JP7418244B2 - Triazine ring-containing polymers and thermoplastic molded products, injection molded products, and optical parts containing the same - Google Patents

Description

The present invention relates to a triazine ring-containing polymer and thermoplastic molded articles, injection molded articles, and optical parts containing the same.

In recent years, research has been actively conducted on optical materials used in various cameras such as cameras and video cameras, and lenses for smartphones and the like. Optical materials for lenses are required to have high refractive index, low birefringence, and excellent heat resistance, light transmittance (transparency), and easy moldability. Compared to glass lenses, resin lenses have the advantage of being lighter, less likely to break, have lower material costs, and can be processed into various shapes through injection molding, which is suitable for lens molding. However, in recent years, in order to meet the needs for thinner products and higher pixel resolution for cameras, there has been a demand for materials with higher refractive indexes.

Attempts have been made to increase the refractive index of polymers, which are resin materials, by introducing aromatic rings, halogen atoms, and sulfur atoms. Among them, episulfide resins and thiourethane resins into which sulfur atoms have been introduced have a refractive index of 1.7 or more, but their practical application is limited because they lack plasticity.

Many polymers having triazine rings have been studied as high refractive resins with plasticity. For example, Patent Document 1 discloses a triazine ring-containing polymer that includes a repeating unit structure having a triazine ring and has a refractive index of 1.7 or more.

Japanese Patent Application Publication No. 2014-162829

However, the triazine ring-containing polymer described in Patent Document 1 has a problem in that it has high birefringence and cannot obtain sufficient optical properties.

Therefore, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an optical material that has both a high refractive index and low birefringence and can be injection molded.

The present inventors conducted extensive research in order to solve the above problems. As a result, they discovered that the above problem could be solved by combining a structural unit derived from a triazine dithiol compound and a structural unit derived from an aromatic hydrocarbon compound having a specific structure, and were able to complete the present invention. Ta.

That is, the triazine ring-containing polymer according to one embodiment of the present invention has a repeating unit represented by the following formula (1);

In formula (1), A each independently represents a group represented by the following formula (2), and B each independently represents a group represented by the following formula (3-1) to (3-3). represents a group;

In formula (2), L each independently represents a single bond or a linking group, and R ¹ represents a group consisting of an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N), and a selenium atom (Se). represents a group having at least one atom selected from the group;

In the formula (3-1), R ^2a and R ^2b are each independently an alkylene group having 1 to 10 carbon atoms or -(O-C _m H _2m ) _n - (in this case, m is 1 or more) represents an integer of 4 or less, n represents an integer of 1 or more and 3 or less), and Z ¹ and Z ² each independently represent a hydrogen atom or a condensed aromatic hydrocarbon ring (in this case, R ^3a , R ^3b , R ^4a and R ^4b each independently represent a substituent, n1 and n2 each independently represent 0, 1 or 2, m1 and m2 each independently represent 0 or represents an integer from 1 to 4);
In the formula (3-2), Z ³ and Z ⁴ each independently represent an aromatic hydrocarbon ring, and R ^5a , R ^5b , R ^6a and R ^6b each independently represent a substituent. R ^7a and R ^7b are each independently an alkylene group having 1 to 10 carbon atoms or -(O-C _m H _2m ) _n - (in this case, m represents an integer of 1 to 4, n represents an integer from 1 to 3), o1 and o2 each independently represent 0 or an integer from 1 to 4, and p1 and p2 each independently represent 0 or an integer from 1 to 4. represents an integer;
In the formula (3-3), R ^8a and R ^8b each independently represent a substituent, and R ^9a and R ^9b each independently represent an alkylene group having 1 to 10 carbon atoms or -( O-C _m H _2m ) _n - (in this case, m represents an integer of 1 to 4, n represents an integer of 1 to 3), and q1 and q2 each independently represent 0 or 1. Represents an integer greater than or equal to 4 and less than or equal to 4.

According to the present invention, it is possible to provide an optical material that has both a high refractive index and low birefringence and is injection moldable.

FIG. 3 is a diagram for explaining the mechanism by which birefringence decreases in the triazine ring-containing polymer according to the present invention.

Embodiments of the present invention will be described below, but the technical scope of the present invention should be determined based on the claims and is not limited to the following embodiments. In this specification, unless otherwise specified, operations and measurements of physical properties are performed at room temperature (20° C. or higher and 25° C. or lower)/relative humidity of 40% RH or higher and 50% RH or lower. In this specification, a "triazine ring-containing polymer" is also simply referred to as a "polymer."

<Triazine ring-containing polymer>
A triazine ring-containing polymer according to one embodiment of the present invention is characterized by having a repeating unit represented by the following formula (1).

[Constituent unit A]
The structural unit A is represented by the following formula (2).

As shown in formula (2), the structural unit A has a sulfur atom (S) bonded next to the triazine ring in the main chain. It is thought that this makes the glass transition temperature (Tg) of the polymer relatively low, making it suitable for injection molding.

