JP2007039427A - Phthalonitrile compound, method for production thereof and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a phthalonitrile compound that is useful as an additive capable of controlling the refractive index without damage of thermal characteristics of a transparent resin. <P>SOLUTION: The phthalonitrile compound is represented by formula (1) [wherein R<SP>2</SP>is a halogen atom or the like, A is represented by formula (2) (wherein X is O or S, R<SP>1</SP>, R<SP>4</SP>are each halogen atom)]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a phthalonitrile compound, a method for producing the same, and a use thereof. More specifically, in addition to raw materials for various industrial products, phthalonitrile compounds that are being studied for various uses, production methods thereof, and resin additives and resin compositions using such phthalonitrile compounds About.

A phthalonitrile compound is a compound having a structure in which two cyano groups are substituted on a benzene ring, and has been widely used as a raw material for various industrial products. And nowadays, application to various uses has been examined from the characteristics resulting from the cyano group which is a polar group. For example, in the field of optical materials such as optical fibers, optical waveguides, optical recording disks, optical films, display substrates, etc., various characteristics of transparent resins used in optical materials have been developed with the rapid development of information technology in recent years. In order to improve or improve, a phthalonitrile compound which is currently undergoing trial and error and can exhibit the characteristics attributable to the cyano group is also one of those that are being studied for use in such fields. However, at present, no satisfactory product has been developed.

Regarding a conventional phthalonitrile compound, a halogen-containing isophthalonitrile compound having a structure in which a phenoxy group having a CF ₃ group and a halogen is bonded to at least one position of the isophthalonitrile compound and a fluorine atom is bonded to the remaining position ( For example, see Patent Document 1). This compound is an important intermediate in the synthesis of dyes, pharmaceuticals, agricultural chemicals, and polymer compounds, and is suitably used as a raw material for resins having excellent heat resistance, water repellency, chemical resistance and low dielectric properties. It is. However, even in fields where development is strongly demanded, such as optical material applications, there is room for improvement in order to achieve further sufficient performance.
JP 2003-55318 A (page 2, claim 1)

The present invention has been made in view of the above situation, and can be suitably used for applications such as additives that can control the refractive index without impairing various properties such as thermal properties of resins such as transparent resins. It is an object of the present invention to provide a phthalonitrile compound that can be produced, a method for producing the same, and a resin additive and a resin composition comprising such a phthalonitrile compound.

As a result of various investigations on phthalonitrile compounds, the present inventors have substituted all the hydrogen atoms of the benzene ring having two cyano groups as substituents with a specific substituent, and at least one group among the substituents. Found a phthalonitrile compound which is a group having a structure bonded to a benzene ring through an oxygen atom (O) or a sulfur atom (S). And when this compound is used as an additive in a resin such as a transparent resin, it has been found that the refractive index can be controlled without impairing various properties such as the thermal properties inherent in the resin. It has also been found that a resin composition containing an additive comprising a nitrile compound can be particularly suitably applied to an optical material such as, for example, an optical fiber, an optical waveguide, an optical recording disk, an optical film, or a display substrate. The inventors have come up with the idea that the above problems can be solved brilliantly. In addition, a method for efficiently producing a phthalonitrile compound having such 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, R ² is the same or different and represents F, Cl, Br, I, COOR ³ or OR ^3. R ³ represents a deuterated alkyl group or a fully halogenated alkyl group. 1 is an integer of 1 to 4, m is an integer of 0 to 3, and n + m is 4. A is the same or different and is represented by the following general formula (2);

(In the formula, X is O or S. R ¹ is the same or different and represents F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ^3. R ⁴ is the same or different. F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ³ where a and b are each an integer of 1 to 5 and a + b = 5, provided that the general formula (1) In the case where the CN group is located at the meta position, X is O, R ¹ is CF ₃ , and R ⁴ is F, Cl, Br or I.) It is a group. The phthalonitrile compound represented by this.
The present invention is described in detail below.

