Ester composition

Abstract

This ester composition contains (a) an unsaturated dibasic acid monoester represented by formula (1), (b) an unsaturated dibasic acid diester represented by formula (2), and (c) an aliphatic alcohol having 4 to 24 carbon atoms. The content of the component (a) is 70-99 mass%, the content of the component (b) is 0.5-15 mass%, and the content of the component (c) is 0.5-15 mass% with respect to a total of 100 mass% of the components (a)-(c).　According to the present invention, it is possible to provide an ester composition which has good solubility in a solvent, contributes to the improvement of the dispersion stability of metal particles, and can contribute to the improvement of the water repellency of a coating film obtained using the ester composition. (In the formula (1), R1 represents an alkyl group having 2 to 30 carbon atoms.) (In the formula (2), R2 and R3 each represent an alkyl group having 2 to 30 carbon atoms.)

Description

Ester composition

[0001] This invention relates to ester compositions.

[0002] Unsaturated dibasic acid ester compounds can impart various properties to compositions, such as solubility, plasticity, lubricity, and water repellency. Among these, imparting water repellency is one of the main applications of unsaturated dibasic acid ester compounds. For example, Patent Document 1 shows that applying a composition containing an unsaturated dibasic acid ester to a fiber surface can impart excellent liquid repellency. Furthermore, Patent Document 2 shows that a composition containing an unsaturated dibasic acid ester compound can form a coating film exhibiting excellent liquid repellency and durability.

[0003] On the other hand, conductive pastes obtained by kneading metal particles and binder resins have been widely developed, mainly for electronic information products, and among them, copper pastes using relatively inexpensive copper particles as the conductive component are being investigated in particular. Copper paste exhibits conductivity equivalent to silver paste, which is already mass-produced as an industrial product, but the oxidation of the wiring surface formed by copper paste progresses due to the influence of moisture in the atmosphere, etc., and conductivity may deteriorate significantly. For this reason, Patent Document 3 reports an electronic device characterized by forming a protective layer with excellent water repellency for the purpose of preventing oxidation of the wiring surface made of copper paste. Furthermore, Patent Document 4 reports that water repellency can be imparted to a coating film by incorporating raw materials containing water-repellent groups such as siloxane groups and fluoroalkyl groups into the composition.

[0004] Japanese Patent Publication No. Hei 8-291466, International Publication No. 2022 / 220198, Japanese Patent Publication No. 2020-129493, Japanese Patent Publication No. 2012-224764

[0005] However, while the method described in Patent Document 3 is excellent at imparting water repellency to the wiring surface, it requires the addition of a separate step of applying and drying a protective layer, raising concerns about decreased productivity due to increased man-hours. Furthermore, while the method described in Patent Document 4 can impart water repellency to the coating surface without forming a separate coating layer, when metal particles such as copper particles are present in the composition, their dispersion stability may be insufficient, or their solubility in the solvent contained in the composition may be insufficient. Therefore, the present invention aims to provide an ester composition that has good solubility in the solvent, contributes to improving the dispersion stability of metal particles, and contributes to improving the water repellency of the resulting coating film.

[0006] The inventors diligently conducted research to solve the aforementioned problems. As a result, they found an ester composition that can achieve the above objectives and completed the present invention. The gist of the present invention is as follows: [1] An ester composition containing (a) an unsaturated dibasic acid monoester represented by the following formula (1), (b) an unsaturated dibasic acid diester represented by the following formula (2), and (c) an aliphatic alcohol having 4 to 24 carbon atoms, wherein component (a) is 70 to 99% by mass, component (b) is 0.5 to 15% by mass, and component (c) is 0.5 to 15% by mass, based on a total of 100% by mass of components (a) to (c). (In formula (1), R1 represents an alkyl group having 2 to 30 carbon atoms.) (In formula (2), R ２ , R ３ (wherein represents an alkyl group having 2 to 30 carbon atoms.) [2] A liquid repellent composition comprising the ester composition described in [1] above.

[0007] According to the present invention, it is possible to provide an ester composition that has good solubility in dispersion media, contributes to improving the dispersion stability of metal particles, and contributes to improving the water repellency of the resulting coating film.

[0008] The embodiments of the present invention will be described below, but the present invention is not limited to the embodiments described herein and can be modified in various ways without departing from the spirit of the invention. In this specification, numerical ranges defined using the symbol "~" include the numerical values ​​at both ends (upper and lower limits) of "~". For example, "2~5" means 2 or more and 5 or less.

