KR20200023173A - Polymer including triazine ring, and thermoplastic article and optical component including the same - Google Patents

Abstract

The present invention relates to a triazine ring-containing polymer having a repeating unit represented by formula (1) and having a number average molecular weight of more than 20000 and not greater than 50000. (In the formula, R1 independently represents an alkyl group having 1 to 5 carbon atoms, and R2 independently represents a divalent group having one or more aromatic hydrocarbon groups.) According to the present invention, it is possible to provide the triazine ring-containing polymer having a high refractive index and being suitable for molding processes.

Description

POLYMER INCLUDING TRIAZINE RING, AND THERMOPLASTIC ARTICLE AND OPTICAL COMPONENT INCLUDING THE SAME}

The present invention relates to a triazine ring-containing polymer, a thermoplastic molded article and an optical component comprising the same.

In recent years, research into optical materials has been actively conducted, and as a material for optical lenses used in various cameras such as cameras, video cameras, and optical systems such as smartphone lenses, it has a high refractive index and has high heat resistance and light transmittance. (Transparency) There is a demand for the development of materials that are excellent also in inverse formation. Resin lenses have the advantages of being lighter and less fragile than glass lenses, having a low material cost, and being able to be processed into various shapes by injection molding suitable for lens formation. However, in recent years, in order to meet the demand due to thinning of products and high pixelation of cameras, it is required to increase the refractive index of the material itself.

As a method of making the polymer which is a resin material high refractive index, the attempt to introduce an aromatic ring, a halogen atom, and a sulfur atom is made | formed. Especially, although the epi sulfide resin and thiourethane resin which introduce | transduced the sulfur atom become refractive index 1.7 or more, since there is no plasticity, the practical use range is limited.

Many polymers having a triazine ring have been studied as high refractive index resins having plasticity. For example, Japanese Patent Laid-Open No. 2014-162829 and Japanese Patent Laid-Open No. 2014-162830 include a triazine ring-containing polymer having a repeating unit structure having a triazine ring and having a refractive index of 1.7 or more.

However, the polymer having the triazine ring described in the above document has a problem that molding processing by injection molding is difficult because the glass transition temperature (Tg) is high and the viscosity at the time of melting is high.

Therefore, this invention is made | formed in view of the said situation, Comprising: It aims at providing the triazine ring containing polymer which has a high refractive index and is suitable for shaping | molding processes, such as injection molding.

The triazine ring-containing polymer according to one embodiment is the following formula (1):

(In formula, R <^1> represents a C1-C5 alkyl group each independently, and R <^2> represents a bivalent group which has each independently 1 or more aromatic hydrocarbon group.)

The number average molecular weight is more than 20000 and 50000 or less including the repeating unit represented by the following.

R ² may be each independently any one of the groups shown below:

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The triazine ring-containing polymer may have a glass transition temperature of 100 ° C. or higher and 180 ° C. or lower.

In said formula (1), R <^1> is a methyl group and R <^2> may be the group shown below each independently:

또는

or

According to another embodiment, a thermoplastic molded article and an optical part including the triazine ring-containing polymer may be provided.

According to the present invention, it is possible to provide a triazine ring-containing polymer having a high refractive index and suitable for molding processes such as injection molding.

1 is a graph showing shear viscosity versus shear rate of triazine ring-containing polymers obtained in Example 1 and Comparative Example 3. FIG.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described, the technical scope of this invention should be defined based on description of a claim, and is not limited only to the following forms. In the present specification, "X to Y" indicating a range means "X or more and Y or less". In addition, unless otherwise indicated, operation, a measurement of a physical property, etc. are performed on the conditions of room temperature (20-25 degreeC) / relative humidity 40-50% RH. In the present specification, the "triazine ring-containing polymer" is simply referred to as "polymer," and the "thermoplastic molded article" is also referred to simply as "molded product."