In formula (2), L each independently represents a single bond or a connecting group. Here, L being a single bond means that the triazine ring and the substituent R ¹ are directly connected. In addition, when L is a linking group, the linking group is not particularly limited as long as it does not impede the effects of the present invention, but alkylene groups having 1 to 6 carbon atoms (e.g., methylene group, ethylene group, trimethylene group, (propylene group, tetramethylene group, 2-methyltrimethylene group, 1-methyltrimethylene group, 1-ethylethylene group, 1,2-dimethylethylene group, 1,1-dimethylethylene group, etc.), carbon number 6 Examples include divalent aromatic hydrocarbon groups having 14 or less (eg, phenylene, naphthylene, etc.). Among these, from the viewpoint of improving refractive index, heat resistance, etc., L is preferably a single bond, a phenylene group, or a methylene group, more preferably a single bond or a phenylene group, and L is a single bond. is even more preferable.

In formula (2), R ¹ is each independently at least one atom selected from the group consisting of oxygen atom (O), sulfur atom (S), nitrogen atom (N), and selenium atom (Se). represents a group having Here, specific examples of R ¹ are not particularly limited as long as they do not inhibit the effects of the present invention, but groups represented by the following formulas (4-1) to (4-9) are preferably mentioned.

In formulas (4-1), (4-6) and (4-8), o is each independently an integer of 1 or more and 6 or less. From the viewpoint of improving the refractive index, heat resistance, etc., each o is independently preferably an integer of 1 or more and 3 or less, more preferably 1 or 2. Preferred specific examples include the following groups.

In formulas (4-3), (4-7) and (4-9), p is each independently an integer of 1 or more and 6 or less. From the viewpoint of improving the refractive index, heat resistance, etc., n is preferably an integer of 1 or more and 3 or less, and more preferably 1 or 2, each independently. Preferred specific examples include the following groups.

In formula (4-5), q is each independently an integer of 1 or more and 6 or less. From the viewpoint of improving the refractive index, heat resistance, etc., q is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, each independently. Preferred specific examples include the following groups.

Among these, from the viewpoint of improving refractive index, heat resistance, etc., it is more preferable that R ¹ is each independently a group represented by formulas (4-1) to (4-5). That is, in a preferred embodiment of the present invention, R ¹ is each independently selected from the groups represented by formulas (4-1) to (4-5). More preferably selected from groups represented by formulas (4-1), (4-4) and (4-5), still more preferably groups represented by formulas (4-4) and (4-5). and particularly preferably selected from the group represented by formula (4-4).

[Constituent unit B]
Structural unit B represents a group selected from the following formulas (3-1) to (3-3).

In formula (3-1), R ^2a and R ^2b are each independently an alkylene group having 1 to 10 carbon atoms or -(O-C _m H _2m ) _n - (in this case, m is 1 to 4 represents the following integer, n represents an integer from 1 to 3), and Z ¹ and Z ² each independently represent a hydrogen atom or a condensed aromatic hydrocarbon ring (in this case, R ^3a , R ^3b , R ^4a and R ^4b each independently represent a substituent, n1 and n2 each independently represent 0, 1 or 2, and m1 and m2 each independently represent 0 or 1. represents an integer greater than or equal to 4 and less than or equal to 4).

In formula (3-2), Z ³ and Z ⁴ each independently represent an aromatic hydrocarbon ring, and R ^5a , R ^5b , R ^6a and R ^6b each independently represent a substituent. , R ^7a and R ^7b are each independently an alkylene group having 1 to 10 carbon atoms or -(O-C _m H _2m ) _n - (in this case, m represents an integer of 1 to 4, and n represents an integer of 1 to 3), o1 and o2 each independently represent 0 or an integer of 1 to 4, p1 and p2 each independently represent 0 or an integer of 1 to 4 represents.

In formula (3-3), R ^8a and R ^8b each independently represent a substituent, and R ^9a and R ^9b each independently represent an alkylene group having 1 to 10 carbon atoms or -(O -C _m H _2m ) _n - (in this case, m represents an integer of 1 to 4, and n represents an integer of 1 to 3), and q1 and q2 are each independently 0 or 1 or more. Represents an integer less than or equal to 4.

The group represented by formula (3-1) includes a group represented by the following formula.

The definitions of R ^2a , ^2b , Z ¹ , Z ² , R ^3a , R ^3b , R ^4a , R ^4b , n1, n2, m1, and m2 in these formulas are the same as those in formula (3-1). It is.

In formulas (3-1) to (3-3), the alkylene group having 1 or more and 10 or less carbon atoms includes a methylene group (-CH ₂ -), an ethylene group (-CH ₂ CH ₂ -), and a trimethylene group (- _CH2CH2CH2- ), propylene group (-CH _{( CH3 ) CH2-} ), 2 _- ethylhexamethylene group ( _{-CH2CH ( CH2CH3 ) CH2CH2CH2CH2- )} Examples include straight chain and branched alkylene groups such as. Among these, ethylene group and trimethylene group are preferred.

In formulas (3-1) to (3-3), m in the alkyleneoxy group (-(O-C _m H _2m ) _n -) represents an integer of 1 or more and 4 or less, and 2 is preferable. Further, n represents an integer of 1 or more and 3 or less, and 1 is preferable. Preferred specific examples of the alkyleneoxy group (-(O-C _m H _2m ) _n -) include -O-CH ₂ -, -O-CH ₂ CH ₂ -, -O-CH ₂ CH ₂ CH ₂ -, Examples include -O-CH(CH ₃ )CH ₂ -, -(O-CH ₂ ) ₂ -, -(O-CH ₂ CH ₂ ) ₂ -, and the like.