[0009] [Ester Composition] The composition of the present invention comprises component (a) represented by formula (1) above: an unsaturated dibasic acid monoester, component (b) represented by formula (2) above: an unsaturated dibasic acid diester, and component (c): an aliphatic alcohol. Details of each component are described below.

[0010] <Component (a): Unsaturated dibasic acid monoester> Component (a): Unsaturated dibasic acid monoester contained in the ester composition of the present invention is a compound represented by the following general formula (1). (In formula (1), R １ This indicates an alkyl group having 2 to 30 carbon atoms.

[0011] In formula (1), the unsaturated dibasic acid monoester is composed of an unsaturated dibasic acid and an alcohol (R １ It is a monoester with OH), and examples of the unsaturated dibasic acid include fumaric acid and maleic acid.

[0012] In formula (1), R １ R represents a linear or branched alkyl group having 2 to 30 carbon atoms. Examples of alkyl groups include ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, isooctadecyl group, eicosyl group, and docosyl group. From the viewpoint of improving water repellency and solubility, １ A C6-C24 alkyl group is preferred, a C12-C22 alkyl group is more preferred, and a C16-C18 alkyl group is even more preferred. １ It is preferable that it is a linear alkyl group.

[0013] The unsaturated dibasic acid monoester may be used alone or in combination of two or more kinds. The content of the unsaturated dibasic acid monoester is 70 to 99% by mass, preferably 80 to 98% by mass, more preferably 85 to 95% by mass, based on 100% by mass of the total of components (a) to (c). When the content of the unsaturated dibasic acid monoester is less than 70% by mass, the water repellency of the coating film obtained using the ester composition may decrease. When the content of the unsaturated dibasic acid monoester exceeds 99% by mass, the solubility of the ester composition may decrease. The unsaturated dibasic acid monoester can be produced according to a known method such as an esterification reaction using an unsaturated dibasic acid and a predetermined aliphatic alcohol, and is also available as a commercial product.

[0014] <Component (b): Unsaturated dibasic acid diester> The component (b) contained in the composition of the present invention: the unsaturated dibasic acid diester is a compound represented by the following general formula (2). (In formula (2), R ２ , R ３ represents an alkyl group having 2 to 30 carbon atoms.)

[0015] The unsaturated dibasic acid diester in formula (2) is a diester of an unsaturated dibasic acid and alcohols (R ２ OH and R ３ OH). Examples of the unsaturated dibasic acid include fumaric acid and maleic acid.

[0016] In formula (2), R ２ , R ３ represents a linear or branched alkyl group having 2 to 30 carbon atoms. The alkyl groups of R ２ , R ３ may have the same number of carbon atoms or different numbers of carbon atoms. Examples of the alkyl group include an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, an isooctadecyl group, an eicosyl group, a docosyl group, etc. From the viewpoint of improving water repellency and solubility, R ２ , R ３The alkyl group is preferably a C6-C24 alkyl group, more preferably a C12-C22 alkyl group, and even more preferably a C16-C22 alkyl group.

[0017] Unsaturated dibasic acid diesters may be used alone or in combination of two or more types. The content of unsaturated dibasic acid diesters is 0.5 to 15% by mass, preferably 1 to 10% by mass, and more preferably 1 to 5% by mass, based on 100% by mass of the total of components (a) to (c). If the content of unsaturated dibasic acid diesters is less than 0.5% by mass, the solubility of the ester composition may decrease. Also, if the content of unsaturated dibasic acid diesters exceeds 15% by mass, the water repellency of the coating film obtained using the ester composition may decrease. Unsaturated dibasic acid diesters can be produced by known methods such as esterification reactions using an unsaturated dibasic acid and a predetermined aliphatic alcohol, but they are also available commercially.

[0018] <Component (c): Aliphatic Alcohol> Component (c): Aliphatic alcohol included in the composition of the present invention is an aliphatic alcohol having 4 to 24 carbon atoms. The aliphatic alcohol that can be used in the present invention is preferably a monovalent linear or branched aliphatic alcohol, and examples include butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, nonyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, isooctadecyl alcohol, eicosyl alcohol, and docosyl alcohol. From the viewpoint of improving water repellency and solubility, the aliphatic alcohol preferably has 8 to 24 carbon atoms, more preferably 12 to 22 carbon atoms, and even more preferably 16 to 18 carbon atoms. The aliphatic alcohol may be used alone, or two or more types may be used in combination.

