TW202128794A - Thermoplastic copolymer and resin molded body - Google Patents

Abstract

A thermoplastic copolymer that is a polymer of a monomer (I) which is represented by general formula (1) and a monomer (II) which is different from the monomer (I), while being at least one compound that is selected from the group consisting of monosubstituted ethylenes and 1, 1-disubstituted ethylenes.

Description

Thermoplastic copolymer and resin molded body

The present invention relates to a thermoplastic copolymer and a resin molded body.

In recent years, attention has been paid to polymers showing flame retardancy. For example, the paper by A. Dumitrascu et al. described on pages 2611-2618 of Polymer Degradation and Stability (Vol. 97) published in 2012, "Containing nitrogen at the same time by incorporation Flame retardant polymeric materials achieved by incorporation of styrene monomers containing both nitrogen and phosphorus (Non-Patent Document 1)” reported in the following formula:

[化1]

The homopolymer shown shows high flame retardancy. [Prior Technical Literature] [Non-Patent Literature]

[Non-Patent Document 1] A. Dumitrascu et al., "Flame retardant polymeric materials achieved by incorporation of styrene monomers containing both nitrogen and phosphorus phosphorus)", Polymer Degradation and Stability, vol.97, 2012, page 2611-page 2618

[The problem to be solved by the invention]

However, even in such a homopolymer described in Non-Patent Document 1, the flame retardancy is not necessarily sufficient, and a polymer with higher flame retardancy is expected.

The present invention was made in view of the above-mentioned problems of the prior art, and its purpose is to provide a thermoplastic copolymer that can have higher flame retardancy and sufficiently high refractive index and transparency, and to form the thermoplastic copolymer. The resin molded body. [Technical means to solve the problem]

In order to achieve the above-mentioned object, the inventors have conducted intensive research and found that by copolymerizing monomer (I) and monomer (II), the obtained polymer can be made to have higher flame retardancy and A thermoplastic copolymer with sufficiently high refractive index and transparency to complete the present invention. The above-mentioned monomer (I) is represented by the following general formula (1), and the above-mentioned monomer (II) is other than the monomer (I) , Is at least one compound selected from the group consisting of monosubstituted ethylene and 1,1-disubstituted ethylene.

That is, the thermoplastic copolymer of the present invention is a polymer of monomer (I) and monomer (II), The above monomer (I) is represented by the following general formula (1):

[化2]

Express, The above-mentioned monomer (II) is at least one compound selected from the group consisting of monosubstituted ethylene and 1,1-disubstituted ethylene other than the monomer (I).

In the above-mentioned thermoplastic copolymer of the present invention, the above-mentioned compound selected as the above-mentioned monomer (II) is preferably a compound having a refractive index of 1.35 or more.

In addition, in the thermoplastic copolymer of the present invention, the monomer (II) is preferably selected from the group consisting of styrenes, acrylates, methacrylates, N-vinylamines and acrylonitrile. At least one compound in the group.

In addition, the resin molding system of the present invention is a molded body of the above-mentioned thermoplastic copolymer of the present invention. [Effects of Invention]

According to the present invention, it is possible to provide a thermoplastic copolymer having higher flame retardancy and sufficiently high refractive index and transparency, and a resin molded body formed by molding the thermoplastic copolymer.

Hereinafter, the present invention will be described in detail in conjunction with its preferred embodiments.

[Thermoplastic Copolymer] The thermoplastic copolymer of the present invention is a polymer (copolymer) of monomer (I) and monomer (II), The above monomer (I) is represented by the above general formula (1), The above-mentioned monomer (II) is at least one compound selected from the group consisting of monosubstituted ethylene and 1,1-disubstituted ethylene other than the monomer (I).

The monomer (I) used as the monomer of the thermoplastic copolymer of the present invention is a compound represented by the above general formula (1). Such a monomer (I) may use one kind of the compound represented by the above general formula (1) alone or in combination of two or more kinds of the compound represented by the above general formula (1). In addition, as such a monomer (I), from the viewpoint of having higher radical polymerizability and heat resistance, the following formula (2) is more preferable:

[化3]

The compound represented, and/or the following formula (3):

[化4]

The compound represented. Furthermore, such a monomer (I) can also be prepared by the method described in Non-Patent Document 1 above.