The phthalonitrile compound of the present invention is represented by the above general formula (1). That is, as represented by the general formula (1), the A group is bonded to at least one position of phthalonitrile (a compound having a structure in which two cyano groups are substituted on the benzene ring), and R ² is bonded to the remaining position. A compound having a group bonded thereto. The cyano group of the phthalonitrile compound may be located at any of the ortho, meta, and para positions, but is particularly preferably located at the ortho or meta position.

In the general formula (1), R ² represents a halogen atom, that is, a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br) or an iodine atom (I), COOR ³ or OR ^3. It is preferable that at least one of ² is a halogen atom. More preferably, all of R ² are halogen atoms. Thus, for example, when used by adding to a resin, not only the refractive index is controlled but also the water absorption is sufficiently reduced, Therefore, it can be suitably used for an optical material or the like. As the halogen atom, a fluorine atom and a chlorine atom are preferable, and a chlorine atom is more preferable. This makes it possible to achieve both sufficient control of refractive index and reduction in water absorption. When a plurality of R ² are present, they may be the same or different.

Here, R ³ represents a deuterated alkyl group or a fully halogenated alkyl group, and the deuterated alkyl group is a part or all of hydrogen atoms bonded to carbon atoms constituting the alkyl group. The all-halogenated alkyl group is a group in which all of the hydrogen atoms bonded to the carbon atoms constituting the alkyl group are halogen atoms (that is, fluorine atoms (F), chlorine atoms (Cl), bromine Substituted with at least one kind of atom (Br) and iodine atom (I)). The structure of these groups is not particularly limited, and may be any structure of a straight chain, a branched chain, and a cyclic alkyl group.
In the above deuterated alkyl group or all halogenated alkyl group, the number of carbon atoms constituting these alkyl groups is preferably 1-12, more preferably 1-8. Moreover, as a C1-C12 alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group etc. are suitable, for example.

In the general formula (1), n represents the number of bonds of the A group to phthalonitrile, and is a number of 1, 2, 3 or 4. Among these, 1 or 2 is preferable, and 1 is more preferable in consideration of heat resistance. The bonding position of the A group to the phthalonitrile varies depending on the positional relationship between the two cyano groups, the number and type of bonding of the A group, the characteristics required for the resulting phthalonitrile compound, etc. In the ortho position, when n = 1, it is preferable to bond to the 4-position or 5-position of phthalonitrile in consideration of the reactivity of phthalonitrile. In the case of n = 2, it is preferable to bond to the 4th and 5th positions, the 3rd and 5th positions, or the 3rd and 4th positions, particularly preferably the 4th and 5th positions. In the case of n = 3, it is preferable to bond to the 3rd, 4th and 5th positions. In the case where the cyano group is in the meta position, when n = 1, it is preferable to bond to the 4-position or 6-position of phthalonitrile in consideration of the reactivity of phthalonitrile. In the case of n = 2, it is preferable to bond to the 4th and 6th positions, or the 2nd and 4th positions, particularly preferably the 4th and 6th positions. In the case of n = 3, it is preferable to bond to the 2nd, 4th and 6th positions.

In the general formula (1), m represents the number of R ² groups bonded to phthalonitrile, and is 0, 1, 2, or 3. Among these, 2 or 3 is preferable, and 3 is more preferable in consideration of heat resistance. In the above formula (1), the sum of n and m is always 4 (n + m = 4).

In the general formula (1), A is a group represented by the general formula (2). That is, the R ¹ group and the R ⁴ group are bonded to all remaining positions of the phenoxy group (C ₆ H ₅ O—) or the thiophenoxy (C ₆ H ₅ S—) group.
In the general formula (2), R ¹ and R ⁴ are the same or different and are a halogen atom, that is, a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), an iodine atom (I), or a cyano group. (CN), trifluoromethyl group (CF ₃ ), COOR ³ or OR ³ is represented, and at least one of all R ¹ and R ⁴ is preferably a halogen atom. Thus, for example, when used by adding to a resin, it is possible to sufficiently achieve both control of the refractive index and reduction in water absorption of the resin. The halogen atom is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom. In this case, it is possible to more fully achieve both refractive index control and water absorption reduction. When there are a plurality of R ^{1 s} , they may be the same or different, and the same applies to R ⁴ . R ³ is as described above.