[0019] The aliphatic alcohol content is 0.5 to 15% by mass, preferably 1 to 10% by mass, and more preferably 2 to 10% by mass, based on 100% by mass of the total of components (a) to (c). If the aliphatic alcohol content is less than 0.5% by mass, the solubility of the ester composition may decrease. If it exceeds 15% by mass, the effect of improving the dispersibility of metal particles obtained by adding the ester composition may decrease. Aliphatic alcohols can be produced by known methods such as the hydrogenation reaction of fatty acid esters, but they are also available commercially.

[0020] The ester composition of the present invention may contain other components besides components (a) to (c), but the total amount of components (a) to (c) in the ester composition is preferably 95% by mass or more, more preferably 98% by mass or more, and even more preferably 100% by mass, based on the total amount of the ester composition.

[0021] <Method for Producing Ester Compositions> The method for producing the ester composition of the present invention is not particularly limited and can be produced by any method. For example, it can be prepared by blending predetermined amounts of component (a): unsaturated dibasic acid monoester, component (b): unsaturated dibasic acid diester, and component (c): aliphatic alcohol. Alternatively, it can be produced by adjusting the amount of component (a): unsaturated dibasic acid monoester, component (b): unsaturated dibasic acid diester produced and the amount of component (c): aliphatic alcohol remaining by an esterification reaction using an unsaturated dibasic acid and a predetermined aliphatic alcohol.

[0022] <Uses of the Ester Composition> The ester composition of the present invention can be used as is, for example, by being incorporated into repellents or coatings, but it can also be used after being polymerized using radical polymerization or the like. As an example of the uses of the ester composition of the present invention, it can be incorporated into metal particles, resins, solvents, etc., to form a liquid-repellent composition. The liquid-repellent composition may be in paste form. The liquid-repellent composition is a composition that has one or both of the properties of water repellency and oil repellency.

[0023] A coating film can be formed by heating the above-described liquid-repellent composition. The ester composition has good solubility in the solvent and contributes to the dispersion stability of the metal particles. The formed coating film exhibits good water repellency. The above-described metal particles are not particularly limited, but examples include copper particles, silver particles, gold particles, platinum particles, and nickel particles. The above-described solvent is not particularly limited, but examples include toluene, 2-propanol, diethylene glycol monoethyl ether, and terpineol.

[0024] The liquid-repellent composition can impart liquid repellency to an object to be treated by applying it to the object and drying it as needed. The object to be treated is not particularly limited, but examples include textiles, leather, and paper. Application to the object can be carried out by common methods such as spray coating, bar coating, or dip coating.

[0025] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited in any way to these examples.

[0026] Regarding the structures of the unsaturated dibasic acid monoesters (a1-a4) and unsaturated dibasic acid diesters (b1-b4) used in each example and comparative example, the R of formula (1) １ , and R in equation (2) ２ , R ３ This information is described and shown in Table 1.

[0027] [Example 1] In a 1 L four-necked flask equipped with a thermometer, nitrogen inlet tube, stirrer, and Liebig condenser, 90 g of mono-2-ethylhexyl maleate (a1), 3 g of di-2-ethylhexyl maleate (b1), and 7 g of dodecyl alcohol were mixed, and the mixture was heated in an oil bath until the internal temperature reached 85°C while blowing nitrogen gas at a flow rate of 100 mL / min. After stirring the mixture for 3 hours after the internal temperature of the mixture reached 85°C, it was cooled to 75°C and the mixture was stored in a metal container. After storage, the mixture was cooled to room temperature and solidified, and the resulting pale yellow solid was pulverized into flakes to obtain an ester composition containing predetermined amounts of component (a) unsaturated dibasic acid monoester, component (b) unsaturated dibasic acid diester, and component (c) aliphatic alcohol.

[0028] [Examples 2-11, Comparative Examples 1-3] Ester compositions were prepared in the same manner as in Example 1, except that the types and proportions of each component were as shown in Table 2. The ester compositions obtained in each example and comparative example were evaluated as described below, and the results are shown in Table 2.