In formulas (3-1) and (3-2), examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, a benzene ring and a naphthalene ring are preferred, and a benzene ring is more preferred.

In formulas (3-1) to (3-3), the substituents include an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, Examples include a secondary or tertiary amino group having 1 to 30 carbon atoms, a cyano group, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and a heteroaryl group having 3 to 30 ring atoms. Among these, an alkyl group having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 12 carbon atoms are preferred.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and isopentyl group. group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n- Heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl- 1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, etc. can be mentioned. Among these, methyl, ethyl, and n-propyl groups are preferred.

Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include phenyl group, biphenyl group, fluorenyl group, naphthyl group, and the like. Among these, phenyl group, biphenyl group, and naphthyl group are preferred.

According to a preferred form, in formula (3-1), Z ¹ and Z ² represent a benzene ring, and R ^3a , R ^3b , R ^4a and R ^4b are an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms. Represents an aromatic hydrocarbon group of 6 or more and 12 or less; in formula (3-2), Z ³ and Z ⁴ represent a benzene ring, and R ^5a , R ^5b , R ^6a and R ^6b each independently represent , represents an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms; in formula (3-3), R ^8a and R ^8b each independently represent an alkyl group having 1 to 10 carbon atoms; Represents an alkyl group having 10 or less or an aromatic hydrocarbon group having 6 or more and 12 or less carbon atoms.

According to studies conducted by the present inventors, it has been found that the birefringence of the triazine ring-containing polymer according to the present invention becomes significantly smaller when an external force is applied to the polymer by injection molding, stretching, or the like. This is because when an external force is applied, the triazine ring in structural unit A coordinates parallel to the main chain in the polymer, whereas the aromatic hydrocarbon groups (binaphthalene ring, biphenyl ring, This is thought to be because the fluorene rings (fluorene rings, fluorene rings) are oriented orthogonally to the main chain (Figure 1). Such effects are achieved by introducing a specific aromatic hydrocarbon group (binaphthalene ring, biphenylfluorene ring, fluorene ring) as the structural unit B, as well as by introducing R ^2a and R ^2b of formula (3-1), A linking group (linker) of appropriate length (length of 1 to 6 atoms) such as R ^7a and R ^7b in (3-2) or R ^9a and R ^9b in formula (3-3). ) is presumed to be produced by bonding to the triazine ring in the structural unit A.

The triazine ring-containing polymer according to the present invention may contain repeating units other than the repeating unit represented by formula (1) (hereinafter also referred to as "other repeating units"). However, from the viewpoint of satisfactorily exhibiting the effects of the present invention, it is preferable that other repeating units are not included. Even when other repeating units are included, the ratio of the number of other repeating units to the total number of repeating units is preferably 10% or less. More preferably, it is 5% or less, still more preferably 3% or less, particularly preferably 1% or less (lower limit 0%). If the ratio of other repeating units is within the above range, it is possible to prevent a decrease in refractive index, an increase in birefringence, and difficulty in molding processes such as injection molding.

When the triazine ring-containing polymer contains two or more types of repeating units (ie, when it is a copolymer), the arrangement form of the repeating units is not particularly limited. The arrangement form may be block-like (block copolymer), random (random copolymer), or alternately arranged (alternating copolymer).

The terminal end of the triazine ring-containing polymer according to the present invention is not particularly limited, but the terminal end may be capped with a hydrocarbon group (for example, an alkyl group, an aromatic hydrocarbon group, or a combination thereof). preferable. In particular, it is preferable that at least some of the hydrogen atoms of the terminal SH groups are substituted with hydrocarbon groups. By sealing the end portion in this manner, coloring and haze of the polymer can be reduced.

The refractive index n _d of the triazine ring-containing polymer according to the present invention is, for example, 1.68 or more, preferably 1.69 or more, more preferably 1.7 or more, and still more preferably 1.71 or more. be. In addition, in this specification, the refractive index n _d employs a value measured by the method described in Examples below.

The birefringence of the triazine ring-containing polymer according to the present invention is, for example, 300×10 ⁻⁴ or less, preferably 100×10 ⁻⁴ or less, more preferably 60×10 ⁻⁴ or less, and still more preferably 40×10 −4 or less. ×10 ⁻⁴ or less, particularly preferably 30×10 ⁻⁴ or less, and most preferably 20×10 ⁻⁴ or less. In addition, in this specification, the value measured by the method described in the below-mentioned Example is adopted as birefringence.

The triazine ring-containing polymer according to the present invention has a glass transition temperature (Tg). That is, an inflection point is observed in the differential calorimetry curve obtained by differential scanning calorimetry. A resin having such a glass transition temperature has thermoplasticity and can be processed by injection molding. The glass transition temperature of the triazine ring-containing polymer is preferably 80°C or higher and 180°C or lower, more preferably 100°C or higher and 160°C or lower. The glass transition temperature can be adjusted by controlling the structure of the structural unit A and/or the structural unit B. For example, by introducing a bulky structure or a rigid structure into R ¹ in formula (2), the glass transition temperature can be increased. Conversely, the length of the connecting group (linker) of R ^2a and R ^2b in formula (3-1), R ^7a and R ^7b in formula (3-2), or R ^9a and R ^9b in formula (3-3) By increasing the length, the glass transition temperature can be lowered. In addition, in this specification, the glass transition temperature employ|adopts the value measured by the method described in the below-mentioned Example.