In addition, as a method for producing such monomer (I), it is preferable to adopt a method in which the following formula is used due to the presence of a solvent and a reaction reagent:

[化5]

The compound represented (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and the following general formula (4):

[化6]

(In the formula, X represents a halogen atom (more preferably a chlorine atom)) The halogenated compound shown undergoes an addition reaction to obtain monomer (I). In addition, as such a solvent, alcohols (for example, methanol, ethanol, etc.), ketones (for example, acetone, etc.), amides (for example, formazan, etc.), etc. can be suitably used. In addition, as such a reaction reagent, it is preferable to use an alkali metal alkoxide (sodium methoxide, sodium ethoxide, lithium methoxide, lithium ethyl oxide) in terms of suppressing side reactions and further improving the yield. Oxide, etc.). In addition, the reaction temperature of such an addition reaction is usually preferably about 10 to 60°C.

In addition, the monomer (II) used as the monomer of the thermoplastic copolymer of the present invention is selected from the group consisting of monosubstituted ethylene and 1,1-disubstituted ethylene in addition to the above-mentioned monomer (I) At least one compound in the group.

Examples of compounds that can be used as such monosubstituted ethylene include styrenes, acrylic esters, vinyl pyridines, vinyl ketones, acrylonitrile, acrylamides, and N-vinyl amines. In addition, specific examples of such monosubstituted ethylene include styrene, 4-methylstyrene, methyl acrylate, butyl acrylate, acrylonitrile, and N-vinylpyrrolidone. In addition, examples of compounds that can be used as 1,1-disubstituted ethylene include methacrylates, methacrylamide, vinylidene halides, and α-substituted styrenes. In addition, as such 1,1-disubstituted ethylene, specific examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, phenyl methacrylate, and 2-hydroxy methacrylate. Ethyl ester, vinylidene chloride, α-methylstyrene.

Furthermore, in the present invention, the above-mentioned compound selected as the above-mentioned monomer (II) is preferably a compound having a refractive index of 1.35 or higher (more preferably 1.39 or higher). In this way, when the above-mentioned compounds selected as the monomer (II) are all compounds with a refractive index of 1.35 or higher, a thermoplastic copolymer with a high refractive index such as a refractive index of 1.6 or higher can be obtained more efficiently. Furthermore, the "refractive index" of the compound selected as the monomer (II) is the refractive index (nD ), the value obtained by measuring with a so-called Abbe refractometer (for example, "Multi-wavelength Abbe refractometer DR-M2" manufactured by Atago Co., Ltd., etc.) can be used. The refractive index of the above-mentioned compound used as the monomer (II) can be obtained, for example, by preparing a film or plate-shaped molded article of the above-mentioned compound as a measurement sample, and performing the above-mentioned Abbe refraction Measure the refractive index of light (D-ray) with a wavelength of 589 nm at a temperature of 23°C.

Furthermore, in terms of being able to be more flame-retardant, the monomer (II) is preferably selected from the group consisting of styrenes, acrylics, methacrylates, N-vinylamides, and acrylics. At least one compound in the group consisting of nitriles, more preferably selected from styrene, butyl acrylate, 2-hydroxyethyl methacrylate, methyl methacrylate, N-vinylpyrrolidone and propylene At least one compound in the group consisting of nitriles. In addition, as the above-mentioned compound that can be selected as the monomer (II), it is possible to achieve a higher flame retardancy such as the grade "V-0" in the UL94V test more efficiently by using the compound. In other words, styrene, butyl acrylate, methyl methacrylate, N-vinylpyrrolidone, and acrylonitrile are more preferred, and from the viewpoint that higher heat resistance can also be exhibited, styrene, Butyl acrylate, methyl methacrylate, N-vinylpyrrolidone. In addition, the above-mentioned compounds which can be selected as such monomer (II) may be used alone or in combination of two or more kinds.

In addition, the above-mentioned compound selected as the above-mentioned monomer (II) is preferably a compound having a boiling point of 40°C or higher (more preferably 60°C or higher). If the boiling point does not reach the above lower limit, it will become a gaseous state under the heating for the polymerization reaction. Therefore, it will become a reaction under pressure. A special reactor is required. It is difficult to efficiently produce the polymer. The tendency of the manufacturing cost of things to increase.