The triazine ring-containing polymer of one embodiment of the present invention is represented by the following formula (1):

It is characterized by including the repeating unit represented by (In formula, R <^1> represents a C1-C5 alkyl group each independently, and R <^2> represents the bivalent group which has each independently one or more aromatic hydrocarbon group.).

N of the side chain of a triazine ring containing polymer couple | bonded with the phenyl group. In addition, the main chain is connected by a thio ether bond (-S-). The phenyl group of a side chain and the thio ether bond of a principal chain are considered to contribute to high refractive index of a polymer. Moreover, by introducing a phenyl group into the side chain, it becomes possible to make the glass transition temperature of a polymer into the range (for example, 80-200 degreeC) suitable for injection molding.

As a C1-C5 alkyl group couple | bonded with N of a side chain, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pen And a methyl group, isopentyl group, neopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, cyclopentyl group, straight chain, branched chain and cyclic alkyl group. Especially, a C1-C4 alkyl group is preferable, a C1-C3 alkyl group is more preferable, a methyl group or an ethyl group is still more preferable, and a methyl group is the most preferable. By including the said alkyl group, compared with the case of having a hydrogen atom, glass transition temperature can be reduced and the viscosity at the time of melting can be reduced. Moreover, the solubility to a solvent can be improved by including the said alkyl group compared with the case where it has other groups.

Divalent group having one or more of which is located in the main chain an aromatic hydrocarbon group of the polymer (R ²⁾ roneun, a divalent group formed from at least one aromatic hydrocarbon group; Divalent groups formed by combining at least one aromatic hydrocarbon group and at least one aliphatic hydrocarbon group; And divalent groups formed by combining at least one aromatic hydrocarbon group, at least one aliphatic hydrocarbon group, and at least one -S- or -O-. As a specific example, group shown below is mentioned.

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By introducing a divalent group having at least one aromatic hydrocarbon group into the main chain of the polymer, the polymer becomes high in refractive index. At the same time, it becomes possible to make the glass transition temperature of a polymer into the range suitable for injection molding (for example, 80-200 degreeC).

According to one preferable aspect, the triazine ring-containing polymer includes the following repeating unit.

또는

or

The triazine ring-containing polymer may include repeating units (hereinafter also referred to as "other repeating units") other than the repeating unit represented by Formula (1), but from the viewpoint of making the effect of the present invention satisfactory, It is preferable not to include other repeating units. Even when it contains another repeating unit, it is preferable that the ratio of the number of the other repeating units with respect to the total number of repeating units is 10% or less, It is more preferable that it is 5% or less, It is still more preferable that it is 3% or less, 1% It is especially preferable that it is the following (lower limit 0%). If the ratio of another repeating unit is the said range, it can prevent that the fall of refractive index and molding process, such as injection molding, become difficult.

When the triazine ring-containing polymer includes two or more kinds of repeating units, that is, a copolymer, the arrangement of the repeating units is not particularly limited, and may be random or block.

The number average molecular weight (Mn) of a triazine ring containing polymer is essentially more than 20000 and 50000 or less, Preferably it is 20500 or more and 49000 or less, More preferably, it is 21000 or more and 48000 or less. If the number average molecular weight is 20000 or less, the viscosity is too low. If the number average molecular weight is more than 50000, the viscosity is too high, and molding processability such as injection molding is lowered. On the other hand, when the number average molecular weight is in the above numerical range, there is an advantage that the transmittance (transparency) and heat resistance of the molded article are particularly good, and the mechanical strength of the obtained molded article is excellent. Although the method of controlling a number average molecular weight in the said numerical range is not specifically limited, A value can be adjusted by controlling a polymerization reaction time between 10 minutes and 40 hours. In addition, in this specification, the number average molecular weight employ | adopts the value measured by the method as described in the Example mentioned later.

