Composition and method for producing article having coating

Abstract

To provide a composition containing an organic zinc compound and a saturated aliphatic hydrocarbon-based solvent and having excellent storage stability.SOLUTION: A composition contains: an organozinc compound represented by a formula (1); a saturated aliphatic hydrocarbon organic solvent; and one or more hydrocarbon compounds selected from the group consisting of aromatic hydrocarbon compounds represented by a formula (2) and liquid at 1 atm and 25°C, and unsaturated hydrocarbon compounds represented by a specific formula and liquid at 1 atm and 25°C. Formula (1) R11-Zn-R12 (In formula (1), R11 and R12 represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.) (In formula (2), R2 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a hydrogen atom, and m represents an integer of 1 to 6.)SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition, and more particularly to a composition containing an organozinc compound. Further, the present invention also relates to a method for manufacturing an article having a film formed using the above composition.

Background Art

[0002] In recent years, various compounds have been proposed as precursors for producing zinc oxide (see Patent Documents 1 to 6). Further, organozinc compounds have been proposed as catalysts for polymerizing monomers (see Patent Documents 7 and 8).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Summary of the Invention

Problems to be Solved by the Invention

[0004] For example, as a precursor for producing zinc oxide, a zinc complex compound to which an organic ligand (ligand) is bonded is known. Specific examples of such zinc complex compounds include zinc acetate, zinc acetylacetonate, etc. However, in order to convert them into a zinc oxide-based film of sufficient quality to exhibit the expected functions, a temperature of 350°C or higher is required (see, for example, Patent Document 1 and Patent Document 2). In addition, metal halide compounds are also frequently used as precursors for producing zinc oxide, but due to their low volatility, high temperatures are required, resulting in difficulties in the process.

[0005] Also, examples have been reported in which the organic ligand of the complex is selected to enable film formation at 300°C or lower in order to convert it into a zinc oxide-based film at a lower temperature (see, for example, Patent Document 3). However, for example, when converting a precursor of zinc oxide into a zinc oxide-based film on a resin substrate, in addition to the adaptability to the resin substrate, damage reduction to the substrate, etc. are required. Therefore, it is desirable to be able to convert it into a zinc oxide-based film at the lowest possible temperature.

[0006] In addition, it has also been proposed to deposit a zinc oxide-based film on a substrate by chemical vapor deposition using diethylzinc, a diethylzinc octane solution, etc. as raw material substances (see, for example, Patent Document 4). By using highly reactive diethylzinc, it is possible to produce a zinc oxide-based film at a relatively low temperature. Patent Document 4 proposes the use of a solvent system in which two or more chain-like aliphatic hydrocarbon solvents are combined.

[0007] Although organic zinc compounds such as diethylzinc are suitable for film formation on substrates with low heat resistance because they can be converted into zinc oxide at relatively low temperatures, they generally have very high reactivity. Therefore, for example, regarding diethylzinc, additives for enhancing the thermal stability of diethylzinc-containing compositions have been studied (see, for example, Patent Document 5 and Patent Document 6).

[0008] Organic zinc compounds such as diethylzinc become unstable in solution during storage due to their excessive reactivity, and metallic zinc may precipitate or the solution may become colored. In particular, when metallic zinc precipitates in the solution during storage, the concentration of the organic zinc compound, which is the active ingredient, decreases. Also, for example, when a solution containing an organic zinc compound is applied and formed into a film by a spraying method or the like, the low storage stability of the solution may cause clogging of the nozzle, a decrease in the transparency of the formed zinc oxide-based film, or the inability to form a film with a predetermined film thickness, leading to a decrease in productivity and a decrease in the quality of the zinc oxide-based film.

[0009] In recent years, it has been proposed to use an organic zinc compound as a catalyst (for example, a Lewis acid catalyst) or a catalyst precursor (see, for example, Patent Documents 7 and 8). When an organic zinc compound is used in such applications, if precipitation occurs in the solution containing the organic zinc compound, the charged amount of the catalyst may be insufficient and a predetermined reaction activity may not be exhibited, or impurities by-produced due to deterioration may inhibit the original catalyst function.

[0010] From the above viewpoints, for example, it is desired to improve the storage stability of a solution containing an organic zinc compound.