The weight average molecular weight (Mw) of the triazine ring-containing polymer is preferably 5,000 or more and 1,000,000 or less, more preferably more than 5,000 and 300,000 or less, and particularly preferably It is more than 20,000 and less than 200,000. When the weight average molecular weight is within the above numerical range, the molded article has particularly excellent transmittance (transparency) and heat resistance, and also has the advantage that the obtained molded article has excellent mechanical strength. The method of controlling the weight average molecular weight within the above numerical range is not particularly limited, but includes a method of controlling the polymerization reaction time. In addition, in this specification, the weight average molecular weight employ|adopts the value measured by the method described in the below-mentioned Example.

The method for producing the triazine ring-containing polymer according to the present invention is not particularly limited. To give an example, first, as shown in the formula below, a triazine dithiol compound and an aromatic compound having a leaving group (in the formula (3-1), n1, n2, m1 and m2 are A polymer is obtained by reacting a compound in which a leaving group is bonded to a certain structural unit in the presence of a phase transfer catalyst. Thereafter, the triazine ring-containing polymer according to the present invention can be produced by reacting the polymer and a sealing agent in the presence of a phase transfer catalyst, if necessary.

In the formula, R ¹ has the same definition as in formula (2), R ^2a and R ^2b have the same definition as in formula (3-1), and each X independently represents a leaving group. represents.

Specific examples of X (leaving group) include fluorine atom, chlorine atom, bromine atom, iodine atom, tosyl group (p-toluenesulfonyl group), triflate group (trifluoromethylsulfonyl group), methanesulfonyl group, and chloromethyl group. Examples include sulfonyl group and nitro group.

The triazinedithiol compound is not particularly limited, but includes, for example, 2-methylthio-1,3,5-triazine-4,6-dithiol, 2-ethylthio-1,3,5-triazine-4,6-dithiol, 2-ethylthio-1,3,5-triazine-4,6-dithiol, -benzylthio-1,3,5-triazine-4,6-dithiol, 2-(2'-phenylethylthio)-1,3,5-triazine-4,6-dithiol, 2-methoxy-1,3, 5-triazine-4,6-dithiol, 2-ethoxy-1,3,5-triazine-4,6-dithiol, 2-benzyloxy-1,3,5-triazine-4,6-dithiol, 2-anilino Examples include -1,3,5-triazine-4,6-dithiol and 2-(N-methylanilino)-1,3,5-triazine-4,6-dithiol. Examples of aromatic compounds having a leaving group include 9,9-bis(6-(2-chloroethoxy)-(1,1'-biphenyl)-3-yl)fluorene, 9,9-bis(6 -(2-bromoethoxy)-(1,1'-biphenyl)-3-yl)fluorene, 2,2'-bis(2-chloroethoxy)-1,1'-binaphthyl, 2,2'-bis( 2-bromoethoxy)-1,1'-binaphthyl, 9,9-bis(4'-(2''-chloroethoxy)phenyl)fluorene, 9,9-bis(4'-(2''-bromoethoxy) ) phenyl)fluorene, 9,9-bis(4'-(3'-chloropropyl)fluorene, 9,9-bis(4'-(3'-bromopropyl)fluorene), etc. can be used. One type can be used alone or two or more types can be used in combination.

As the capping agent, a compound in which a leaving group is bonded to the above-mentioned hydrocarbon group can be used. Here, the leaving group is the same as X above, and includes a fluorine atom, chlorine atom, bromine atom, iodine atom, tosyl group (p-toluenesulfonyl group), triflate group (trifluoromethylsulfonyl group), and nitro group. Can be mentioned. Specific examples of the sealant include benzyl chloride, benzyl bromide, 2-bromoethylbenzene, bromomethane, iodomethane, α-chloro-p-xylene, α-chloro-o-xylene, 1-(chloromethyl)naphthalene, etc. It will be done. These can be used alone or in combination of two or more.

The phase transfer catalyst used for the reaction between the triazine dithiol compound and the aromatic compound having a leaving group and/or the reaction between the polymer and the sealing agent is a long-chain alkyl quaternary catalyst that can be used for interfacial polycondensation. Preferred are ammonium salts, crown ethers, and the like. More specifically, for example, tetrabutylammonium bromide, hexadecyltrimethylammonium bromide, etc. can be preferably used.

The reaction system can be a two-phase system of water and an organic solvent, and is preferably a two-phase system of water and an organic solvent such as chloroform, dichloromethane, cyclohexanone, benzonitrile, or nitrobenzene. During the reaction, it is preferable to add a base such as sodium hydroxide or potassium hydroxide and carry out the reaction at -10°C or more and 100°C or less for 1 hour or more and 120 hours or less.

The triazine ring-containing polymer obtained above may be purified by a general purification method such as reprecipitation method, dialysis method, ultrafiltration method, or extraction method. Further, the obtained triazine ring-containing polymer may be dried, for example, under vacuum at a temperature ranging from room temperature to 120° C. in order to completely remove residual solvent contained in the polymer. Using the polymer from which the residual solvent was completely removed in this manner, evaluations of refractive index, birefringence, glass transition temperature, etc. were performed.

