JP5013830B2 - Novel fluorine-containing pentaerythritol derivative and method for producing wet coating film using the same - Google Patents

Description

  The present invention relates to a novel fluorine-containing pentaerythritol derivative and a method for producing a wet coating film using the same. More specifically, in a novel fluorine-based compound in which a fluorinated alkyl group and pentaerythritol are cross-linked with an oxyalkylene chain, and a method for producing a wet coating film in which a substrate is coated with a wet coating liquid, The present invention relates to a method for producing a wet coating film, which comprises previously mixing the above novel fluorine-based compound in a wet coating liquid.

  Conventionally, a surfactant having a fluorinated alkyl group or the like has been used as a leveling agent or a wetting agent for various coating liquids. However, the conventional fluorosurfactant has a problem that it is difficult to efficiently orient on the surface because the number of fluorinated alkyl groups per molecule is small. A conventional fluorosurfactant is sufficient because the fluorinated alkyl group, etc., is separated from other functional groups and hydrocarbon skeletons, and the latter functional group and the like are compatible with various solvents. It is considered that surface activity may not be expressed.

  Moreover, although patent document 1 has pentaerythritol tetraester, it is a compound useful as a lubricating oil etc., and cannot expect the effect of leveling property and wettability improvement.

  Furthermore, Patent Document 2 discloses the following general formula (A):

Wherein, A 'represents an ethylene group and / or a propylene _group, R 1 _{to R 3 +} at least one fluorine-containing group of _{n C 6 F 11 -~C 8 F} 17 - or _C 8 _F 17 O · _{C 6} H ₄ · CO— indicates the remaining hydrogen atom, m ₁ , m ₂ ,... M _{3 + n} represents 0-30, and n represents 0 or a number from 1 to 9]
It is described that the fluorine-containing glycerin derivative represented by these is used as a polymer surface modifier, an antifogging antifoggant and a leveling agent. However, a fluorine-containing glycerin derivative having a more stable quality than the fluorine-containing glycerin derivative having the structure is desired.
JP-A-10-330314 Japanese Patent Laid-Open No. 4-150441

  An object of the present invention is to provide a novel fluorine-containing pentaerythritol derivative and a method for improving the leveling properties of various wet coating films using the same.

  As a result of intensive studies to solve the above problems, the present inventor succeeded in synthesizing a novel fluorine-based compound in which a fluorinated alkyl group and a pentaerythritol are cross-linked with an oxyalkylene chain. It was also found that by adding a small amount of the novel fluorine-based compound to various wet coating liquids and coating it, the coating film can be made smoother and the water repellency can be improved. Furthermore, the present inventors have found that the quality of the novel fluorine-based compound is more stable than conventional fluorine-based compounds due to the symmetry of the structure. The present invention has been completed based on such findings.

  That is, this invention provides the invention of the aspect hung up below.

  Item 1. Fluorine-containing pentaerythritol derivative represented by the following general formula (1):

[In the formula, A represents an alkylene group;
n1 represents a numerical value of 1 to 80,
n2, n3 and n4 are the same or different and represent a value of 0 to 79;
n1 + n2 + n3 + n4 shows a numerical value of 4-80.
X ₁ represents a fluorinated hydrocarbon group,
X ₂ , X ₃ and X ₄ are the same or different and each represents hydrogen or a fluorinated hydrocarbon group. ]
Item 2. The fluorine-containing pentaerythritol derivative according to claim 1, wherein the fluorinated hydrocarbon group is a perfluoroalkenyl group.

  Item 3. 3. The fluorinated pentaerythritol derivative according to claim 1, wherein the fluorinated hydrocarbon group is a branched perfluorononenyl group.

  Item 4. In the manufacturing method of the wet coating film | membrane which coats a base material using a wet coating liquid, the fluorine-containing pentaerythritol derivative as described in any one of Claims 1-3 is previously mixed with this wet coating liquid, It is characterized by the above-mentioned. A method for producing a wet coating film.