[0011] On the other hand, in applications for producing a coating film by a spraying method or the like, in recent years, saturated aliphatic hydrocarbon solvents are often used in consideration of environmental impact and / or human impact. Even when an organic zinc compound is used as a catalyst or a catalyst precursor, from the viewpoint of environmental impact and / or human impact, saturated aliphatic hydrocarbon solvents are desirable solvents.

[0012] In view of the above, one aspect of the present invention aims to provide a composition containing an organic zinc compound and a saturated aliphatic hydrocarbon solvent, which has excellent storage stability.

Means for Solving the Problems

[0013] One aspect of the present invention is as follows. [1] An organozinc compound represented by the following formula (1) (hereinafter also referred to as "component (1)"), a saturated aliphatic hydrocarbon-based organic solvent, and one or more hydrocarbon-based compounds selected from the group consisting of an aromatic hydrocarbon-based compound represented by the following formula (2) and being liquid at 1 atm and 25°C (hereinafter also referred to as "component (2)") and an unsaturated hydrocarbon-based compound represented by the following formula (3) and being liquid at 1 atm and 25°C (hereinafter also referred to as "component (3)"). A composition containing the above.

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0014] According to one aspect of the present invention, there can be provided a composition containing an organozinc compound and a saturated aliphatic hydrocarbon solvent, and having excellent storage stability.

Embodiments for Carrying Out the Invention

[0015] One aspect of the present invention relates to a composition comprising an organozinc compound represented by formula (1), a saturated aliphatic hydrocarbon organic solvent, and one or more hydrocarbon compounds selected from the group consisting of an aromatic hydrocarbon compound represented by formula (2) and being liquid at 1 atm and 25 °C and an unsaturated hydrocarbon compound represented by formula (3) and being liquid at 1 atm and 25 °C.

[0016] As a result of intensive studies by the present inventors, it has been newly found that by containing the above hydrocarbon compound as an additive in a composition containing an organozinc compound represented by formula (1) and a saturated aliphatic hydrocarbon organic solvent, it is possible to improve the storage stability of the composition. The present inventors speculate the following two reasons for the reason why the above hydrocarbon compound can contribute to the improvement of the storage stability of the composition. The first is related to the formation of a complex. Since component (2) has an aromatic ring and component (3) has an alkene bond and can interact with zinc due to donation and back-donation of electrons, it is presumed that π coordination can form a stable complex. It is considered that due to the contribution of such an interaction, the additive can cause stabilization of the complex while repeating desorption and adsorption to zinc. It is presumed that this point can contribute to the storage stability of the composition. The second is related to the deactivation of active species generated from the solvent. For example, in the case of a solvent such as methylcyclohexane that generates active species such as radicals upon dehydrogenation, it is presumed that the decomposition of an active organozinc compound such as diethylzinc by this active species leads to a decrease in the storage stability of the composition. On the other hand, for example, if a radical scavenger having a hydrogen-donating ability (tetralin as an example) is contained in the system, it can be expected to act as a radical scavenger that deactivates the active species generated from the solvent and contribute to the improvement of the storage stability of the composition. For example, in this way, it is presumed that the active species generated from the solvent can be deactivated by the additive and can contribute to the storage stability of the composition. However, the above is speculation, and the present invention is not limited to the speculation described in this specification.

[0017] The above composition will be described in more detail below. In the present invention and this specification, the alkyl groups of the alkyl group and alkoxy group include linear alkyl groups, branched alkyl groups, and cyclic alkyl groups.

[0018] <Component (1): Organozinc compound> Component (1) contained in the above composition is an organozinc compound represented by the following formula (1). The above composition may contain only one kind of the organozinc compound represented by formula (1) as component (1), or may contain two or more kinds in any ratio.

[0019]

Chemical formula

[0020] Component (1) will be described in more detail below.

[0021] In formula (1), R 11 and R 12 each independently represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. However, at least one of R 11 and R 12 represents an alkyl group having 1 to 4 carbon atoms. When R 11 represents an alkyl group having 1 to 4 carbon atoms and R 12 represents an alkyl group having 1 to 4 carbon atoms, that is, when component (1) is dialkylzinc, R 11 and R 12 represent the same alkyl group in one form and different alkyl groups in another form.

[0022] The above alkyl group may be an alkyl group having 1 to 4 carbon atoms and is not particularly limited. For example, it can be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, etc.