In the general formula (2), a and b represent the number of bonds of R ¹ and R ⁴ to the phenoxy group (C ₆ H ₅ O—) or thiophenoxy (C ₆ H ₅ S—) group, 2, 3, 4 or 5. In the above formula (2), the sum of a and b is always 5 (a + b = 5).
When the cyano (CN) group in the general formula (1) is located at the meta position, from the A group represented by the general formula (2), X is O, and R ¹ is CF. ₃ and R ⁴ is F, Cl, Br or I.

As a particularly preferred form of the compound represented by the general formula (1), for example, a compound in which at least one of R ¹ is F, R ² is F and / or Cl, n = 1, m = 3, etc. is there. Most preferably, R ² is all F or all Cl.

Examples of the phthalonitrile compound of the present invention include the following general formula (3);

(In the formula, R ² is the same or different and represents F, Cl, Br, I, COOR ³ or OR ^3. R ³ represents a deuterated alkyl group or a fully halogenated alkyl group. A compound represented by the following general formula (4);

(In the formula, X is O or S. R ¹ is the same or different and represents F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ^3. R ⁴ is the same or different. Represents F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ^3. Each of a and b is an integer of 1 to 5, and a + b = 5, provided that the general formula (3) In the case where the CN group is located at the meta position, X is O, R ¹ is CF ₃ , and R ⁴ is F, Cl, Br or I.) It can be obtained by reacting with a compound. That is, a method for producing the phthalonitrile compound, wherein the production method comprises a step of reacting the compound represented by the general formula (3) with the compound represented by the general formula (4) (below) The method for producing a phthalonitrile compound comprising simply “reaction step” is also one aspect of the present invention.
In addition, these compounds can use 1 type, or 2 or more types, respectively.

In the compound represented by the general formula (3), the two cyano groups may be located at any of the ortho position, the meta position, and the para position, but are located at the ortho position or the meta position. Is particularly preferred. R ² represents a halogen atom, that is, a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br) or an iodine atom (I), COOR ³ or OR ^3, and at least one of R ² is A halogen atom is preferred. Thereby, the reactivity with the compound represented by the general formula (4) can be more sufficiently improved, and the compound represented by the general formula (1) can be efficiently produced. More preferably, all of R ² are halogen atoms. As a halogen atom, a fluorine atom and a chlorine atom are preferable, and a chlorine atom is more preferable. When a plurality of R ² are present, they may be the same or different.
In addition, about the preferable form of the number of bonds of the deuterated alkyl group or the all halogenated alkyl group represented by said R < ³ > group, and R < ² > group represented by m is as having mentioned above.

Particularly suitable forms of the compound represented by the general formula (3) include tetrachloroisophthalonitrile, tetrafluoroisophthalonitrile and the like.

In the compound represented by the general formula (4), R ¹ and R ⁴ are each a halogen atom, that is, a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), an iodine atom (I), or a cyano group. (CN), trifluoromethyl group (CF ₃ ), COOR ³ or OR ³ is represented, and at least one of all R ¹ and R ⁴ is preferably a halogen atom. Thereby, the reactivity with the compound represented by the general formula (3) can be more sufficiently improved, and the compound represented by the general formula (1) can be efficiently produced. The halogen atom is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom. When there are a plurality of R ^{1 s} , they may be the same or different, and the same applies to R ⁴ . R ³ , a and b are as described above. In the case where a cyano (CN) group in the general formula (3) is positioned in the meta position from compounds represented by the above general formula (4), X is a O, R ¹ is CF ₃ And R ⁴ is F, Cl, Br or I.

A particularly preferred form of the compound represented by the general formula (4) is a form in which at least one of all R ¹ and R ⁴ is a fluorine atom.

In the reaction step, the amount of the compound represented by the general formula (3) and the compound represented by the general formula (4) may be the same as that in the general formula (3) of the compound represented by the general formula (4). Depending on the number of moles added to the compound represented (that is, n in the above general formula (1)), these are not particularly limited as long as they can be reacted efficiently, but considering reaction efficiency and reaction selectivity, The compound represented by the general formula (3) is preferably in an excess amount relative to the compound represented by the general formula (4).