Since the fluorine-containing pentaerythritol derivative according to the present invention has a plurality of three-dimensionally fluorinated alkyl groups, the degree of migration to the surface or interface is high and high leveling properties are exhibited. Thereby, various coating films having high smoothness and water / oil repellency can be formed. In addition, due to the highly symmetric structure, in the production process, it becomes easy to uniformly substitute the fluorinated hydrocarbon group at the end of the molecule (X _{1 to} X ₄ in the general formula (1)) (the general formula ( In 1), X _{1 to} X ₄ can be easily replaced by fluorinated hydrocarbons instead of hydrogen). As a result, the quality of the fluorine-containing pentaerythritol derivative of the present invention is stable as compared with conventional fluorine-containing compounds such as fluorine-containing glycerin derivatives. Specifically, since the fluorine-containing pentaerythritol derivative of the present invention has a symmetric structure, the four reaction points are equivalent and the reaction is likely to proceed equally. In addition, since reaction points spread in three dimensions, reaction failure due to steric hindrance is less likely to occur. From these, it is excellent in that a product with a stable reaction rate can be obtained regardless of slight fluctuations in production conditions. .

Fluorine-containing pentaerythritol derivative The fluorine-containing pentaerythritol derivative of the present invention is formed by crosslinking between a fluorinated alkyl group and pentaerythritol with an n-oxyalkylene chain.

  In the general formula (1), A represents an alkylene group. In the present invention, A is preferably an ethylene group or a propylene group, more preferably an ethylene group.

In the general formula (1), X ₁ represents a fluorinated hydrocarbon group. X ₂ , X ₃ and X ₄ represent hydrogen or a fluorinated hydrocarbon group, and at least one of X _{2 to} X ₄ represents a fluorinated hydrocarbon group.

  In General formula (1), n1 shows the numerical value of 1-80. N2, n3 and n4 are the same or different and represent 0-79.

  Here, n1, n2, n3, and n4 are 4 to 80 in total. Preferably it is 4-40, More preferably, it is 4-30.

  In the general formula (1), the fluorinated hydrocarbon group is partially fluorinated or all fluorinated, and is linear or branched having about 3 to 12 carbon atoms (preferably about 6 to 9 carbon atoms). And a perfluoroalkenyl group, preferably a perfluoroalkenyl group, and more preferably a branched perfluorononenyl group.

  The fluorine-containing pentaerythritol derivative represented by the general formula (1) is obtained by, for example, adding an alkylene oxide to pentaerythritol and then substituting the active hydrogen at the terminal of the adduct with the above-mentioned fluorinated hydrocarbon group. Manufactured. As a method for introducing a fluorinated hydrocarbon group, for example, the method of Japanese Patent No. 2883925 can be followed.

  In addition, you may introduce | transduce reactive functional groups, such as hydrocarbon groups, such as long-chain alkyl, acrylic acid, methacrylic acid, an epoxy group, etc. with respect to the active hydroxyl group which has not introduce | transduced the fluorinated alkyl group. Moreover, you may use as a polymer modifier or a crosslinking agent by making it react with respect to a reactive polymer.

Method for producing wet coating film The present invention is a method for producing a wet coating film in which a substrate is coated with a wet coating solution, wherein the fluorine-containing pentaerythritol derivative of the present invention is added to and mixed with the wet coating solution in advance. A method for producing a wet coating film is provided.

  The wet coating liquid to which the fluorine-containing pentaerythritol derivative of the present invention can be added is a wet coating liquid that contains an organic solvent or does not contain a diluting solvent.

  Examples of the components of the wet coating liquid include, but are not limited to, acrylic resins, ester resins, urethane resins, epoxy resins, phenol resins, styrene resins, melamine resins, carbonate resins, vinyl resins, imide resins, and the like.

  When the wet coating liquid contains an organic solvent, the organic solvent is not particularly limited as long as it can sufficiently dissolve or disperse the components of the coating liquid and the fluorine-containing pentaerythritol derivative of the present invention. Examples include, but are not limited to, ester solvents, alcohol solvents, ketone solvents, aromatic solvents, ether solvents, and the like.

  In the present invention, the amount of the fluorine-containing pentaerythritol derivative added to the wet coating solution is 0.0001 to 5% by weight based on the solid content excluding the diluent solvent. Preferably it is 0.0005 to 1 weight%, More preferably, it is 0.001 to 0.1 weight%. Adding a fluorine-containing pentaerythritol derivative within the above range to a wet coating solution provides sufficient leveling and wettability, is not expensive and uneconomical, and causes problems such as component separation due to poor solubility. This is preferable because

  Materials for base materials targeted by the wet coating film manufacturing method include metals such as glass, iron, stainless steel, aluminum, copper, polytetrafluoroethylene, polyethylene, polyester, polycarbonate, polyurethane, polyvinyl chloride, polystyrene, TAC, etc. However, it is not limited to these.

  The method for producing a wet coating film of the present invention includes, for example, a structure; means for transportation and transportation; equipment for commercial, industrial and research purposes; equipment for household use and furniture; equipment for games, sports and leisure; Suitable for coating equipment.