[0023] Component (1) preferably has an alkyl group having 1 to 3 carbon atoms as the above alkyl group, and since it is highly available, diethylzinc (i.e., R 11 and R 12 are both ethyl groups) is more preferred.

[0024] [Hydrocarbon compound] The above composition contains one or more hydrocarbon compounds selected from the group consisting of an aromatic hydrocarbon compound (component (2)) represented by the following general formula (2) and being liquid at 1 atm and 25°C, and an unsaturated hydrocarbon compound (component (3)) represented by the following general formula (3) and being liquid at 1 atm and 25°C. The aromatic hydrocarbon compound of component (2) and the unsaturated hydrocarbon compound of component (3) are each liquid at 1 atm and 25°C as a single compound. The above composition may contain only one compound as the above hydrocarbon compound, or may contain two or more compounds in any ratio. Further, the above composition may contain only one or more of component (2) as the above hydrocarbon compound, may contain only one or more of component (3), or may contain one or more of component (2) and one or more of component (3).

[0025] (Component (2): Aromatic hydrocarbon compound) Component (2) is an aromatic hydrocarbon compound represented by the following general formula (2) and being liquid at 1 atm and 25°C.

[0026] [Chemical formula]

[0027] Hereinafter, component (2) will be described in more detail.

[0028] In formula (2), R 2 represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a hydrogen atom, and m represents an integer of 1 to 6. When m represents an integer of 2 to 6, a plurality of R 2 may be the same or different from each other, and a plurality of R 2They may be bonded to each other to form a cyclic structure. Also, when there are a plurality of R 2 The substitution positions thereof are not particularly limited.

[0029] m represents an integer of 1 or more and 6 or less. m can represent, for example, 1 or 2.

[0030] The above alkyl group may be an alkyl group having 1 to 8 carbon atoms and is not particularly limited. For example, it can be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a 2-hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, etc.

[0031] The above alkoxy group may be an alkoxy group having 1 to 8 carbon atoms and is not particularly limited. For example, it can be a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, an isobutyloxy group, a sec-butyloxy group, a tert-butyloxy group, a pentyloxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, a hexyloxy group, an isohexyloxy group, a sec-hexyloxy group, a tert-hexyloxy group, a 2-hexyloxy group, a heptyloxy group, a 2-ethylhexyloxy group, a cyclohexyloxy group, an octyloxy group, etc.

[0032] When a plurality of R's present in formula (2) 2 are bonded to each other to form a cyclic structure, the cyclic structure thus formed is a divalent group formed by the bonding of a plurality of R's 2 For example, it can have an alkylene group such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a cyclohexylene group, etc. as part of the cyclic structure. When forming a cyclic structure, the substitution positions of the plurality of R's 2 forming the cyclic structure may or may not be adjacent to each other.

[0033] As the aromatic hydrocarbon compound of component (2), from the viewpoint of further improving the storage stability of the composition, a compound having a boiling point of 80°C or higher is preferable. The upper limit of the boiling point is not particularly limited, but it can be, for example, 250°C or lower.

[0034] Specific examples of the aromatic hydrocarbon compound of component (2) include toluene, xylene, ethylbenzene, cumene, pseudocumene, mesitylene, butylbenzene, tetramethylbenzene, tert-butylbenzene, hexylbenzene, heptylbenzene, octylbenzene, tetralin, cyclohexylbenzene, ethoxybenzene, isopropoxybenzene, butoxybenzene, tert-butoxybenzene, hexyloxybenzene, heptyloxybenzene, octyloxybenzene, cyclohexyloxybenzene, anisole, methylanisole, dimethylanisole, ethylanisole, butylanisole, pentylanisole, hexylanisole, heptylanisole, octylanisole, dimethoxybenzene, trimethoxybenzene, and the like. However, the present invention is not limited to the above specific examples. Preferred aromatic hydrocarbon compounds as component (2) from the viewpoint of further improving the storage stability of the composition include methylanisole, ethylbenzene, and tetralin.

[0035] (Component (3): Unsaturated hydrocarbon compound) Component (3) is an unsaturated hydrocarbon compound represented by the following general formula (3) and being liquid at 1 atm and 25°C.

[0036]

Chemical formula

[0037] Hereinafter, component (3) will be described in more detail.