The thermoplastic copolymer of the present invention is a polymer (copolymer) of the above-mentioned monomer (I) and the above-mentioned monomer (II). In this way, by setting the thermoplastic copolymer as a polymer obtained by polymerizing the above-mentioned monomer (I) and the above-mentioned monomer (II), it can perform higher than the homopolymer of the above-mentioned monomer (I). It is flame retardant, and can fully maintain a high level of transparency and refractive index. In this way, in the thermoplastic copolymer of the present invention, a polymer obtained by combining the above-mentioned specific monomer (I) with the above-mentioned specific monomer (II) can exhibit a higher level of flame retardancy. In this regard, although the aforementioned Non-Patent Document 1 describes the formation of homopolymers of the monomers described in this document, it does not mention at all that the monomers described in this document are copolymerized with other monomers.

In addition, the thermoplastic copolymer of the present invention is obtained by polymerizing the above-mentioned monomer (I) and the above-mentioned monomer (II). When performing such polymerization, the ratio of the above monomer (I) to the above monomer (II) is not particularly limited. In order to obtain higher flame retardancy and higher strength of the molded body, it is more preferably set as For example, the molar ratio ([monomer(I)]/[monomer(II)]) becomes 10/1～1/10 (further preferably 5/1～1/5, particularly preferably 3/1～1 /3) ratio.

Furthermore, such a thermoplastic copolymer may be a polymer (copolymer) of the above-mentioned monomer (I) and the above-mentioned monomer (II), and the type is not particularly limited. For example, it may be a random copolymer or a block copolymer. Any of materials, or alternating copolymers. Furthermore, from the viewpoint of easier preparation, such a thermoplastic copolymer is preferably a random copolymer of the aforementioned monomer (I) and the aforementioned monomer (II).

In addition, as a method for preparing the thermoplastic copolymer of the present invention, in addition to using the above monomer (I) and the above monomer (II) as monomers, it can be obtained by polymerizing two or more monomers. The well-known method of copolymers. Among them, the form of the polymerization reaction when preparing the thermoplastic copolymer of the present invention is not particularly limited, but in terms of both the monomer (I) and the monomer (II) having a radical polymerizable group, it is preferably Free radical polymerization is carried out between these monomers. In the case of performing radical polymerization in this way, it is preferable to react the monomer (I) and the monomer (II) in the reaction solvent in the presence of a radical polymerization initiator.

The radical polymerization initiator is not particularly limited. For example, azobisisobutyronitrile (AIBN), di-tertiary butyl peroxide, tertiary butyl hydroperoxide, and benzyl peroxide can be suitably used. (BPO), methyl ethyl ketone peroxide, triethyl borane (Et ₃ B), diethyl zinc (Et ₂ Zn) and other known radical polymerization initiators.

In addition, there are no particular restrictions on the above-mentioned reaction solvent. Well-known solvents that can be used in radical polymerization can be suitably used. For example, tetrahydrofuran (THF), dioxane, dioxolane, acetone, chloroform can be suitably used. , Toluene, dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfide (DMSO), γ-butyrolactone, cyclic Glycol dimethyl ether solvents such as pentanone, cyclohexanone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, diethylene glycol dimethyl ether, ethyl cellosolve, etc. Cellulose solvents, glycol ester solvents such as propylene glycol monomethyl ether acetate, glycol ether solvents such as propylene glycol monomethyl ether, and the like. As such a reaction solvent, from the viewpoint of the solubility of the monomer (I), DMF, DMAc, NMP, and DMSO are particularly preferred.