Specifically, for example, the number of moles added to the compound represented by the general formula (3) of the compound represented by the general formula (4) is 1 (that is, n in the general formula (1) is 1), the compound represented by the general formula (3) is preferably 1 to 40 mol relative to 1 mol of the compound represented by the general formula (4). More preferably, it is 1-20 mol.
When the added mole number is 2 (that is, n in the general formula (1) is 2), the compound represented by the general formula (3) is represented by the general formula (4). It is preferable that it is 0.5-20 mol with respect to 1 mol of compounds. More preferably, it is 0.5-10 mol.
When the added mole number is 3 (that is, n in the general formula (1) is 3), the compound represented by the general formula (3) is represented by the general formula (4). It is preferable that it is 0.3-10 mol with respect to 1 mol of compounds. More preferably, it is 0.3-5 mol.
Here, when the compound represented by the general formula (3) falls below the lower limit described above, there is a possibility that the compound represented by the general formula (4) cannot be sufficiently reacted, and the target phthalonitrile compound is not collected. The rate cannot be increased and the reaction selectivity may not be sufficient. Moreover, even if the compound represented by the general formula (3) exceeds the above-described upper limit value, an effect corresponding to the addition cannot be obtained and it is not economical, and an excess of the compound represented by the general formula (3) remains. However, there is a possibility that the recovery cost cannot be reduced sufficiently.

The reaction step is preferably performed in the presence of a catalyst, and the catalyst is preferably a base catalyst. Although it does not specifically limit as a base catalyst, What is necessary is just to use what is used normally, For example, potassium fluoride, sodium fluoride, lithium fluoride, cesium fluoride, potassium chloride, sodium chloride, lithium chloride, cesium chloride, etc. Alkaline metal salts such as calcium chloride and magnesium chloride; alkali metal salts such as sodium hydrogen carbonate, lithium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, sodium carbonate, lithium carbonate, potassium carbonate and cesium carbonate Carbonates; carbonates of alkaline earth metals such as calcium carbonate and magnesium carbonate; tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, tricyclohexylamine, tribenzylamine, triphenylamine and pyridine And the like, can be used alone or in combination of two or more thereof. Of these, potassium fluoride, sodium carbonate, potassium carbonate, triethylamine, tripropylamine and pyridine are preferable.
The amount of the catalyst used is not particularly limited as long as the reaction with the compound represented by the general formula (3) and the compound represented by the general formula (4) can proceed efficiently. It is preferable that it is 0.5-20 mol with respect to 1 mol of compounds represented by Formula (4). More preferably, it is 1-10 mol.
In the reaction step, an alkali metal salt or alkaline earth metal salt of the compound represented by the general formula (4) can also be subjected to the reaction.

The reaction step is also preferably performed in an organic solvent. Although it does not specifically limit as an organic solvent, What is necessary is just to use what is used normally, For example, Nitriles, such as acetonitrile and benzonitrile; Ketones, such as acetone, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), and cyclohexanone Halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, chloroethane, dichloroethane, trichloroethane and tetrachloroethane; aromatic hydrocarbons such as benzene, toluene and xylene; hydrocarbons such as pentane, hexane, cyclohexane and heptane Diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran (THF), dioxane, diphenyl ether, benzyl ether, methyl tert-butyl ether and cyclopentyl Ethers such as methyl ether; esters such as methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate and butyl acetate; N-methylpyrrolidinone (N-methylpyrrolidone) (NMP), dimethylformamide (DMF) ), Dimethyl sulfoxide (DMSO), dimethylacetamide, and the like, and one or more of these can be used. Of these, acetonitrile, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), N-methylpyrrolidinone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and dimethylacetamide are preferable.
The amount of the organic solvent used is not particularly limited as long as the reaction can proceed efficiently. For example, the compound represented by the general formula (3) and the compound represented by the general formula (4) The total amount is preferably set to 1 to 50% by mass with respect to 100% by mass of the total amount of the total amount and the organic solvent. The amount is more preferably 1 to 20% by mass.