<Thermoplastic molded products, injection molded products, optical parts>
Another aspect of the present invention relates to a thermoplastic molded article containing the above triazine ring-containing polymer. Yet another embodiment of the present invention relates to an injection molded article formed by injection molding the above triazine ring-containing polymer. Yet another embodiment of the present invention relates to an optical component containing the above triazine ring-containing polymer.

The shape of the molded product is not particularly limited, and may be any form such as a lens shape (spherical lens, aspherical lens, Fresnel lens, etc.), film shape, sheet shape, plate shape, rod shape, fiber shape, prism shape, etc. It's good to be there.

When manufacturing molded products, for example, injection molding method, compression molding method, extrusion molding method, transfer molding method, blow molding method, pressure molding method, stretching method, coating method (spin coating method, roll coating method, curtain coating method) are used. A known molding method such as a molding method, a dip coating method, a casting molding method, etc.) can be used. Among these, the composition according to the invention is particularly suitable for injection molding. As described above, even when an external force is applied to the polymer during injection molding, it is possible to avoid an increase in birefringence. This is because the triazine ring in structural unit A is coordinated parallel to the main chain, whereas the aromatic hydrocarbon groups (binaphthalene ring, biphenylfluorene ring, fluorene ring) in structural unit B are aligned parallel to the main chain. This is thought to be due to the orientation being perpendicular to the surface. For example, in the case of injection molding, the external force at this time is preferably 100 1/s or more in terms of shear rate. As long as a similar external force is applied, the molding method is not limited to injection molding, but may also include stretching, compression molding, extrusion, transfer molding, blow molding, pressure molding, stretching, A method such as a coating method (spin coating method, roll coating method, curtain coating method, dip coating method, casting molding method, etc.) may be used. Before molding, the raw materials may be mixed using a kneader such as a Henschel mixer, kneader, Banbury mixer, or extruder. When molding is performed by injection molding, the cylinder temperature is, for example, 150°C or more and 300°C or less, and the mold temperature is 50°C or more and 100°C or less.

The optical components mentioned above include displays (e.g., smartphone displays, liquid crystal displays, plasma displays, etc.), photographic devices (e.g., cameras and videos, etc.), optical pickups, projectors, optical fiber communication devices (e.g., optical amplifiers, etc.), and automobiles. It can be suitably used as an optical component that transmits light (passive optical component) in a headlamp or the like. Examples of such passive optical components include lenses, films, optical waveguides, prisms, prism sheets, panels, optical disks, and LED sealants. Such an optical component may have various functional layers such as an antireflection layer, a light absorption layer, a hard coat layer, and an antiglare layer, if necessary.

EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but these are not intended to limit the present invention in any way. In the following description, all "parts" mean "parts by mass" unless otherwise specified.

<Method for measuring physical property values>
(Number average molecular weight (Mn) and weight average molecular weight (Mw))
A measurement sample was obtained by dissolving the polymer in N-methyl-2-pyrrolidone (NMP) to a concentration of 0.1% by mass and filtering it through a polytetrafluoroethylene membrane filter with a pore size of 0.2 μm. The number average molecular weight and weight average molecular weight were measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a mobile phase and a differential refractometer as a detector. Monodisperse polystyrene was used as a standard substance for molecular weight.
[Example 1] Synthesis of triazine ring-containing polymer (4)

Under a nitrogen atmosphere, 9,9-bis(4'-(2''-hydroxyethoxy)phenyl)fluorene (1) (8.8 g, 20 mmol) was placed in a 200 mL eggplant-shaped flask and dissolved in dichloromethane (100 mL). . After cooling this solution to 0° C., carbon tetrabromide (15.9 g, 48 mmol) was added, and triphenylphosphine (12.6 g, 48 mmol) was added little by little in multiple portions. After stirring for 2 hours, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent, hexane/ethyl acetate = 5/1), and 9,9-bis(4'-(2''-bromoethoxy)phenyl)fluorene (2) (10.5 g ) was obtained as colorless crystals.

2-anilino-1,3,5-triazine-4,6-dithiol (3) (1.0 g, 4.2 mmol) was placed in a 30 mL flask, and water (3.5 mL) and sodium hydroxide (0.34 g, 8.6 mmol) was added and stirred. To this mixture were added 9,9-bis(4'-(2''-bromoethoxy)phenyl)fluorene (2) (2.37 g, 4.2 mmol) and cyclohexanone (10 mL). Tetrabutylammonium bromide (0.1 g) was added to this mixed solution, and the mixture was heated to 50° C. and stirred. After 12 hours, α-chloro-p-xylene (0.1 mL) was added, and the mixture was further stirred for 4 hours. After cooling to room temperature, the mixture was washed three times with water, and the organic layer was added to isopropanol (100 mL). Triazine ring-containing polymer (4) (2.3 g) was obtained by filtering the precipitated white solid. The obtained polymer had a number average molecular weight of 6,100 and a weight average molecular weight of 51,800.

[Example 2] Synthesis of triazine ring-containing polymer (7)

Under a nitrogen atmosphere, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (5) (3.7 g, 10 mmol) was placed in a 200 mL eggplant flask and dissolved in dichloromethane (50 mL). After cooling this solution to 0° C., carbon tetrabromide (8.0 g, 24 mmol) was added, and triphenylphosphine (6.3 g, 24 mmol) was added little by little in multiple portions. After the reaction solution was heated to room temperature and stirred for 12 hours, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 1/1) to obtain 2,2'-bis(2-bromoethoxy)-1,1'-binaphthyl (6) (4.0 g). Obtained as white needle-like crystals.

