JP4562451B2 - Fluorine-containing compound - Google Patents

Description

The present invention relates to fluorine-containing compounds. More specifically, the present invention relates to a fluorine-containing compound that can be used as an additive for transparent resin materials used in various applications such as optical communication, optical waveguide, optical recording, and liquid crystal display.

Fluorine-containing compounds are useful compounds that can exhibit excellent properties such as water repellency due to fluorine atoms, and are used as raw materials for various industrial products. By the way, as a technical field of fluorine chemicals, there is an application to a transparent resin material used for optical communication, optical waveguide, optical recording, liquid crystal display and the like. Conventionally, many of the transparent resins used in these applications exhibit water absorption, and the absorption of moisture into the transparent resin has various adverse effects such as warpage and distortion of the molded product, and increased transmission loss. For this reason, various studies have been made on reducing the water absorption rate of the transparent resin. Fluorine-containing compounds capable of exhibiting characteristics attributable to fluorine atoms have been attracting attention for use in transparent resin materials used in such fields as recent IT (information technology) progresses.

Regarding a material containing a conventional transparent resin, a resin composition comprising a polymer (A) containing a repeating unit having a 6-membered ring structure containing an ether bond and a (meth) acrylic polymer (B) (for example, Obtained by casting polymerization of a composition containing phenyl methacrylate, dicyclopentenyl acrylate, alkyl acrylate having an alkyl group having 1 to 5 carbon atoms and a crosslinking agent in the presence of a radical polymerization initiator. A low water-absorbing transparent resin (see, for example, Patent Document 2) is disclosed. It is described that these resin compositions are used for optical parts such as lenses, optical information recording media such as optical disks, optical transmission materials, and the like. In addition, a polymer material for optical communication including a repeating unit in which a compound containing a nitrogen atom in the main chain is ester-bonded is disclosed (for example, see Patent Document 3).
However, in the materials containing these transparent resins, it is possible to further improve the low water absorption and to be suitably used for various applications such as optical communication, optical waveguide, optical recording, and liquid crystal display. There was room.
JP 2000-239325 A (page 2-3) JP-A-5-32731 (pages 2 and 4) JP 2000-89049 A (page 2-3)

The present invention has been made in view of the above situation, and is used for applications such as additives for reducing the water absorption and water repellency of a transparent resin material without impairing various properties such as transparency of the transparent resin. It is an object of the present invention to provide a fluorine-containing compound that can be used.

The present inventors have made various studies on fluorine-containing compounds. As a result, a hydrogen atom of a benzene ring having a cyano group as a substituent is substituted with a fluorine atom, and a fluorinated alkyl group is an oxygen atom (O) or a sulfur atom (S). A novel fluorine-containing compound having a structure in which one or more are bonded to the benzene ring via a hydrogen atom was found. When this compound is added as an additive to a transparent resin such as an acrylic resin, fluorine is excellent in water repellency. Therefore, the water absorption in the transparent resin is lowered and water repellency is reduced. The inventors have found that the refractive index can be controlled without impairing various characteristics such as thermal characteristics, and have conceived that the above problems can be solved brilliantly. In addition, a production method for efficiently producing such a fluorine-containing compound having a specific structure has also been found, and the present invention has been achieved.

That is, the present invention provides the following general formula (1);

(In the formula, X represents O or S. Rf is a fluorine-containing alkyl group having 4 or more carbon atoms. R is the number of Rf-X- bonded to the aromatic ring, and 1 or more. S is the number of fluorine atoms bonded to the aromatic ring and is an integer of 1 or more, and r + s is an integer of 2 to 5.) is there.
The present invention also includes the following general formula (3) obtained by reacting a fluorine-containing alkyl alcohol having 4 or more carbon atoms or a fluorine-containing alkylthiol having 4 or more carbon atoms with a fluorine-containing benzonitrile;

(In the formula, X represents O or S. Rf is a fluorine-containing alkyl group having 4 or more carbon atoms. R is the number of Rf-X- bonded to the aromatic ring, and 1 or more. S is the number of fluorine atoms bonded to the aromatic ring, and is an integer of 1 or more, and r + s is an integer of 2 to 5.) It is also a manufacturing method.
The present invention is described in detail below.