The reaction conditions in the reaction step are not particularly limited as long as the reaction between the compound represented by the general formula (3) and the compound represented by the general formula (4) can proceed efficiently. It may be appropriately selected depending on the kind and amount of the reaction raw materials such as the above compound, base and organic solvent, and other various conditions. For example, the reaction temperature is preferably −20 to 200 ° C., more preferably −5 to 150 ° C. The reaction time is preferably 0.1 to 40 hours, more preferably 0.1 to 20 hours. Moreover, although the said reaction process may be performed under any pressure of pressurization, a normal pressure, or pressure reduction, when handling property and an equipment surface are considered, it is suitable to carry out under a normal pressure.

As said manufacturing method, as long as it includes the reaction process mentioned above, although it does not specifically limit about other processes, For example, after performing the solvent distillation after removing the precipitation salt after the said reaction process. It is preferable to separate the reaction product from other components by distillation or solvent distillation, followed by extraction with an organic solvent, and column chromatography.

The phthalonitrile compound of the present invention can be suitably used as a raw material for various industrial products, but among them, it can be particularly suitably used as an additive to be added to a resin, that is, an additive for a resin. When used as an agent, the refractive index can be controlled without impairing various properties inherent to the resin, and the water absorption of the resin can be sufficiently reduced. Thus, the additive for resin comprising the phthalonitrile compound of the present invention is also one of the preferred embodiments of the present invention.

The present invention can also exhibit the same effect as an additive for resin having the following constitution.
That is, an additive for a resin comprising a phthalonitrile compound, the phthalonitrile compound having the following general formula (5);

(Wherein R ² is the same or different and represents F, Cl, Br, I, COOR ³ or OR ^3. R ³ represents a deuterated alkyl group or a fully halogenated alkyl group. P and q Are the same or different and are integers of 0 to 4. A is the same or different and is represented by the following general formula (6);

(In the formula, X is O or S. R ⁵ is the same or different and represents F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ^3. r is 0-5. It is an integer.) The additive for resin which is represented by this is also one aspect of the present invention.

In the phthalonitrile compound represented by the general formula (5), p represents the number of bonds of the A group to phthalonitrile, and is an integer of 0 to 4. Among these, the number is preferably 1, 2 or 3, more preferably 1 or 2, and even more preferably 1 in consideration of heat resistance. Q represents the number of bonds of the R ² group to phthalonitrile, and is an integer of 0 to 4. Among them, the number is preferably 1, 2 or 3, more preferably 2 or 3, and further preferably 3 in consideration of heat resistance. Note that the sum of p and q is preferably 4.

R ⁵ is the same or different and is a halogen atom, that is, a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br) or an iodine atom (I), a cyano group (CN), a trifluoromethyl group (CF ₃ ), COOR ³ or OR ^3, and at least one of R ⁵ is preferably a halogen atom. Thereby, it becomes possible to sufficiently satisfy both the refractive index control of the resin and the reduction in water absorption. The halogen atom is preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom. In this case, it is possible to more fully achieve both refractive index control and water absorption reduction. When a plurality of R ⁵ are present, they may be the same or different. R represents the number of bonds of the R ⁵ group and is an integer of 0 to 5. Especially, it is preferable that it is an integer of 1-5, More preferably, it is 5. The symbols other than R ⁵ , p, q, and r are as described above in the general formula (1).
Thus, it is preferable that p and q are n and m in the general formula (1) described above, respectively, and R ⁵ is R ¹ (or R ⁴ ) in the general formula (1). And r is preferably the total number of a and b in the general formula (1). That is, the compound represented by the general formula (5) is particularly preferably the one represented by the general formula (1).

The additive for resin of the present invention contains the phthalonitrile compound represented by the above general formula (6), but due to having such a structure, the heat of the resin such as a transparent resin. Thus, the effect of controlling the refractive index can be sufficiently exhibited without impairing various characteristics such as the optical characteristics.
In such a resin additive, the content ratio of the phthalonitrile compound is preferably 1 to 100% by mass, more preferably 20 to 100% by mass with respect to 100% by mass of the resin additive. It is.