[0038] In formula (3), R 3 , R 4 , R 5 and R 6each independently represents an alkyl group having 1 to 8 carbon atoms or a hydrogen atom. R 3 R 4 R 5 and R 6 may be the same or different from each other. n1 represents an integer of 1 or more and 4 or less, and n2 represents an integer of 1 or more and 12 or less.

[0039] n1 represents an integer of 1 or more and 4 or less, and can represent, for example, 1 or 2. When n1 represents an integer of 2 or more and 4 or less, there are a plurality of structural units of the number of structural units n1 in formula (3), and R 3 and R 4 in these plurality of structural units may be the same or different from each other.

[0040] n2 represents an integer of 1 or more and 12 or less, can represent 2 or more, 3 or more, or 4 or more, and can also represent 11 or less, 10 or less, 9 or less, 8 or less, or 7 or less. When n2 represents an integer of 2 or more and 12 or less, there are a plurality of structural units of the number of structural units n2 in formula (3), and R 5 and R 6 in these plurality of structural units may be the same or different from each other.

[0041] In formula (3), one or more of R 3 R 4 R 5 and R 6 may combine with one or more of R 3 R 4 R 5 and R 6 within the same structural unit or different structural units to form a cyclic structure.

[0042] In one form, R 3 R 4 R 5 and R 6 can all represent hydrogen atoms.

[0043] R 3 R 4 R 5 and R 6When one or more of them represent an alkyl group having 1 to 8 carbon atoms, specific examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a 2-hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, and the like. However, the present invention is not limited to the above specific examples.

[0044] In formula (3), the structural units of the number of structural units n1 and the structural units of the number of structural units n2 may each be arranged continuously or may be arranged alternately or randomly with each other. n1 represents an integer of 1 or more and 4 or less, and n2 represents an integer of 1 or more and 12 or less. Therefore, the unsaturated hydrocarbon-based compound represented by formula (3) is a compound having one or more carbon-carbon double bonds. In the case of a chain-like unsaturated hydrocarbon compound, the position of the double bond may be at the end or inside, and is not particularly limited.

[0045] R 7 and R 8 both represent a hydrogen atom or R 7 and R 8 are bonded to each other to form a cyclic structure. R 7 and R 8 When they are bonded to each other to form a cyclic structure, the unsaturated hydrocarbon-based compound represented by formula (3) can be an unsaturated hydrocarbon-based cyclic compound. R 7 and R 8 When they are bonded to each other to form a cyclic structure, R 7 and R 8 can each independently be an alkyl group, and these alkyl groups can be bonded. Such an alkyl group is not particularly limited, and examples thereof include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. As an example, the unsaturated hydrocarbon-based compound represented by formula (3) is R 7 and R 8each represents a methyl group, and an unsaturated hydrocarbon cyclic compound having "-CH2-CH2-" formed by the bonding of these methyl groups as part of the cyclic structure can be used.

[0046] As the aromatic hydrocarbon compound of component (3), from the viewpoint of further improving the storage stability of the composition, a compound having a boiling point of 80°C or higher is preferable. The upper limit of the boiling point is not particularly limited, but it can be, for example, 250°C or lower.

[0047] Specific examples of the unsaturated hydrocarbon compound of component (3) include octene, octadiene, cyclohexene, cyclohexadiene, cyclooctene, cyclooctadiene, norbornene, norbornadiene, and the like. However, the present invention is not limited to the above specific examples. Preferred unsaturated hydrocarbon compounds as component (3) from the viewpoint of further improving the storage stability of the composition include cyclohexene and cyclooctadiene.

[0048] <Stoichiometric ratio of component (1), component (2), and component (3) in the composition> Regarding the stoichiometric ratio of component (1), component (2), and component (3) in the above composition, the molar ratio of the content of the above hydrocarbon compound to the content of the organozinc compound of component (1), that is, "(component (2) + component (3)) / component (1)", is preferably 0.001 or more, more preferably 0.010 or more, and still more preferably 0.050 or more from the viewpoint of further improving the storage stability of the composition. The above molar ratio ((component (2) + component (3)) / component (1)) is preferably 10.0 or less, more preferably 9.0 or less, still more preferably 8.0 or less, 7.0 or less, 6.0 or less, and 5.0 or less from the viewpoint of reducing the cost of manufacturing the composition. Regarding the above molar ratio, when the above hydrocarbon compound contains two or more kinds, the content thereof is the total amount thereof. This also applies to the content of the organozinc compound of component (1).

