the following general formula [2], Solvent composition.

(In the general formula [1], R ¹ , R ² and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O). _b R ^{8 represents} (CR ^6c ₂ CR ^7c ₂ O) _c R ⁹ or (CR ^6d ₂ CR ^7d ₂ O) _d R ^10. R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or 2 carbon atoms. Represents an alkenyl group having ˜30 or COR ^11. R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring. ^{6a to} R ^6d and R ^{7a to} R ^7d each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, and R ^{8 to} R ¹⁰ each independently represent a hydrogen atom or carbon. Number 1-30 Alky Represents a group or an alkenyl group having 2 to 30 carbon atoms ^{.R 11} is .a is 1 represents an integer of .n is 0-9 for an alkenyl group of alkyl or C2-30 C1-30 Represents an integer of 50, and b to d each independently represents an integer of 0 to 50, and satisfy a + b + c + d = 50, at least one of R ³ and R ^{8 to} R ¹⁰ represents a hydrogen atom, and R ⁴ represents a plurality. when present, may be the same or different types from each other ^is the same for ^{R 5, R 6a ~R 6d,} R 7a ~R 7d and ^R 8 ^{to R 10.}
In general formula [2], R ² and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O) _b R ⁸ or It represents a _{^{(CR 6c 2 CR 7c 2 O}} ) c R 9. R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or COR ¹¹ . R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring. R ^{6a to} R ^6c and R ^{7a to} R ^7c each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. R ^{8 to} R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms. n represents an integer of 0 to 9. a represents an integer of 1 to 50, b to c each independently represents an integer of 0 to 50, and a + b + c = 50 is satisfied. At least one of R ³ and R ^{8 to} R ⁹ represents a hydrogen atom. When a plurality of R ⁴ are present, they may be the same or different from each other, and the same applies to R ⁵ , R ^{6a to} R ^6c , R ^{7a to} R ^7c, and R ^{8 to} R ⁹ . ) A solvent composition comprising at least Z-1-chloro-3,3,3-trifluoropropene and a stabilizer,
The stabilizing agent is at least one selected from compounds represented by the following formula (A) ~ (N), solvent composition.

(In the formula (A), x, y and z each independently represent an integer of 1 or more and satisfy x + y + z = 13.
In the formula (K), R ¹³ represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms.
In the formula (L), v and w each independently represent an integer of 0 to 5 and satisfy v + w = 5.
In the formula (N), R ¹⁴ represents an aliphatic hydrocarbon group having 12 to 18 carbon atoms. ) The solvent composition according to any one of claims 1 to 3 , further comprising 500 ppm to 1% by mass of water based on the total amount of Z-1-chloro-3,3,3-trifluoropropene and the stabilizer. object. The solvent as described in any one of Claims 1-4 whose content of a stabilizer is 0.01-10 mass% with respect to Z-1-chloro-3,3,3-trifluoropropene. Composition. Using a solvent composition according to any one of claim 1 to 5, a method of cleaning articles. A method for dry-cleaning clothing using the solvent composition according to any one of claims 1 to 5 . A method for preventing clothing from being charged, using the solvent composition according to any one of claims 1 to 5 . A method for stabilizing Z-1-chloro-3,3,3-trifluoropropene comprising the steps of:
Blending Z-1-chloro-3,3,3-trifluoropropene and a stabilizer,
The stabilizing agent is an amide compound having a human Dorokishiru group method. A method for stabilizing Z-1-chloro-3,3,3-trifluoropropene comprising the steps of:
Blending Z-1-chloro-3,3,3-trifluoropropene and a stabilizer,
The stabilizing agent is a compound represented by the compound represented by the following general formula [1] or the following general formula [2], Methods.

(In the general formula [1], R ¹ , R ² and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O). _b R ^{8 represents} (CR ^6c ₂ CR ^7c ₂ O) _c R ⁹ or (CR ^6d ₂ CR ^7d ₂ O) _d R ^10. R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or 2 carbon atoms. Represents an alkenyl group having ˜30 or COR ^11. R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring. ^{6a to} R ^6d and R ^{7a to} R ^7d each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms, and R ^{8 to} R ¹⁰ each independently represent a hydrogen atom or carbon. Number 1-30 Alky Represents a group or an alkenyl group having 2 to 30 carbon atoms ^{.R 11} is .a is 1 represents an integer of .n is 0-9 for an alkenyl group of alkyl or C2-30 C1-30 Represents an integer of 50, and b to d each independently represents an integer of 0 to 50, and satisfy a + b + c + d = 50, at least one of R ³ and R ^{8 to} R ¹⁰ represents a hydrogen atom, and R ⁴ represents a plurality. when present, may be the same or different types from each other ^is the same for ^{R 5, R 6a ~R 6d,} R 7a ~R 7d and ^R 8 ^{to R 10.}
In general formula [2], R ² and R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, (CR ^6b ₂ CR ^7b ₂ O) _b R ⁸ or It represents a _{^{(CR 6c 2 CR 7c 2 O}} ) c R 9. R ³ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or COR ¹¹ . R ⁵ represents an alkylene group having 1 to 6 carbon atoms, and some or all of the carbon atoms in the alkylene group may be substituted with an aromatic ring. R ^{6a to} R ^6c and R ^{7a to} R ^7c each independently represent a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. R ^{8 to} R ⁹ each independently represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, or an alkenyl group having 2 to 30 carbon atoms. R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms. n represents an integer of 0 to 9. a represents an integer of 1 to 50, b to c each independently represents an integer of 0 to 50, and a + b + c = 50 is satisfied. At least one of R ³ and R ^{8 to} R ⁹ represents a hydrogen atom. When a plurality of R ⁴ are present, they may be the same or different from each other, and the same applies to R ⁵ , R ^{6a to} R ^6c , R ^{7a to} R ^7c, and R ^{8 to} R ⁹ . ) A method for stabilizing Z-1-chloro-3,3,3-trifluoropropene comprising the steps of:
Blending Z-1-chloro-3,3,3-trifluoropropene and a stabilizer,
The stabilizing agent is at least one selected from compounds represented by the following formula (A) ~ (N), Methods.

(In the formula (A), x, y and z each independently represent an integer of 1 or more and satisfy x + y + z = 13.
In the formula (K), R ¹³ represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms.
In the formula (L), v and w each independently represent an integer of 0 to 5 and satisfy v + w = 5.
In the formula (N), R ¹⁴ represents an aliphatic hydrocarbon group having 12 to 18 carbon atoms. ) The method according to any one of claims 9 to 11 , further comprising 500 ppm to 1% by mass of water based on the total amount of Z-1-chloro-3,3,3-trifluoropropene and a stabilizer. . The method as described in any one of Claims 9-12 whose compounding quantity of a stabilizer is 0.01-10 mass% with respect to Z-1-chloro-3,3,3-trifluoropropene. .