The refractive index n _d of the triazine ring-containing polymer is, for example, 1.65 or more, and preferably 1.7 or more. If it is the said range, the high refractive index molded article suitable for an optical component can be obtained. Abbe number v _d of a triazine ring containing polymer is 15 or more, for example, Preferably it is 18 or more. In addition, in this specification, the refractive index n _d and the Abbe number v _d employ | adopt the value measured by the method of the Example description mentioned later.

The triazine ring-containing polymer has a glass transition temperature. In other words, an inflection point is observed in the differential calorific curve obtained by differential scanning calorimetry. Thus, the resin possessing the glass transition temperature has thermoplasticity and can be processed by injection molding. The glass transition temperature of a triazine ring containing polymer becomes like this. Preferably it is 80 degreeC or more and 200 degrees C or less, More preferably, it is 100 degreeC or more and 180 degrees C or less. The glass transition temperature can be adjusted by controlling the structure of the repeating unit shown in Formula (1). For example, a glass transition temperature can be made high by introducing a bulky structure and a rigid structure to R <^2> in Formula (1). In addition, in this specification, the glass transition temperature employ | adopts the value measured by the method as described in the Example mentioned later.

The viscosity of the triazine ring-containing polymer in the molten state is preferably 100 Pa · s or more and less than 100000 Pa · s, more preferably 1000 Pa · s or more and 50000 Pa · s or less, still more preferably 6000 Pa · s or more and 30000 Pa · s. It is as follows. If the viscosity in a molten state is in the said numerical range, it is excellent in the moldability, such as injection molding. In addition, in this specification, the viscosity of the melt state of a polymer employ | adopts the value measured by the method as described in the Example mentioned later.

A triazine ring containing polymer can be synthesize | combined using a well-known method. For example, as shown in the following formula, a triazinedithiol compound and a dihalogenated aromatic compound can be manufactured by making it react in presence of a phase transfer catalyst.

In formula, R <^1> and R <^2> are the same as the definition in Formula (1), Y represents a halogen atom.

Examples of the halogen atom of Y include a chlorine atom, bromine atom or urea atom.

Although it does not restrict | limit especially as a triazinedithiol compound, For example, 2-N-methylanilino-1,3,5-triazine-4,6-dithiol, 2-N-ethyl anilin-1,3 , 5-triazine-4,6-dithiol, 2-Nn-propyl anilin-1,3,5-triazine-4,6-dithiol, 2-N-isopropyl anilin-1,3, 5-triazine-4,6-dithiol etc. can be illustrated. As the dihalogenated aromatic compound, for example, α, α'-dibromo-p-xylene, α, α'-dichloro-p-xylene, α, α'-dibromo-o-xylene, α , α'-dichloro-o-xylene, α, α'-dibromo-m-xylene, α, α'-dichloro-m-xylene, 4,4'-bis (bromomethyl) biphenyl, 4, 4'-bis (chloromethyl) biphenyl and the like can be used. These can be used individually by 1 type or in combination of 2 or more type.

As a phase transfer catalyst used for reaction of a triazinedithiol compound and a dihalogenated aromatic compound, the long-chain alkyl quaternary ammonium salt which can be used for interfacial polycondensation, a crown ether, etc. are preferable, For example, hexadecyl trimethylammonium bromide etc. Can be used more preferably.

As a reaction system, the biphasic system of water and an organic solvent can be used, It is preferable to set it as a biphasic system of water and organic solvents, such as chloroform, dichloromethane, benzonitrile, and nitrobenzene. In the reaction, it is preferable to add a base such as sodium hydroxide or potassium hydroxide, and carry out at -10 ° C or more and 100 ° C or less for 2 hours or more and 120 hours or less.

The triazine ring containing polymer obtained by the above can also be refine | purified by general purification methods, such as a reprecipitation method, a dialysis method, an ultrafiltration method, and an extraction method.

<Thermoplastic molded parts, optical parts>

Another embodiment of the present invention relates to a thermoplastic molded article comprising the triazine ring-containing polymer described above. Another embodiment of the present invention relates to an optical component containing the triazine ring-containing polymer described above.