[0049] <Saturated aliphatic hydrocarbon organic solvent> The above composition contains a saturated aliphatic hydrocarbon-based organic solvent. In the present invention and this specification, the "saturated aliphatic hydrocarbon-based organic solvent" refers to a saturated aliphatic hydrocarbon-based compound that is liquid at 1 atm and 25°C. When the above composition contains a mixed solvent of two or more saturated aliphatic hydrocarbon-based organic solvents as the saturated aliphatic hydrocarbon-based organic solvent, each saturated aliphatic hydrocarbon-based organic solvent is liquid at 1 atm and 25°C as a single compound. In the above composition, the saturated aliphatic hydrocarbon-based organic solvent can be referred to as the main solvent.

[0050] The above composition can contain only one kind of saturated aliphatic hydrocarbon-based organic solvent, or can also contain two or more kinds in any ratio.

[0051] As the saturated aliphatic hydrocarbon-based organic solvent, a saturated alicyclic hydrocarbon-based organic solvent is preferred. Specific examples of the saturated alicyclic hydrocarbon-based organic solvent include cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, etc. However, the present invention is not limited to the above specific examples. Considering easy availability, safety, price, etc., substituted or unsubstituted cyclohexane is preferred, cyclohexane substituted by one or two or more alkyl groups or unsubstituted cyclohexane is more preferred, cyclohexane, methylcyclohexane or ethylcyclohexane is still more preferred, and cyclohexane or methylcyclohexane is even more preferred.

[0052] <Concentration of the organozinc compound of component (1) in the composition> The concentration of the organozinc compound of component (1) in the above composition can be, for example, 0.1% by mass or more and 30% by mass or less with respect to the whole composition, that is, taking the whole as 100% by mass. From the viewpoint of improving safety during composition handling, it is preferably 1% by mass or more and 20% by mass or less.

[0053] <Turbidity of the composition> Regarding the above composition, for the stability of the solution after storage for a certain period (storage stability), for example, turbidity can be used as an index. Turbidity can be determined with a turbidimeter. Since a solution with high stability has less turbidity, the turbidity is preferably 100 NTU or less, more preferably 80.0 NTU or less, still more preferably 70.0 NTU or less, 60.0 NTU or less, 50.0 NTU or less, 40.0 NTU or less, 30.0 NTU or less, 20.0 NTU or less, and 10.0 NTU or less in that order. The lower the value of turbidity, the more preferable. Note that the above turbidity refers to the turbidity of the composition measured with a turbidimeter calibrated with a formazin standard solution. Therefore, NTU (Nephelometric Turbidity Unit) is adopted as the unit of turbidity.

[0054] In one form, the above composition can be a coating composition. In the present invention and this specification, the "coating composition" means a composition that is applied onto a substrate or the like to form a film. In another form, the above composition can be used as a catalyst composition or a catalyst precursor composition.

[0055] [Method for manufacturing an article having a film] One aspect of the present invention relates to a method for manufacturing an article having a film, which includes applying the above composition onto a substrate.

[0056] Hereinafter, the above manufacturing method will be described in more detail.

[0057] [Substrate]< The material constituting the substrate onto which the above composition is applied is not particularly limited. For example, metals, metal oxides, glass, concrete, various plastics, paper, wood, etc. can be mentioned, and a composite material containing one or more of these may also be used. The shape of the substrate may be plate-shaped or curved, and may be a three-dimensional shape such as a container shape, for example. The substrate may have irregularities on its surface.

[0058] The article manufactured by the above manufacturing method can have a film formed using the above composition on at least a part of the base material. Further, the above film can be located, for example, as the outermost layer of the article at the location where the film is provided. When the base material has a shape with a front surface and a back surface, the above film can be provided, for example, on a part or the whole of either one or both of the front surface and the back surface. Also, the above film may be provided on at least a part or the whole of the side surface of the base material. The base material on which the above film is provided may be the base material alone or may be one on which one or more layers are laminated on the base material. For example, when the organozinc compound represented by the formula (1) is dialkylzinc, a film containing zinc oxide can be formed by the hydrolysis of dialkylzinc. The above manufacturing method is a method capable of forming a zinc oxide-containing film without a binder, as opposed to a method of forming a zinc oxide-containing film with a coating solution containing zinc oxide particles and a binder. Further, according to the above manufacturing method, it is also possible to firmly adhere zinc oxide to the surface of the base material which is the surface to be coated. Furthermore, from the viewpoint that the zinc oxide-containing film formed by the above manufacturing method may exhibit high heat resistance, the zinc oxide-containing film formed by the above manufacturing method is also preferable with respect to the zinc oxide-containing film formed using zinc oxide particles and a binder.