The resin additive is preferably used by blending with the resin, and a resin composition comprising the resin additive is also one aspect of the present invention.
In such a resin composition, the content of the resin additive of the present invention is not particularly limited. For example, the phthalonitrile compound is 1 to 100 parts by weight with respect to 100 parts by weight of the resin. Is preferred. If it is less than 1 part by weight, the refractive index may not be sufficiently controlled, and the resin may not have a sufficiently low water absorption and water repellency. If it exceeds 100 parts by weight, basic properties such as transparency and mechanical strength that the resin may have may not be sufficiently exhibited. More preferably, it is 5-80 weight part, More preferably, it is 5-70 weight part.

The resin composition is not particularly limited as long as it contains a resin. Among them, it is preferable that the resin composition contains a polymer that forms a molded article having transparency. Such a polymer only needs to form a molded article having transparency, and the resin composition containing the polymer contains, for example, a transparent resin such as an acrylic resin as described later. Those are particularly preferred.
Here, the transparency means having a high light transmittance, and the resin composition containing a polymer that forms a transparent molded product has a total light transmittance of 70% or more. It points to what is. The total light transmittance is preferably 80% or more, and more preferably 90% 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. 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, calendar molding, powder molding, foam molding, laminate molding, and solvent casting are suitable.

As the transparent resin, acrylic resin, polycarbonate resin, fluorine resin, epoxy resin, polyether resin, polyester resin, polyarylate resin, polyimide resin, cycloolefin resin, silicon resin, norbornene Resins, polysulfone resins, polyketone resins, and the like are suitable, and one or more of these can be used. More preferred are acrylic resins and polycarbonate resins.
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 types of monomers. A mixture or copolymer of these acrylic resins is also suitable.
The polycarbonate resin preferably includes a polymer having a carbonate bond (—O—CO—O—) in the main chain.

The resin composition of the present invention includes optical films used for substrates, antireflection layers, refractive index control layers, optical compensation layers, optical communication materials such as optical fibers and optical waveguides, optical switches, recording materials such as optical recording disks, The liquid crystal display, plasma display, digital paper, organic EL, inorganic EL, rear pro, etc. can be used particularly suitably for various optical material applications, such as optical pickup lenses, fθ for laser beam printers, etc. Lenses such as lenses, eyeglass lenses, camera lenses, video camera lenses, and lamp lenses; discs such as video discs, audio discs, and write-once discs for computers; optical transmission materials such as plastic optical fibers (POF), optical connectors, and light guides Etc. can be used. An optical fiber, an optical waveguide, an optical recording disk, an optical film, and a display substrate using such a resin composition of the present invention are also one preferred embodiment of the present invention.

The phthalonitrile compound of the present invention is configured as described above, and can be suitably used for applications such as additives that can control the refractive index without impairing various properties such as thermal properties of resins such as transparent resins. Therefore, it can be particularly suitably used for various optical material applications such as optical fibers, optical waveguides, optical recording disks, optical films, display substrates and the like.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Note that “%” means “mass%” unless otherwise specified.
In the following examples and the like, ¹⁹ F-NMR measurement was performed under the following conditions.
< ¹⁹ F-NMR measurement conditions>
Structural analysis was performed by measuring F-NMR (376 MHz) spectrum using Unity Plus 400 (manufactured by Varian) and solvent heavy acetone. In the F-NMR spectrum, the position of F in hexafluorobenzene was set to 0 ppm as an internal standard.