The shape of the molded article is not particularly limited, and for example, arbitrary shapes such as lens type (spherical lens, aspherical lens, Fresnel lens, etc.), film type, sheet type, plate type, rod type, fiber type, prism type, etc. And become. In the production of the molded article, for example, injection molding, compression molding, extrusion molding, transfer forming, blow forming, pressure forming, coating (spin coating, roll coating, curtain coating, dip coating, casting / casting) Well-known formation methods, such as formation method) can be used. Especially, the composition which concerns on this invention is especially suitable for injection molding. Before formation, the raw materials may be mixed using a kneader such as a Henschel mixer, a kneader, a half-barrier mixer, an extruder, or the like. When forming by injection molding, cylinder temperature is 150 degreeC or more and 300 degrees C or less, for example, 50 degrees C or more and 100 degrees C or less.

The optical component may be a display (e.g., a display for a smartphone, a liquid crystal display, a plasma display, etc.), an imaging device (e.g., a camera or a video, etc.), an optical pickup, a projector, an optical fiber communication device (e.g., , Optical amplifiers, and the like, and optical heads (passive optical parts) for transmitting light in automobile headlamps and the like. As such a passive optical component, a lens, a film, an optical waveguide, a prism, a prism sheet, a panel, an optical disk, the sealing material of LED, etc. are mentioned, for example. Such an optical component may have various functional layers, such as an antireflection layer, a light absorption layer, a hard coat layer, an antiglare layer, as needed.

EXAMPLE

Hereinafter, although an Example demonstrates this invention in detail, these do not limit this invention. In addition, in the following description, unless otherwise indicated, "part" means a "mass part."

<Measurement method of physical property value>

(Number average molecular weight (Mn), weight average molecular weight (Mw))

It was made to melt | dissolve in tetrahydrofuran (THF) so that the density | concentration of a polymer might be 0.1 mass%, and it filtered it with the membrane filter made from polytetrafluoro ethylene of diameter 0.2 micrometer as a measurement sample. The measurement of a number average molecular weight and a weight average molecular weight was performed by the gel permeation chromatography (GPC) which makes a differential refractometer a detector using tetrahydrofuran as a mobile phase. As a standard substance of molecular weight, monodisperse polystyrene was used.

Glass transition temperature (Tg)

After using a differential scanning calorimeter (DSC), the temperature was raised to 300 ° C. at a rate of 10 ° C./minute, and the sample held for 10 minutes was cooled to 25 ° C. at a temperature decrease rate of 10 ° C./min, and held for 10 minutes. It heated up to 300 degreeC at 10 degreeC / min, and measured. After completion of the measurement, the solution was cooled to room temperature (25 ° C) at 10 ° C / min.

(Refractive index n _d and Abbe number ν _d )

The polymer 2g was compression-molded for 5 minutes on 200 degreeC and 10 Mpa conditions, and the forming plate of 3 cm x 3 cm x 0.5 mm in thickness was produced. Using the obtained formation plate, the refractive index in wavelength 473nm, 594nm, and 657nm was measured with the prism coupler (Model2010, the product made by Metricon). From the measured value, the refractive index in C line (656.3 nm), d line (587.6 nm), and F line (486.1 nm) was computed by calculation. Abbe number v _d was computed using the value of the refractive index in these three wavelengths.

(Measurement of rheology)

The viscosity in the molten state of the polymer was measured at 250 ° C. under a nitrogen atmosphere at a shear rate of 0.1 (1 / s) using a rheometer (MCR302, manufactured by Anton paar).