  Buildings include, for example, building interiors and exteriors, floors and stairs made of natural stone, concrete, floor plastic coverings, skirting boards, windows, Venetian blinds, roller blinds, WC, pipes, radiators, mirrors, Light switches, wall and floor tiles, lights, roof tiles, fences, mailboxes, parabolic antennas, antennas, solar collectors, winter gardens, lift walls, monuments, sculptures and generally made from natural stone, metal, etc. Art works that have been made.

  Transportation and transportation means include, for example, headlamps, internal and external mirrors, windshields, rear windows, side windows, motorbike plastic visors, motorbike equipment, steering wheels, tire rims, fuel tank ports, bicycles And motorbike mudguards, license plates, net racks, car roof containers, and cockpits.

  Commercial, industrial and research instruments and equipment include, for example, various molds, hoppers, filling units, printing presses, screen-printing stencils, housings, injection molded parts, drill bits, turbines, pipes, pumps, saws. , Screens, ball bearings, shafts, screws, displays, solar cells, solar units, tools, extruders, water wheels, rollers, conveyor belts, insulators, capillary tubes, lenses, laboratory equipment (eg, chromatography columns and hoods) And a computer (particularly a casing and a motor screen).

  Examples of the household items and furniture furniture include furniture veneers, toilet brushes, stereo devices, television devices, trash cans, lamps and lights.

  Examples of equipment for games, sports and leisure include gardening tools, tools, balls, tables, and the like.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these.

[Example 1]
Compound (1A) was prepared by the following procedure.
In a four-necked flask (1000 mL) equipped with a thermometer, a condenser and a dropping funnel, 60 g (0.19 mol) of raw material (1a), 110 g (0.80 mol) of potassium carbonate, and acetonitrile (600 mL) were placed. 360 g (0.80 mol) of hexafluoropropene trimer was gradually added dropwise at room temperature over about 30 minutes. After completion of the addition, the mixture was further stirred at room temperature for about 12 hours.
The solid was filtered off from the reaction mixture and poured into 1 L of water, which was allowed to stand after stirring. The upper water was removed. After repeating this several times, 230 g of compound (1A) was obtained by heating the lower layer portion under reduced pressure to distill off the volatile component (yield 58%). The physical properties of the compound (1A) are shown in Table 2.

  In the examples of the present application, n1 + n2 + n3 + n4 represents an average value.

[Examples 2 to 4]
In the same manner as in Example 1, compounds (1B), (1C) and (1D) were prepared using raw materials (1b), (1c) and (1d). The synthesis conditions are shown in Table 1. In addition, Table 2 shows the physical properties of these compounds.

[Examples 5 to 9]
Resin solutions to which the compounds of Examples 1 to 4 were added were prepared. The formulation is shown in Table 3.

3 mL of these solutions were dropped on a 100 mm × 100 mm glass substrate, spin-coated, and then dried. The appearance of the formed thin film was visually evaluated. Moreover, the water contact angle with respect to the thin film was measured to evaluate water repellency. The evaluation results are shown in Tables 4 and 5.
[Comparative Examples 1-2]
As comparative examples, resin solutions to which compound (2) and compound (3) were added were prepared, and the appearance of a thin film formed from these solutions was visually evaluated. Moreover, the water contact angle with respect to the thin film was measured to evaluate water repellency. The blending and evaluation results are shown in Table 3, Table 4, and Table 5.

  As is clear from the above results, the thin film formed using the resin solution to which the compound of the present invention is added has no interference unevenness and the leveling property is improved as compared with the thin film using the conventional resin solution. I understand. In addition, the surface of the thin film can be modified to be more water repellent.

  According to the present invention, a novel fluorine-containing pentaerythritol derivative and a method for improving the leveling property and water repellency of various wet coating films using the same can be obtained.

Claims (2)

Fluorine-containing pentaerythritol derivative represented by the following general formula (i) :

[Wherein n 1 represents a numerical value of 1 to 80,
n2, n3 and n4 are the same or different and represent a value of 0 to 79;
n1 + n2 + n3 + n4 shows a numerical value of 4-80 . ] In the manufacturing method of the wet coating film | membrane which coat | covers a base material using a wet coating liquid, the fluorine-containing pentaerythritol derivative | guide_body of Claim 1 is mixed with this wet coating liquid previously, Manufacturing of a wet coating film | membrane characterized by the above-mentioned. Method.