The fluorine-containing compound of the present invention is represented by the general formula (1). In the general formula (1), the fluorine-containing alkyl group is a hydrogen atom bonded to a carbon atom constituting the alkyl group. Is partially or entirely substituted with a fluorine atom, and the structure is not particularly limited, and may be any of linear, branched, and cyclic alkyl groups, but the fluorine atom bonded to the carbon atom The number is preferably larger than the number of hydrogen atoms bonded to carbon atoms. When the number of fluorine atoms is larger than the number of hydrogen atoms, for example, when the fluorine-containing compound is used as an additive for the transparent resin material, the transparent resin material can exhibit sufficient water repellency. Preferably, in the general formula (1), r + s is 5, that is, a fluorine atom or Rf-X- is bonded to all carbon atoms of the aromatic ring. More preferably, r = 1 and s = 4.
When adding the fluorine-containing compound of this invention as an additive to transparent resin material, 1 type (s) or 2 or more types can be added.

In the general formula (1), examples of the compound where r = 1 and s = 4 include compounds represented by the following formulas (1-1) to (1-6).

The fluorine-containing compound of the present invention is a fluorine-containing compound represented by the above general formula (1), and among the compounds in which r + s is 5, the following general formula (2);

It is more preferable that it is a compound represented by these. When the fluorine-containing compound has such a structure, the transparent resin material can be made to have lower water absorption and water repellency when added to the transparent resin material.

The present invention also provides the following general formula (3) obtained by reacting a fluorine-containing alkyl alcohol having 4 or more carbon atoms or a fluorine-containing alkylthiol having 4 or more carbon atoms with a fluorine-containing benzonitrile;

(In the formula, Rf is a fluorine-containing alkyl group having 4 or more carbon atoms. R is the number of Rf-X- bonded to the aromatic ring and is an integer of 1 or more. S is an aromatic ring. And is an integer of 1 or more, and r + s is an integer of 2 to 5). By this production method, a compound in which one or two or more fluorine-containing alkoxyl groups are substituted on the aromatic ring of fluorine-containing benzonitrile can be efficiently produced. In this reaction, the fluorine-containing alkyl alcohol having 4 or more carbon atoms and the fluorine-containing benzonitrile may be used singly or in combination of two or more.

In the above reaction, the ratio of the amount of fluorine-containing alkyl alcohol or fluorine-containing alkyl thiol and the amount of fluorine-containing benzonitrile used is the number of fluorine-containing alkoxyl groups or fluorine-containing alkylthio groups substituted for the fluorine-containing compound produced by the reaction, etc. What is necessary is just to determine suitably according to. For example, when a mono-substituted product in which one fluorine-containing alkyl group is substituted on pentafluorobenzonitrile by reacting a fluorine-containing alkyl alcohol with pentafluorobenzonitrile (PFBN), 1 mol of the fluorine-containing alkyl alcohol is used. Thus, it is preferable to add pentafluorobenzonitrile at a ratio of 1 to 5 moles for reaction. More preferably, pentafluorobenzonitrile is added at a ratio of 1 to 2 mol with respect to 1 mol of the fluorine-containing alkyl alcohol and reacted.

The above reaction is preferably performed in the presence of a basic catalyst. The basic catalyst is not particularly limited as long as it is a basic substance capable of capturing hydrogen fluoride (HF) in the reaction system, and potassium carbonate, calcium carbonate, potassium hydroxide, calcium hydroxide, potassium fluoride. , Triethylamine, tributylamine, pyridine and the like can be used. The amount of these basic substances used may be appropriately determined depending on the number of fluorine-containing alkoxyl groups or fluorine-containing alkylthio groups to be substituted for the fluorine-containing compound produced by the reaction. For example, when a monosubstituted product in which one fluorine-containing alkyl group is substituted on the above pentafluorobenzonitrile as a product is produced, the amount is preferably 0.5 to 5 mol with respect to 1 mol of pentafluorobenzonitrile. More preferably, it is 0.5-1 mol. These basic substances may be used alone or in combination of two or more.

Solvents that can be used in the above reaction include acetonitrile, N-methylpyrrolidone (NMP), N-methyl-2-pyrrolidinone, dimethylacetamide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), nitrobenzene, nitromethane, and the like. Examples include polar solvents and mixed solvents of these polar solvents and nonpolar solvents such as toluene and xylene. By using a mixed solvent of a polar solvent and a nonpolar solvent such as toluene as a solvent in the initial stage of the reaction, water by-produced during the reaction can be removed as an azeotrope of toluene by azeotropic dehydration. These solvents may be used alone or in combination of two or more.
The concentration of the fluorine-containing benzonitrile in these solvents is preferably 1 to 40% by mass. If the concentration of the fluorine-containing benzonitrile in the solvent is outside this range, the efficiency of the reaction will decrease. More preferably, it is 5-30 mass%.