2-anilino-1,3,5-triazine-4,6-dithiol (3) (0.4 g, 1.6 mmol) was placed in a 30 mL flask, and water (1.5 mL) and sodium hydroxide (0.13 g, 3.3 mmol) was added and stirred. 2,2'-bis(2-bromoethoxy)-1,1'-binaphthyl (6) (0.8, 1.6 mmol) and cyclohexanone (3 mL) were added to this mixture. Tetrabutylammonium bromide (0.1 g) was added to this mixed solution, and the mixture was heated to 70° C. and stirred. After 12 hours, α-chloro-p-xylene (0.1 mL) was added, and the mixture was further stirred for 4 hours. After cooling to room temperature, the mixture was washed three times with water, and the organic layer was added to isopropanol (50 mL). The precipitated white solid was collected by filtration to obtain triazine ring-containing polymer (7) (0.7 g). The obtained polymer had a number average molecular weight of 8,500 and a weight average molecular weight of 67,000.

[Example 3] Synthesis of triazine ring-containing polymer (10)

Under a nitrogen atmosphere, 9,9-bis(6-(2-hydroxyethoxy)-(1,1'-biphenyl)-3-yl)fluorene (8) (10 g, 17 mmol) was placed in a 200 mL eggplant flask, and dichloromethane was added. (60 mL). After cooling this solution to 0° C., carbon tetrabromide (13 g, 40 mmol) was added, and triphenylphosphine (10 g, 40 mmol) was added little by little in multiple portions. After the reaction solution was heated to room temperature and stirred for 12 hours, the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: hexane/dichloromethane = 1/1) to give 9,9-bis(6-(2-bromoethoxy)-(1,1'-biphenyl)-3-yl). Fluorene (9) (7.3 g) was obtained as a white powder.

2-anilino-1,3,5-triazine-4,6-dithiol (3) (1.0 g, 4.2 mmol) was placed in a 30 mL flask, and water (3.5 mL) and sodium hydroxide (0.34 g, 8.6 mmol) was added and stirred. Add 9,9-bis(6-(2-bromoethoxy)-(1,1'-biphenyl)-3-yl)fluorene (9) (2.9 g, 4.2 mmol) and cyclohexanone (10 mL) to this mixture. added. Tetrabutylammonium bromide (0.1 g) was added to this mixed solution, and the mixture was heated to 70° C. and stirred. After 12 hours, α-chloro-p-xylene (0.1 mL) was added, and the mixture was further stirred for 4 hours. After cooling to room temperature, the mixture was washed three times with water, and the organic layer was added to isopropanol (100 mL). The precipitated white solid was collected by filtration to obtain triazine ring-containing polymer (10) (3.1 g). The obtained polymer had a number average molecular weight of 13,700 and a weight average molecular weight of 154,000.

[Example 4] Synthesis of triazine ring-containing polymer (13)

In Example 3, 9,9-bis(3'-hydroxypropyl)fluorene (11) was used as a raw material instead of 9,9-bis(4'-(2''-hydroxyethoxy)phenyl)fluorene (8). ) was used in the same manner as in Example 3 to obtain 9,9-bis(3'-bromopropyl)fluorene (12) as colorless crystals. The yield was 80%.

In Example 3, 9,9-bis(3'-bromopropyl)fluorene (12) was used as a comonomer instead of 9,9-bis(4'-(2''-bromoethoxy)phenyl)fluorene (9). ) A triazine ring-containing polymer (13) was obtained in the same manner as in Example 3, except that the compound (13) was used. The obtained polymer had a number average molecular weight of 15,300 and a weight average molecular weight of 120,800.

[Example 5] Synthesis of triazine ring-containing polymer (18)

Potassium tert-butoxide (3.4 g, 30 mmol) was placed in a 100 mL flask under a nitrogen atmosphere, dispersed in THF (10 mL), and then cooled to 0°C. Fluorene (14) (1.7 g, 10 mmol) was dissolved in THF (10 mL) and added dropwise to the flask. After stirring for 30 minutes, tert-butyl bromoacetate (5.9 g, 30 mmol) was added dropwise, followed by stirring for 3 hours. After adding water and ethyl acetate, the organic layer was separated and the solvent was distilled off under reduced pressure to obtain di-tert-butyl fluorene-9,9-diacetate (15) (3.5 g).

Lithium aluminum hydride (0.8 g, 20 mmol) was placed in a 100 mL flask under a nitrogen atmosphere, dispersed in THF (35 mL), and then cooled to 0°C. Di-tert-butyl fluorene-9,9-diacetate (15) (3.9 g, 10 mmol) was dissolved in THF (6 mL) and added dropwise to the flask. After stirring at room temperature for 2 hours, saturated aqueous Rochelle salt solution (20 mL) was added dropwise. After separating the organic layer, the solvent was distilled off. After adding dichloromethane, the solid was collected by filtration to obtain fluorene-9,9-diethanol (16) (1.0 g) in a yield of 40%.