[0059] <Coating of the composition> As the coating method of the above composition, known methods such as a droplet coating method, electrostatic coating, spin coating, dip coating, etc. can be used. From the point that the shape of the base material is not selected, the droplet coating method is preferable. Specific examples of the droplet coating method include a spray coating method, a mist CVD (Chemical Vapor Deposition) method, etc. The spray coating method is a method of spraying the coating solution from a nozzle. As the spray coating apparatus, a commercially available spray coating apparatus and a spray coating apparatus with a known configuration can be used. The mist CVD method is a method of atomizing the coating solution with an ultrasonic mist generator or the like and supplying this mist to the surface of the base material. As the mist CVD coating apparatus, a commercially available mist CVD coating apparatus and a mist CVD coating apparatus with a known configuration can be used.

[0060] The application of the above composition can be carried out in an atmosphere where water and oxygen are present. The relative humidity of the "atmosphere where water and oxygen are present" can be, for example, 20% or more and 100% or less. From the viewpoint of smooth film formation, the relative humidity of the "atmosphere where water and oxygen are present" is preferably 40% or more and 100% or less, more preferably 50% or more and 100% or less or 50% or more and 90% or less. The oxygen concentration in the "atmosphere where water and oxygen are present" can be, for example, 5% by volume or more and 50% by volume or less, 10% by volume or more and 40% by volume or less, or 15% by volume or more and 30% by volume or less, with the total amount of gas in the atmosphere (excluding water vapor) being 100% by volume. The "atmosphere where water and oxygen are present" can be, for example, air, and preferably can be air containing water with a relative humidity within the above range. Alternatively, the "atmosphere where water and oxygen are present" may be an atmosphere of a mixed gas obtained by mixing nitrogen, oxygen, and water instead of the above air. As is well known, the oxygen concentration in air is approximately 20% by volume with respect to the total amount of gas excluding water vapor. The application of the above composition can be carried out, for example, under atmospheric pressure or under pressure, preferably under atmospheric pressure, in an atmosphere where water and oxygen are present. Carrying out under atmospheric pressure is preferable because it is simple in terms of equipment.

[0061] The application of the above composition onto a substrate can be carried out by heating the substrate. The temperature of the substrate during application can be, for example, 300°C or lower, and the temperature of the substrate can be controlled by known heating means such as a heater. In the present invention and this specification, the "substrate temperature" refers to the temperature of the surface of the substrate on which the coating liquid (specifically, the above composition) is applied. If necessary, the substrate temperature can be set to a predetermined temperature, and after drying the solvent, heating for zinc oxide formation can be carried out at the predetermined temperature. It is also possible to make the solvent drying temperature and the subsequent substrate temperature for zinc oxide formation the same and carry out solvent drying and zinc oxide formation simultaneously. The substrate temperature can be appropriately set, such as increasing the temperature in multiple steps according to the type of solvent contained in the coating liquid, etc.

[0062] The atmosphere temperature of the atmosphere for coating can be, for example, 50°C or lower. The coating of the above composition is preferably carried out with the atmosphere temperature being 50°C or lower and the substrate temperature being 300°C or lower. The atmosphere temperature for coating can be, for example, 0°C or higher and 40°C or lower, and the substrate temperature can be, for example, 100°C or higher and 250°C or lower. Also, various coating conditions such as the coating amount, coating speed, size of droplets discharged from the spray nozzle when spray coating, distance between the substrate and the spray nozzle during coating, and spray pressure of the above composition can be set according to the content rate of the organozinc compound represented by formula (1) of the above composition, the specifications of the coating apparatus used, the film thickness of the film to be formed, etc. Furthermore, taking "coating - drying - heating" as one cycle, the number of such cycles can be 1 or 2 or more. The more the number of cycles, the thicker the film can be made. The film thickness of the film of the article manufactured by the above manufacturing method can be appropriately adjusted according to the use of the article and is not particularly limited.