The reaction conditions for the above reaction are not particularly limited, but the reaction temperature is preferably 0 to 150 ° C., and the reaction time is preferably 1 hour or more. By performing the reaction under these conditions, the above-described fluorine-containing compound can be obtained in a high yield. The reaction may be performed under normal pressure or under reduced pressure.
The product produced by the above reaction is distilled after removing the deposited salt and then distilling the solvent, or after distilling off the solvent, extracting with an organic solvent, and using other methods such as column chromatography. And can be obtained separately.

The fluorine-containing compound of the present invention can be suitably used as an additive for transparent resin materials. When the fluorine-containing compound of the present invention is used as an additive for a transparent resin material, it is possible not only to reduce the water absorption of the transparent resin and to make it water repellent due to the excellent water repellency of fluorine atoms. By appropriately setting the content of the fluorine-containing compound, the refractive index of the transparent resin material can be changed according to the content of the additive without impairing various properties such as thermal properties.

When using the fluorine-containing compound of this invention as an additive of transparent resin material, it is preferable that 1-100 mass% is added with respect to the transparent resin which transparent resin material contains. If it is less than 1% by mass, the transparent resin material may not be sufficiently reduced in water absorption and water repellency, and if it exceeds 100% by mass, basic properties such as transparency and mechanical strength may not be sufficiently exhibited. There is. As a lower limit, More preferably, it is 5 mass%, More preferably, it is 10 mass%. As an upper limit, More preferably, it is 80 mass%, More preferably, it is 70 mass%.

The transparent resin material contains a polymer that forms a molded article having transparency. Such a transparent resin material only needs to form a molded article having transparency, and may be any material containing a transparent resin such as an acrylic resin as described later.
The transparency means having a high light transmittance. The transparent resin material here refers to a material having a total light transmittance of 70% or more. Examples of the measuring method include a method using a colorimetric color difference meter NDH-1001DP type (manufactured by Nippon Denshoku Industries Co., Ltd.) as a measuring device.

As the molded product, fibers, molded products, thick film, and the like are suitable.
In the molded product, the fiber is a fibrous molded product, and the diameter is preferably 10 μm or more and 10,000 μm or less. The molded body is a molded product having a predetermined shape, for example, a molded body such as a pellet shape, a sheet shape such as a flat plate or a corrugated plate, a pipe shape; a semicircle, an L shape, a T shape, a U shape, a mountain shape, etc. An irregular shaped body having a shape of The thick film is a film or a sheet-like molded product, and the thickness is preferably 10 μm or more and 1000 μm or less.
As the molding method of the molded product, methods such as injection molding, extrusion molding, vacuum molding, blow molding, thermoforming, compression molding, calender molding, powder molding, foam molding, laminate molding, and solvent casting are suitable.

As the transparent resin, an acrylic resin, a polycarbonate resin, a fluorine resin, an epoxy resin, a polyether resin, a polyester resin, and the like are preferable. An acrylic resin and a polycarbonate resin are preferable.
The acrylic resin is preferably one comprising a polymer obtained by polymerizing a monomer component containing (meth) acrylic acid or an ester compound thereof as an essential component, for example, polymethyl methacrylate, Preference is given to polymethyl methacrylate, maleimide-modified polymethyl methacrylate, deuterated polymethyl methacrylate, etc. copolymerized with other monomers. Among these, a mixture or copolymer of these acrylic resins is preferable.
The polycarbonate resin includes a polymer having a carbonate bond (—O—CO—O—) in the main chain.

The transparent resin material containing the fluorine-containing compound of the present invention can be used for various applications such as optical communication, optical waveguide, optical recording, and liquid crystal display. Examples thereof include lenses such as optical pickup lenses and camera lens lamp lenses; discs such as video discs, audio discs and write-once discs for computers; and optical transmission materials such as optical fibers, optical connectors, and light guides.