<Synthesis of Triazine Ring-Containing Polymer>

Example 1

200 g (1.08 mol) of cyanuric chloride and 1 L of tetrahydrofuran were put into the 2 L three-necked flask equipped with the 500 mL dropping funnel, and it cooled at 0 degreeC by the ice bath. 116.23 g (1.08 mol) of tetrahydrofuran 300 mL solutions of N-methyl aniline were dripped over 120 minutes with the dropping funnel. After completion of the dropwise addition, 300 mL of an aqueous solution in which 115 g of sodium carbonate was dissolved was added, followed by stirring for 30 minutes. The upper tetrahydrofuran layer was taken out, and the solvent was distilled off under reduced pressure to obtain 263 g (yield 95%) of 2-N-methyl anilin-4,6-dichloro triazine.

Subsequently, in a 1 L three-necked flask equipped with a nitrogen introduction tube and a 200 mL dropping funnel, 100 g (392 mmol) of 2-N-methyl anilin-4,6-dichloro triazine, N, N-dimethylformamide (DMF) 350 mL 50 mL of distilled water was put and cooled to 0 degreeC by the ice bath. A solution obtained by dissolving 103 g of sodium hydrogen sulfide (purity 65%, manufactured by Wako Pure Chemical Industries, Ltd.) in 200 mL of pure water was added dropwise over 120 minutes with a dropping funnel. After completion of the dropwise addition, the reaction solution was heated to 90 ° C using an oil bath, and stirred for 60 minutes. The reaction solution was added dropwise to 3 liters of distilled water, diluted, and then the aqueous solution of 1N hydrochloric acid was added to make the pH lower than 3.0 to precipitate a solid. The solid was collected by filtration and washed with pure water to obtain 83.4 g (yield 85%) of the desired 2-N-methyl anilin-1,3,5-triazine-4,6-dithiol.

102.1 g (408 mmol) of 2-N-methyl anilin-1,3,5-triazine-4,6-dithiol was added to a 2 L beaker, and 350 mL of pure water was added, followed by addition of 82 mL of 10M NaOH aqueous solution, and 50 ° C. Heated to. 70 g (400 mmol) of α, α'-dichloro-p-xylene was dissolved in 500 mL of chloroform and added to the aqueous solution. 7.43 g of hexadecyltrimethylammonium bromide were added, and the mixture was stirred vigorously at 50 ° C for 3 hours. The reaction solution was dripped in methanol, and it was made to precipitate, and the white triazine ring containing polymer (2) was obtained. The polymer obtained was a number average molecular weight 45000 and a weight average molecular weight 90000.

Example 2

In the polymerization reaction of Example 1, it carried out similarly to Example 1 except having used 4,4'-bis (chloro methyl) biphenyl instead of (alpha), (alpha) '-dichloro- p-xylene, and made it the target white Triazine ring-containing polymer (3) was obtained. The polymer obtained was a number average molecular weight 25000 and a weight average molecular weight 60000.

 Comparative Example 1

In the polymerization reaction of Example 1, a white triazine ring-containing polymer was prepared in the same manner as in Example 1 except that 1,4-dibromo butane was used instead of α and α'-dichloro-p-xylene. 4) was obtained. The polymer obtained was a number average molecular weight 20000 and a weight average molecular weight 52000.

Comparative Example 2

In the polymerization reaction of Example 1, 2-dibutyl amino-1,3,5-triazine-4 instead of 2-N-methylanilino-1,3,5-triazine-4,6-dithiol Except using 6-dithiol, it carried out similarly to Example 1, and obtained target triazine ring containing polymer (5). The polymer obtained was a number average molecular weight 50000 and a weight average molecular weight 120000.

 Comparative Example 3

In the synthesis reaction of Example 1, the target white triazine ring-containing polymer (6) was obtained in the same manner as in Example 1 except that aniline was used instead of N-methylaniline. The polymer obtained was a number average molecular weight 40000, a weight average molecular weight 78000, and a glass transition temperature of 125 ° C.