The reaction conditions that can be used for radical polymerization (polymerization reaction) between the monomer (I) and the monomer (II) are not particularly limited. For example, they may be under an inert gas atmosphere (for example, under a nitrogen atmosphere). ), the reaction temperature (polymerization temperature) is set to room temperature (25°C) to about 150°C to carry out the polymerization reaction. Furthermore, the polymerization temperature is preferably to satisfy the following conditions: the boiling point of the monomer (II), the boiling point of the reaction solvent, and the radical generation temperature of the radical polymerization initiator (for example, the 10-hour half-life temperature). Way to set (select). Moreover, the reaction time of such a polymerization reaction is not specifically limited, For example, it can react under the above-mentioned reaction conditions for about 1 to 48 hours. Furthermore, when carrying out such radical polymerization, from the viewpoint of increasing the conversion rate of monomers, for example, when azobisisobutyronitrile is used as the radical polymerization initiator, the following conditions can also be adopted, namely In an inert gas atmosphere, the reaction temperature is set to 50 to 100°C for 3 to 30 hours, and then the reaction temperature is set to 80 to 150°C for 1 to 15 hours. In addition, the amount of the radical polymerization initiator used in such radical polymerization is not particularly limited, as long as it is appropriately adjusted within the range in which radical polymerization can be carried out. Furthermore, when such polymerization is carried out, when the finally obtained polymer (copolymer) is within a range that does not impair the gist of the present invention, various additives (anti-aging agents, antioxidants, etc.) or Other types of monomers, etc. In this way, the thermoplastic copolymer of the present invention may contain various additives (anti-aging agents, antioxidants, etc.) according to its use, etc., and the copolymer may also include other monomers within a range that does not impair the gist of the present invention. The repeating unit of the body.

In this way, the above-mentioned thermoplastic copolymer of the present invention can be prepared by polymerizing the above-mentioned monomer (I) and the above-mentioned monomer (II) as monomers. Compared with the homopolymer described in Non-Patent Document 1, the thermoplastic copolymer of the present invention can have higher flame retardancy and maintain a sufficiently high level of refractive index and transparency. Here, the refractive index of such a thermoplastic copolymer is preferably 1.5 or more. Since the refractive index of the above-mentioned thermoplastic copolymer satisfies the above-mentioned conditions, it can also be preferably applied to optical applications such as lenses. Furthermore, the refractive index of this thermoplastic copolymer refers to the refractive index (nD) for light (D-ray) with a wavelength of 589 nm measured by the critical angle method (method: Abbe's type). Refractometer (for example, "Multi-wavelength Abbe Refractometer DR-M2" manufactured by Atago Co., Ltd., etc.) measured at a temperature of 23°C. In addition, in order to achieve higher transparency of the thermoplastic copolymer of the present invention, the total light transmittance is more preferably 80% or more (more preferably 85% or more). Such total light transmittance can be obtained by measuring in accordance with JIS K7361-1 (issued in 1997).

[Resin molded body] The resin molding system of the present invention is a molded body of the above-mentioned thermoplastic copolymer of the present invention.

Since this resin molding system is formed by molding the above-mentioned thermoplastic copolymer of the present invention, it has higher flame retardancy, and has sufficiently high refractive index and transparency. Furthermore, there are no particular restrictions on the method for preparing such resin molded bodies. In addition to using the thermoplastic copolymer of the present invention, a known method capable of molding a thermoplastic resin (for example, extrusion molding, injection molding, etc.) can be suitably used. Method, calender molding method, blow molding method, press molding method, etc.). In addition, the form of such a resin molded body is not particularly limited, as long as it is appropriately molded into various shapes according to the application, and it can be formed into a film shape, a plate shape, a sheet shape, a pellet shape, etc., for example. [Example]

Hereinafter, the present invention will be explained more specifically based on examples and comparative examples, but the present invention is not limited to the following examples.

(Synthesis example 1: Synthesis of monomer (I)) In each example, etc., the compound used as the monomer (I) was synthesized in the following manner. That is, first, add 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA, 3 g, 0.0138 mol), methanol (13.2 g: 4.4 times the mass of HCA) To a 50 ml reaction vessel, obtain a suspension. Secondly, under an ice bath, add a solution containing sodium methoxide at a ratio of 28% by mass in methanol (total amount of NaOMe in the solution: 0.0145 mol) to the obtained suspension, and then at the same temperature. 4-(chloromethyl)styrene (CMS, 0.0131 mol) was added dropwise to obtain a mixed solution. After that, the above-mentioned mixed liquid was allowed to stand at 20° C. for 21 hours, whereby the reaction between HCA and CMS was carried out in the mixed liquid to obtain a reaction liquid.