[0029] <Evaluation of water repellency> 0.5 g of the ester compositions of Examples 1 to 11 and Comparative Examples 1 to 3, 10 g of spherical copper powder (product name: FMC-10, manufactured by Furukawa Chemicals Co., Ltd., particle size = approximately 1 μm), and 0.8 g of phenolic resin (product name: PL-5208, manufactured by Gun-ei Chemical Industry Co., Ltd., solid content = 60 wt%, solvent: diethylene glycol monoethyl ether) were mixed and placed in a polypropylene container with a lid. Primary mixing was performed by stirring at 2000 rpm for 3 minutes using a rotary-orbit mixer (product name: Awatori Rentaro ARV-310, manufactured by Thinky Co., Ltd.). Next, secondary mixing was performed using a three-roll mill (product name: EXAKT-M80S, manufactured by Nagase Screen Printing Laboratory Co., Ltd.) under conditions of room temperature and a roll distance of 5 μm to obtain the copper paste composition for evaluation. The obtained copper paste composition was applied to a glass substrate and heated on a hot plate at 150°C for 10 minutes to obtain an evaluation copper film. Using this evaluation copper film, the contact angle of ion-exchanged water with respect to the copper film surface was measured using an automatic contact angle meter DropMasterR501Hi (manufactured by Kyowa Interface Science Co., Ltd.). In this evaluation, a larger contact angle value indicates better water repellency. The evaluation criteria are as follows: A: Contact angle is 100° or more. B: Contact angle is 80° or more and less than 100°. C: Contact angle is less than 80°.

[0030] <Evaluation of Dispersion Stability> Ester composition solutions with a concentration of 1% were prepared using the ester compositions of Examples 1 to 11 and Comparative Examples 1 to 3 and 2-propanol solutions. 10 g of each ester composition solution and 10 g of spherical copper powder (product name: FMC-10, manufactured by Furukawa Chemicals Co., Ltd., particle size = approximately 1 μm) were placed in a glass screw-cap bottle and stirred at 2000 rpm for 3 minutes using a rotary-orbit mixer (product name: Awatori Rentaro ARV-310, manufactured by Thinky Co., Ltd.) to obtain a dispersion for evaluation. The obtained dispersion was left to stand at 25°C, and the stability of the dispersion was evaluated by visually observing the time until the copper particles settled at the bottom of the screw-cap bottle. In this evaluation, a longer time until settling indicates better dispersion stability. The evaluation criteria are as follows: A: Time until settling is 24 hours or more. B: Time until settling is 4 hours or more but less than 24 hours. C: Time until settling is less than 4 hours.

[0031] <Evaluation of solubility> 0.1 g of the ester compositions of Examples 1 to 11 and Comparative Examples 1 to 3 and a toluene / 2-propanol = 50% / 50% solution were charged into a glass screw tube bottle, and a rotation-revolution mixer (product name: Awatori Rentaro ARV-310, manufactured by Shin Kee Co., Ltd.) was used to stir at 2000 rpm for 3 minutes to obtain a mixed solution for evaluation. The turbidity of the mixed solution was measured using a portable turbidimeter (product name: TN100IR, manufactured by EUTECH INSTRUMENTS), and the solubility of each ester composition was evaluated visually. In this evaluation, the smaller the measured value of turbidity (unit: NTU), the better the solubility. The evaluation criteria are as follows. A: The turbidity is less than 10. B: The turbidity is 10 or more and less than 100. C: The turbidity is 100 or more.

[0032]

[0033] The ester compositions of Examples 1 to 11 according to the present invention were excellent in all evaluation results. In contrast, the ester composition of Comparative Example 1 had a high content of component (a) unsaturated dibasic acid monoester and insufficient solubility. The ester composition of Comparative Example 2 had a high content of component (c) aliphatic alcohol and insufficient water repellency and dispersion stability. The ester composition of Comparative Example 3 had a high content of component (b) unsaturated dibasic acid diester and insufficient water repellency and dispersion stability.

Claims

1. An ester composition comprising (a) an unsaturated dibasic acid monoester represented by the following formula (1), (b) an unsaturated dibasic acid diester represented by the following formula (2), and (c) an aliphatic alcohol having 4 to 24 carbon atoms, wherein, based on 100% by mass of the total of components (a) to (c), component (a) is 70 to 99% by mass, component (b) is 0.5 to 15% by mass, and component (c) is 0.5 to 15% by mass. (In formula (1), R １ This indicates an alkyl group having 2 to 30 carbon atoms. (In formula (2), R ２ , R ３ This indicates an alkyl group having 2 to 30 carbon atoms.

2. A liquid-repellent composition comprising the ester composition described in claim 1.

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