The fluorine-containing compound of the present invention has the above-described configuration. For example, when used as an additive of a transparent resin material, the transparent resin material has low water absorption without impairing various properties such as transparency of the transparent resin. Can be water repellent. In addition, when a fluorine-containing compound is added, the refractive index can be lowered or the dielectric constant can be lowered when added to a normal resin.
Further, the method for producing a fluorine-containing compound having a specific structure of the present invention is suitable as a method for efficiently producing a fluorine-containing compound suitable as an additive for such a transparent resin material.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

Synthesis example 1
Synthesis of pentafluorodecanoxytetrafluorobenzonitrile (17FD-TFBN) Pentafluorobenzonitrile (PFBN) 5.66 g (29.31 mmol), alkyl fluorinated alcohol 9.28 g (19.99 mmol), potassium carbonate 1.45 g (10.49 mmol) and 50 g of acetonitrile were charged all at once into the reaction vessel. The reaction solution was heated at 70 ° C. for 24 hours and then cooled. After completion of the reaction, the precipitated salt was filtered, the solvent was distilled off, and the resulting crude product was distilled under reduced pressure at 113 to 118 ° C./0.1 mmHg to obtain 8.92 g of white solid (yield 70%). Got. The product obtained is pentafluorodecanoxy-2,3,5,6-tetrafluorobenzonitrile (p-substituted) / pentafluorodecanoxy-3,4,5,6-tetrafluorobenzonitrile. The mixture was (o-substituted product) = 87.7 / 12.3. The H-NMR and F-NMR charts of the obtained substance are shown in FIG. In addition, the ratio of the p-substituted product / o-substituted product of the obtained product is (i), (j) and (k), (l), (m) of the F-NMR chart shown in FIG. , (N) is calculated from the area ratio of the peaks. H-NMR and F-NMR measurements were performed with the following apparatus and conditions. Thermal characteristics of the obtained 17FD-TFBN were evaluated. The results are shown in Table 1. The measurement apparatus and conditions for thermal property evaluation are as follows.

[H-NMR and F-NMR measurements]
Using Unity Plus 400 (manufactured by Varian), the solvent CDCl ₃ was used, and H-NMR (400 MHz) and F-NMR (376 MHz) spectra were measured for structural analysis. In the H-NMR spectrum, the H position of tetramethylsilane (TMS) was set to 0 ppm as an internal standard, and the F position of F of the hexafluorobenzonitrile was set to 0 ppm as an internal standard.
[Thermal characteristics evaluation]
The decomposition temperature (2% weight reduction temperature) was measured using a Shimadzu differential thermothermal weight simultaneous measurement device (manufactured by Shimadzu Corporation).
The heating rate was 10 ° C./min in a nitrogen atmosphere.

Example 1 and Comparative Example 1
Acrylic resin A (methyl methacrylate (MMA) / t-butyl methacrylate (tBMA) / FM108 = 60/30/10, solvent: methyl ethyl ketone (MEK) / toluene, solid content 30%, FM108: fluorine-containing methacrylic acid derivative, Kyoeisha Chemical 10 parts) 0.9 part of 17FD-TFBN (p-substituted and o-substituted product mixture) obtained in Synthesis Example 1 was dissolved to obtain a transparent resin material.
Using this material as a casting method, a film was obtained by preparing PET and peeling the film.
This film maintained excellent transparency without impairing transparency. About this film, the total light transmittance, the haze, and the water absorption were measured. The results are shown in Table 2. Measuring devices and conditions for measuring total light transmittance, haze, and water absorption are as follows.

[Total light transmittance, haze]
It measured using the side color pigment meter NDH-1001DP type (made by Nippon Denshoku Industries Co., Ltd.).
The total light transmittance and haze of the 50 μm film prepared according to the formulation of Example 1 were measured.
[Water absorption rate]
The film produced by the formulation of Example 1 was immersed for 72 hours at 25 ° C., the change in mass was measured, and the water absorption was calculated.

Pentafluorodecanoxy-2,3,5,6-tetrafluorobenzonitrile (p-substituted product) and pentafluorodecanoxy-3,4,5,6 obtained in Synthesis Example 1 of the present invention -It is a measurement chart of H-NMR of a mixture of tetrafluorobenzonitrile (o-substituted product). F-NMR of the mixture of (p-substituted product) obtained in Synthesis Example 1 of the present invention and pentafluorodecanoxy-3,4,5,6-tetrafluorobenzonitrile (o-substituted product) It is a measurement chart.

Claims (3)

The following formulas (1-1) to (1-6);

An additive for resin, comprising a fluorine-containing compound represented by any one of the following: The additive for resin according to claim 1, wherein the additive for resin is used as an additive for a transparent resin. A resin material comprising the additive for resin according to claim 1 or 2 and an acrylic resin.

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