Under a nitrogen atmosphere, fluorene-9,9-diethanol (16) (1.0 g, 3.9 mmol), triethylamine (1.2 g, 12 mmol), and trimethylamine hydrochloride (76 mg, 0.8 mmol) were placed in a 100 mL eggplant-shaped flask. and dissolved in dichloromethane (15 mL). After cooling this solution to 0° C., a dichloromethane solution (1 mL) of mesyl chloride (1.4 g, 12 mmol) was added dropwise. After 30 minutes, a saturated aqueous sodium bicarbonate solution was added, the organic layer was separated, and the solvent was distilled off. After adding methanol to the residue, the solid was collected by filtration to obtain 9,9-bis(2'-mesyloxyethyl)fluorene (17) (1.5 g) in a yield of 92%.

In Example 4, 9,9-bis(2'-mesyloxyethyl)fluorene (17) was used as a reaction solvent instead of 9,9-bis(3'-bromopropyl)fluorene (12) as a comonomer. A triazine ring-containing polymer (18) was obtained in the same manner as in Example 4, except that nitrobenzene was used instead of cyclohexanone. The obtained polymer had a number average molecular weight of 7,700 and a weight average molecular weight of 21,200.

[Comparative Example 1] Synthesis of triazine ring-containing polymer (20)

2-anilino-1,3,5-triazine-4,6-dithiol (3) (2.0 g, 8.5 mmol) was placed in a 30 mL flask, and water (6.0 mL) and sodium hydroxide (0.70 g, 17.4 mmol) was added and stirred. To this mixture were added α,α'-dichloro-p-xylene (19) (1.42 g, 8.2 mmol) and cyclohexanone (10 mL). Tetrabutylammonium bromide (0.14 g) was added to this mixed solution, and the mixture was heated to 50° C. and stirred. After 12 hours, α-chloro-p-xylene (0.23 mL) was added, and the mixture was further stirred for 4 hours. After cooling to room temperature, the mixture was washed three times with water, and the organic layer was added to isopropanol (100 mL). Triazine ring-containing polymer (20) (2.1 g) was obtained by filtering the precipitated white solid. The obtained polymer had a number average molecular weight of 19,000 and a weight average molecular weight of 175,000.

[Comparative Example 2] Synthesis of triazine ring-containing polymer (22)

2-(N-methylanilino)-1,3,5-triazine-4,6-dithiol (21) (2.0 g, 8.0 mmol) was placed in a 30 mL flask, and water (6.0 mL) and sodium hydroxide ( 0.66 g, 16.4 mmol) was added and stirred. To this mixture were added α,α'-dichloro-p-xylene (19) (1.34 g, 7.7 mmol) and cyclohexanone (10 mL). Tetrabutylammonium bromide (0.13 g) was added to this mixed solution, and the mixture was heated to 50° C. and stirred. After 12 hours, α-chloro-p-xylene (0.22 mL) was added, and the mixture was further stirred for 4 hours. After cooling to room temperature, the mixture was washed three times with water, and the organic layer was added to isopropanol (100 mL). Triazine ring-containing polymer (22) (2.0 g) was obtained by filtering the precipitated white solid. The obtained polymer had a number average molecular weight of 6,400 and a weight average molecular weight of 79,200.

[Comparative Example 3] Synthesis of triazine ring-containing polymer (25)

30 mL of 2-phenylamino-4,6-dichlorotriazine (23) (1.0 g, 4.1 mmol) and 9,9-bis(4-aminophenyl)fluorene (24) (1.45 g, 4.1 mmol) The mixture was placed in a flask and dissolved in N,N-dimethylacetamide (8 mL). After adding triethylamine (1.7 mL, 12.4 mmol) to this solution, it was heated to 100° C. and stirred for 2 days. After adding aniline (1.1 mL) to stop the reaction, the mixture was stirred for 2 hours. After cooling to room temperature, it was added dropwise to water (100 mL) in which potassium carbonate (2.3 g) was dissolved. After the precipitate was collected by filtration, it was dissolved in tetrahydrofuran (50 mL). The tetrahydrofuran solution was added dropwise to a hexane-ethanol mixed solution (150 mL, hexane/ethanol = 4/1) to perform reprecipitation, and the precipitated light pink solid was collected by filtration to obtain triazine ring-containing polymer (25) (1.6 g). ) was obtained. The obtained polymer had a number average molecular weight of 6,700 and a molecular weight of 24,400.

<Evaluation>
(Refractive index n _d )
2 g of polymer was compression molded for 5 minutes at 200° C. and 10 MPa to produce a molded plate measuring 3 cm long x 3 cm wide and 0.5 mm thick. The refractive index n _d of the obtained molded plate at the d-line (587.6 nm) was measured using an Abbe refractometer (DR-M4, manufactured by ATAGO).

(birefringence)
Molding processing Vol. 27 No. Birefringence was measured using the method described in 3 2015, pages 94-97. Specifically, a rectangular molded plate (width 1 cm x length 5 cm x thickness 0.6 mm) was produced using a heat press machine (IMC-16DE manufactured by Imoto Seisakusho), and 5 points above and below were marked at 5 mm intervals from the center. . This molded plate was stretched three times at a temperature 10° C. higher than Tg using a uniaxial stretching machine (IMC-18AF manufactured by Imoto Seisakusho). The retardation of the stretched formed plate was measured using a retardation measuring device (PETS-100 manufactured by Otsuka Electronics Co., Ltd.) (measured at 5 points marked in advance). The value of birefringence was determined based on retardation/thickness.