Example 1
In a 500 mL four-necked flask equipped with a stirrer, cooling device, dropping funnel, thermometer, tetrachloroisophthalonitrile 10.00 g (37.61 mmol), potassium carbonate 1.04 g (7.52 mmol), ethyl methyl ketone 200 g And stirred under reflux conditions under nitrogen. The reaction was carried out for 3 hours while slowly dropping 0.69 g (3.76 mmol) of pentafluorophenol dissolved in 50 g of ethyl methyl ketone from the dropping funnel. After cooling, the mixture was filtered, and the filtrate was added to 1000 g of water to obtain a white solid. The resulting white solid was recrystallized from methanol to remove excess tetrachloroisophthalonitrile. 1.24 g (3.00 mmol) of the compound of the following formula was obtained. The yield was 80%.
Analysis using gas chromatography revealed that the target product had a purity of 90%.
¹⁹ F-NMR chemical shift (standard substance: hexafluorobenzene): 0.9 ppm, 3.9 ppm, 8.2 ppm

Example 2
0.2 g of the compound synthesized in Example 1 was added to 1.8 g of polymethyl methacrylate (PMMA) dissolved in 16.2 g of chloroform. The film was obtained by casting on a glass plate and drying. Each film was evaluated for thermal properties, refractive index and water absorption. The results of thermal characteristic evaluation are shown in Table 1, the results of refractive index are shown in Table 2, and the results of water absorption measurement are shown in Table 3.

Comparative Example 1
As a comparative example, the measurement was performed in the same manner as in Example 7 for the PMMA alone.
Methods for thermal property evaluation, refractive index and water absorption measurement are shown below.

(Thermal characteristics evaluation)
Using a Shimadzu differential thermogravimetric simultaneous measurement apparatus (manufactured by Shimadzu Corporation), the melting point, the glass transition temperature onset (glass transition start temperature) and the weight reduction temperature (5 mass% reduction) were measured. The heating temperature was 10 ° C./min under a nitrogen atmosphere.

(Measurement of water absorption rate)
The obtained film was dried at 130 ° C. for 10 hours, then immersed in water at 25 ° C. for 72 hours, the weight change was measured, and the moisture absorption rate was calculated.

(Refractive index measurement)
The refractive index at 632.8 nm, 830 nm, 1310 nm, and 1550 nm was measured using a prism coupler SPA-4000 (manufactured by SAIRON TECHNOLOGY).

Claims (4)

The following general formula (1);

(In the formula, R ² is the same or different and represents F, Cl, Br, I, COOR ³ or OR ^3. R ³ represents a deuterated alkyl group or a fully halogenated alkyl group. 1 is an integer of 1 to 4, m is an integer of 0 to 3, and n + m is 4. A is the same or different and is represented by the following general formula (2);

(In the formula, X is O or S. R ¹ is the same or different and represents F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ^3. R ⁴ is the same or different. F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ³ where a and b are each an integer of 1 to 5 and a + b = 5, provided that the general formula (1) In the case where the CN group is located at the meta position, X is O, R ¹ is CF ₃ , and R ⁴ is F, Cl, Br or I.) It is a group. A phthalonitrile compound represented by the formula: A method for producing the phthalonitrile compound according to claim 1,
The production method comprises the following general formula (3):

(In the formula, R ² is the same or different and represents F, Cl, Br, I, COOR ³ or OR ^3. R ³ represents a deuterated alkyl group or a fully halogenated alkyl group. A compound represented by the following general formula (4);

(In the formula, X is O or S. R ¹ is the same or different and represents F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ^3. R ⁴ is the same or different. Represents F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ^3. Each of a and b is an integer of 1 to 5, and a + b = 5, provided that the general formula (3) In the case where the CN group is located at the meta position, X is O, R ¹ is CF ₃ , and R ⁴ is F, Cl, Br or I.) A process for producing a phthalonitrile compound comprising a step of reacting with a compound. A resin additive comprising a phthalonitrile compound,
The phthalonitrile compound has the following general formula (5):

(Wherein R ² is the same or different and represents F, Cl, Br, I, COOR ³ or OR ^3. R ³ represents a deuterated alkyl group or a fully halogenated alkyl group. P and q Are the same or different and are integers of 0 to 4. A is the same or different and is represented by the following general formula (6);

(In the formula, X is O or S. R ⁵ is the same or different and represents F, Cl, Br, I, CN, CF ₃ , COOR ³ or OR ^3. r is 0-5. It is an integer.) The additive for resin characterized by the above-mentioned. A resin composition comprising the resin additive according to claim 3.