[0063] Specific examples of articles manufactured by forming a film by the above manufacturing method include glass windows, building materials, containers, etc. Examples of the container include containers used when storing and / or distributing pharmaceuticals. The above composition can be used to form a film on the outer surface and / or inner surface of such containers. Also, the above composition can also be used to form a film on the outer surface and / or inner surface of containers used when storing and / or distributing cosmetics, foods, etc.

Examples

[0064] Hereinafter, the present invention will be described based on examples. However, the present invention is not limited to the embodiments shown in the examples.

[0065] The turbidity shown in the table below was measured using a digital turbidimeter (TBD700 manufactured by AS ONE) under a nitrogen atmosphere at an atmosphere temperature of 25°C. By the nephelometric method conforming to ISO7027, infrared rays with a wavelength of 860 nm were used as the light source.

[0066] [Comparative Example 1] Under a nitrogen atmosphere, dehydrated methylcyclohexane was used as the main solvent. 10.10 g of diethylzinc was added to 90.32 g of the main solvent, and the mixture was stirred thoroughly to obtain the solution of Comparative Example 1. The prepared solution was put into a SUS container sufficiently purged with nitrogen, sealed, and stored in an environment with an ambient temperature of 25°C. The turbidity of the solution was evaluated after 3 months and 6 months.

[0067] [Example 1] Under a nitrogen atmosphere, dehydrated methylcyclohexane was used as the main solvent. 7.47 g (81.1 mmol) of dehydrated 1-hexene (molar ratio to diethylzinc: 1.00) was added as an additive to 81.5 g of the main solvent, and the mixture was stirred thoroughly. Then 10.12 g (81.1 mmol) of diethylzinc was added thereto, and the mixture was stirred thoroughly to prepare the solution of Example 1. The prepared solution was put into a container sufficiently purged with nitrogen, sealed, and stored in an environment with an ambient temperature of 25°C. The turbidity of the solution was evaluated after 3 months and 6 months.

[0068] [Examples 2 to 12] A solution was prepared by the method described for Example 1, except that the 1-hexene used in Example 1 was changed to the additives shown in Table 1, and the turbidity was evaluated after storage.

[0069] [Comparative Example 2] A solution was prepared by the method described for Comparative Example 1, except that the methylcyclohexane as the main solvent used in Comparative Example 1 was changed to the main solvents shown in Table 1 and the turbidity of the solution was evaluated after 3 months, and the turbidity was evaluated after storage.

[0070] [Examples 13, 14] A solution was prepared by the method described for Example 7, except that the methylcyclohexane as the main solvent used in Example 7 was changed to the main solvents shown in Table 1 and the turbidity of the solution was evaluated after 3 months, and the turbidity was evaluated after storage.

[0071] [Examples 15 to 17] The solution was prepared by the method described in Example 7, except that the addition amount of tetralin as the additive used in Example 7 was changed to the molar ratio shown in Table 1 with respect to diethylzinc, and the turbidity of the solution was evaluated after 3 months. After storage, the turbidity was evaluated.

[0072] The above results are shown in the following table. From the comparison between the examples and comparative examples shown in the following table, it can be confirmed that in the composition containing the organozinc compound represented by the formula (1) and the saturated aliphatic hydrocarbon organic solvent, the hydrocarbon compound described above contributes to the improvement of storage stability.

[0073]

Table 1

[0074]

Table 2

[0075] Furthermore, regarding Example 7, when the turbidity of the solution after storage for 10 months by the method described above was evaluated, it was 0.00 (NTU).

[0076] Each composition of Examples 1 to 14 was used as a coating solution, a glass substrate (Eagle XG manufactured by Corning Inc.) with a size of 5 cm × 5 cm was placed in a substrate holder as a substrate, and after heating to a substrate temperature of 200 °C, in air containing water at an atmospheric temperature of 25 °C and a relative humidity of 50%, 1 mL of the coating solution was spray-coated at a pressure of 0.10 MPa using a spray device (rCoater manufactured by Asahi Sunac Co., Ltd.) (number of spray coating times: 5 times). As described above, an article having a zinc oxide-containing film on one surface of the glass substrate was obtained.

Industrial Applicability

[0077] One aspect of the present invention is useful in various technical fields that utilize the organozinc compound represented by the formula (1).