(Glass transition temperature (Tg))
Using a differential scanning calorimeter (DSC) (DSC6200, manufactured by SII), the sample was heated to 300°C at a heating rate of 10°C/min, held for 10 minutes, and then heated to 25°C at a cooling rate of 10°C/min. and held for 10 minutes. Thereafter, the sample was heated to 300° C. at a heating rate of 10° C./min, and the glass transition temperature (Tg) was measured. After the measurement was completed, the sample was cooled to room temperature (25°C) at a rate of 10°C/min. Note that injection molding is possible if the glass transition temperature (Tg) is 180° C. or lower.

The results are shown in Table 1.

As shown in Table 1, the triazine ring-containing polymer according to the present invention was shown to have both a high refractive index equivalent to that of the polymer of the comparative example and a birefringence significantly lower than that of the comparative example. . This effect was obtained by specifying the structural unit B. It was also shown that the triazine ring-containing polymer according to the present invention has a glass transition temperature (Tg) of 180° C. or less and has thermoplasticity.

Next, the fluidity of the polymer was evaluated.

(Melt flow rate (MFR) measurement)
Melt flow rate (MFR) was evaluated in accordance with "JIS K7210". The cylinder of Melt Indexer C-5059D2 (Toyo Seiki Seisakusho Co., Ltd.) was filled with resin, and the MFR (g/10 min) was measured at 280° C. by applying a load (2.16 kg).

The results are shown in Table 2.

As shown in Table 2, the triazine ring-containing polymer according to the present invention having a Tg of 180°C or less had good MFR measurement results, indicating that it had injection moldability.

Claims (7)

A triazine ring-containing polymer having a repeating unit represented by the following formula (1);

In the formula (1), A each independently represents a group represented by the following formula (2), and B is each independently selected from the following formulas (3-1) to (3-3). represents a group;

In the formula (2), L each independently represents a single bond or a connecting group, and R ¹ represents an oxygen atom (O), a sulfur atom (S), a nitrogen atom (N), and a selenium atom (Se). represents a group having at least one atom selected from the group consisting of;

In the formula (3-1), R ^2a and R ^2b are each independently an alkylene group having 1 to 10 carbon atoms or -(O-C _m H _2m ) _n - (in this case, m is 1 or more) represents an integer of 4 or less, n represents an integer of 1 or more and 3 or less), and Z ¹ and Z ² each independently represent a hydrogen atom or a condensed aromatic hydrocarbon ring (in this case, R ^3a , R ^3b , R ^4a and R ^4b each independently represent a substituent, n1 and n2 each independently represent 0, 1 or 2, m1 and m2 each independently represent 0 or represents an integer from 1 to 4);
In the formula (3-2), Z ³ and Z ⁴ each independently represent an aromatic hydrocarbon ring, and R ^5a , R ^5b , R ^6a and R ^6b each independently represent a substituent. R ^7a and R ^7b are each independently an alkylene group having 1 to 10 carbon atoms or -(O-C _m H _2m ) _n - (in this case, m represents an integer of 1 to 4, n represents an integer from 1 to 3), o1 and o2 each independently represent 0 or an integer from 1 to 4, and p1 and p2 each independently represent 0 or an integer from 1 to 4. represents an integer;
In the formula (3-3), R ^8a and R ^8b each independently represent a substituent, and R ^9a and R ^9b each independently represent an alkylene group having 1 to 10 carbon atoms or -( O-C _m H _2m ) _n - (in this case, m represents an integer of 1 to 4, n represents an integer of 1 to 3), and q1 and q2 each independently represent 0 or 1. Represents an integer greater than or equal to 4 and less than or equal to 4. The triazine ring-containing polymer according to claim 1, wherein in the formula (2), L represents a single bond. In the formula (2), R ₁ is each independently selected from groups represented by the following formulas (4-1) to (4-5), the triazine ring-containing compound according to claim 1 or 2. polymer;

In the formula (4-1), o is each independently an integer of 1 or more and 6 or less,
In the formula (4-3), p is each independently an integer of 1 or more and 6 or less,
In the formula (4-5), q is each independently an integer of 1 or more and 6 or less. In the formula (3-1), Z ¹ and Z ² represent a benzene ring, and R ^3a , R ^3b , R ^4a and R ^4b are an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 6 to 12 carbon atoms. represents an aromatic hydrocarbon group;
In the formula (3-2), Z ³ and Z ⁴ represent a benzene ring, and R ^5a , R ^5b , R ^6a and R ^6b each independently represent an alkyl group having 1 to 10 carbon atoms or a carbon Represents an aromatic hydrocarbon group having a number of 6 or more and 12 or less;
In the formula (3-3), R ^8a and R ^8b each independently represent an alkyl group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, 3. The triazine ring-containing polymer according to any one of 3. A thermoplastic molded article comprising the triazine ring-containing polymer according to any one of claims 1 to 4. An injection molded article obtained by injection molding the triazine ring-containing polymer according to any one of claims 1 to 4. An optical component comprising the triazine ring-containing polymer according to any one of claims 1 to 4.