Comparative Example 4

In the synthesis reaction of Example 1, the target white triazine ring-containing polymer (7) was obtained in the same manner as in Example 1 except that diphenyl amine was used instead of N-methylaniline. The obtained polymer had a number average molecular weight of 15000 and a weight average molecular weight of 40000, and was insoluble in solvents such as tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), and chloroform.

<Evaluation 1>

Glass transition temperature (Tg)

About the triazine ring containing polymer obtained in Examples 1 and 2 and Comparative Examples 1 and 2, the refractive index (n _d , 587.6 nm), Abbe number ν _d , the glass transition temperature, and the viscosity of the molten state were measured by the above measuring method. . The viscosity of a molten state was made into (circle) what is less than 100000 Pa.s, and evaluated what is 100000 Pa.s or more as x. The results are shown in Table 1.

Triazine ring-containing polymer Refractive index n _d Abbe ν _d Glass transition temperature (℃) Viscosity Example 1 (2) 1.705 25.3 112 ○ Example 2 (3) 1.714 22.0 130 ○ Comparative Example 1 (4) 1.675 29.2 53 ○ Comparative Example 2 (5) 1.635 33.7 40 ○ Comparative Example 3 (6) 1.729 22.0 125 ×

As shown in Table 1, the side chain amino group is tertiary, has a phenyl group and an alkyl group as a modifier, and has one or more aromatic hydrocarbon groups in the linker structure of the main chain, thereby having a glass transition temperature of 80 to 200. It becomes possible to set it in the range of ° C.

<Evaluation 2>

About the triazine ring containing polymer obtained by Example 1 and the comparative example 3, the viscosity in a molten state was measured with the said measuring method. The results are shown in FIG.

As shown in FIG. 1, the triazine ring containing polymer 6 of the comparative example 3 was remarkably high in melt | melting, and was not able to carry out injection molding. This is considered to be because NH groups in the side chain form hydrogen bonds in and between molecules. On the other hand, the triazine ring-containing polymer (2) of Example 1 having a side chain amino group of tertiary and having a phenyl group and an alkyl group as a modified group was suitable for injection molding because of its low viscosity at the time of melting.

<Evaluation 3>

The polymer which has the same molecular structure as the polymer synthesize | combined in Example 1 WHEREIN: The number average molecular weight synthesize | combined another thing and evaluated the viscosity and injection moldability. When the injection moldability was formed at the temperature of 250 degreeC of the injection nozzle part, it evaluated that "(circle)" which was injectable and was able to take out the formed product, and "x" that the molded product could not take out whether injection molding was impossible. The results are shown in Table 2.

Number average molecular weight (Mn) Viscosity (Pas) Injection Molding 13000 3300 × 20500 6000 ○ 27000 10000 ○ 40000 14000 ○ 50000 30000 ○ 100000 100000 ×

As shown in Table 2, the triazine ring containing polymer whose number average molecular weight is more than 20000 and 50000 or less was suitable for injection molding.

As mentioned above, since the triazine ring containing polymer which concerns on this invention is high in refractive index and excellent in moldability, it is especially suitable for uses, such as a lens for smartphones.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.

Claims (6)

Formula (1):

(In formula, R <^1> represents a C1-C5 alkyl group each independently, and R <^2> represents a bivalent group which has each independently 1 or more aromatic hydrocarbon group.)
Contains repeating units represented by
The triazine ring containing polymer whose number average molecular weight is more than 20000 and 50000 or less. The method of claim 1,
R ² is each independently a triazine ring-containing polymer, which is any one of the groups shown below:

,

,

,

,

,

,

, or

The method of claim 1,
Triazine ring containing polymer whose glass transition temperature is 100 degreeC or more and 180 degrees C or less. The method of claim 1,
In said formula (1), R <^1> is a methyl group and R <^2> is a triazine ring containing polymer which is each independently group shown below:

or

The thermoplastic molded article containing the triazine ring containing polymer of any one of Claims 1-4. The optical component containing the triazine ring containing polymer of any one of Claims 1-4.

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