Claims

1. an organozinc compound represented by the following formula (1); a saturated aliphatic hydrocarbon organic solvent; and one or more hydrocarbon compounds selected from the group consisting of an aromatic hydrocarbon compound represented by the following formula (2) and being liquid at 25°C under 1 atm, and an unsaturated hydrocarbon compound represented by the following formula (3) and being liquid at 25°C under 1 atm; A composition containing the above. 【Chemical 1】 (In formula (1), R １１ and R １２ each independently represent an alkyl group having 1 to 4 carbon atoms or a hydrogen atom. However, at least one of R １１ and R １２ represents an alkyl group having 1 to 4 carbon atoms.) [Chemical Formula 2] (In formula (2), R ２ represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a hydrogen atom, and m represents an integer of 1 to 6. When m represents an integer of 2 to 6, a plurality of R ２ may be the same or different from each other, and a plurality of R ２ may be bonded to each other to form a cyclic structure.) 【Chemical Formula 3】 (In formula (3), R ３ , R ４ , R ５ and R ６ each independently represents an alkyl group having 1 to 8 carbon atoms or a hydrogen atom, n1 represents an integer of 1 to 4, n2 represents an integer of 1 to 12, R ７ and R ８ both represent a hydrogen atom or R ７ and R ８ are bonded to each other to form a cyclic structure.) When n1 represents an integer of 2 or more and 4 or less, there are a plurality of structural units of the structural unit number n1 in the formula (3), and R in the plurality of structural units ３ and R ４ may be the same or different from each other. When n2 represents an integer of 2 or more and 12 or less, there are a plurality of structural units of the structural unit number n2 in the formula (3), and R in the plurality of structural units ５ and R ６ may be the same or different from each other. In the formula (3), one or more of R ３ , R ４ , R ５ and R ６ may combine with one or more of R ３ , R ４ , R ５ and R ６ within the same structural unit or different structural units to form a cyclic structure. The structural units of the structural unit number n1 and the structural units of the structural unit number n2 may be arranged continuously in each case, or may be arranged alternately or randomly with each other. )

2. The composition according to Claim 1, wherein the boiling point of the aromatic hydrocarbon compound represented by the formula (2) and being liquid at 25°C under 1 atm is 80°C or higher.

3. The composition according to Claim 2, wherein the aromatic hydrocarbon compound represented by the formula (2) and being liquid at 25°C under 1 atm is one or more selected from the group consisting of toluene, xylene, ethylbenzene, cumene, pseudocumene, mesitylene, butylbenzene, tetramethylbenzene, tert-butylbenzene, hexylbenzene, heptylbenzene, octylbenzene, tetralin, cyclohexylbenzene, ethoxybenzene, isopropoxybenzene, butoxybenzene, tert-butoxybenzene, hexyloxybenzene, heptyloxybenzene, octyloxybenzene, cyclohexyloxybenzene, anisole, methylanisole, dimethylanisole, ethylanisole, butylanisole, pentylanisole, hexylanisole, heptylanisole, octylanisole, dimethoxybenzene, and trimethoxybenzene.

4. The composition according to Claim 1, wherein the boiling point of the unsaturated hydrocarbon compound represented by the formula (3) and being liquid at 25°C under 1 atm is 80°C or higher.

5. The composition according to Claim 4, wherein the unsaturated hydrocarbon compound represented by the formula (3) is one or more selected from the group consisting of octene, octadiene, cyclohexene, cyclohexadiene, cyclooctene, cyclooctadiene, norbornene, and norbornadiene.

6. The composition according to any one of Claims 1 to 5, wherein the saturated aliphatic hydrocarbon organic solvent contains one or more saturated alicyclic hydrocarbon organic solvents.

7. The composition according to any one of claims 1 to 5, wherein the saturated aliphatic hydrocarbon-based organic solvent contains one or more saturated alicyclic hydrocarbon-based organic solvents selected from the group consisting of cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, and decahydronaphthalene.

8. The composition according to any one of claims 1 to 5, wherein the molar ratio of the content of the hydrocarbon-based compound to the content of the organozinc compound represented by the formula (1) is 0.001 or more and 10.0 or less.

9. The composition according to any one of claims 1 to 5, wherein the concentration of the organozinc compound represented by the formula (1) is 1% by mass or more and 20% by mass or less with respect to the whole composition.

10. A method for manufacturing an article having a film, comprising applying the composition according to any one of claims 1 to 5 onto a substrate.

Images