Next, add water (1 ml), 4-tert-butylcatechol (2.3 mg), and hexane (30 ml) to the reaction solution obtained after the above reaction, and stir to obtain an organic layer and The two-layer suspension of the water layer. After that, the obtained suspension was poured into water (40-50 ml), and the precipitated solid was collected by filtration. After that, the solid was washed with water and then washed with hexane. Next, the washed solid was dried under reduced pressure at 40°C overnight to obtain a reaction product.

^{After dissolving the reaction product thus obtained in deuterated chloroform, 1} H-NMR measurement was carried out using an NMR measuring machine (trade name "AL-400" manufactured by JEOL). As a result, it can be seen that the ¹ H- The NMR measurement results are similar to the "4-[(6-oxide-6H-dibenzo[c,e][1,2]oxaphosphahexan-6-yl)] described in Non-Patent Document 1 above. The value of the spectral data of styrene (M4)" is roughly the same, so the obtained compound has the following formula:

[化7]

The indicated compound (HCA-MS) (Furthermore, the compound will be referred to as "HCA-MS" as appropriate below. The characteristics of HCA-MS: molecular weight 332, melting point 128°C, and refractive index of 1.65 when made into a homopolymer (Refer to Comparative Example 1 described later)). ^{Furthermore, the 1} H-NMR measurement results of the obtained reaction product are shown below.

^[1 H-NMR spectrum data of reaction products ^{] 1} H NMR (400 MHz, CDCl ₃ , δ) 3.4-3.41 (m, 2H, P-CH ₂ ), 5.19-5.21 (d, 1H, CH = CH ₂ ) , 5.64-5.69 (d, 1H, CH = CH ₂ ), 6.59-6.66 (dd, 1H, CH = CH ₂ ), 7.00-7.02 (m, 2H, aromatic), 7.16-7.23 (m, 4H, aromatic) , 7.34-7.46 (m, 2H, aromatic), 7.65-7.74 (m, 2H, aromatic), 7.83-7.91 (m, 2H, aromatic).

(About monomer (II)) The name, abbreviation and characteristics of the compound used as the monomer (II) in the following examples are shown in Table 1 below. In addition, in the following Examples, etc., the compound used as the monomer (II) is described by abbreviations.

[Table 1] Compound name abbreviation Molecular weight Refractive index (monomer) Boiling point (℃) Styrene St 104 1.546 145 Butyl acrylate BA 128 1.417 148 2-hydroxyethyl methacrylate HEMA 130 1.449 250 Methyl methacrylate MMA 100 1.415 101 N-vinylpyrrolidone N-VPy 111 1.512 148 Acrylonitrile AN 53 1.391 77

(Example 1) Using HCA-MS (the compound obtained in Synthesis Example 1) as the monomer (I) and St as the monomer (II), a thermoplastic copolymer was produced by the following first and second steps.

(First step) Dissolve HCA-MS (100 g, 0.30 mol), St (31 g, 0.30 mol), azobisisobutyronitrile (AIBN: 47 mg, used as a radical polymerization initiator) in dehydrated dimethylacetate Amine (dehydrated DMAc: 86 g, used as a reaction solvent) to obtain a mixed solution. Next, under a nitrogen atmosphere, the mixture was heated while continuously stirring the mixture, and then kept at 90°C (the first reaction temperature) for 13 hours, and then kept at 110°C (the second reaction temperature) for 13 hours to obtain a reaction solution (In this way, the HCA-MS (monomer (I)) and St (monomer (II)) are reacted by stirring while heating the mixed solution).

(Second step) After heating and stirring to obtain a reaction solution, DMAc (300 ml) was added to the obtained reaction solution, and the reaction solution was poured into water (2 L) to analyze the solid content. Secondly, filter out the precipitated solid components. Next, after dispersing the obtained solid content in methanol (1.5 L), it was filtered again. After that, the obtained solid content was dried and pulverized to obtain a thermoplastic copolymer (126 g: powder form).

^{After dissolving the thus-obtained thermoplastic copolymer in deuterated chloroform, 1} H-NMR measurement was performed using an NMR measuring machine (trade name "AL-400" manufactured by JEOL). The result obtained by such NMR measurement ( ¹ H-NMR spectrum of the compound) is shown in FIG. 1. In addition, with respect to the thermoplastic copolymer (powder), IR measurement (ATR method) was performed using an infrared absorption spectrometer (IR measuring machine: trade name "SI-50" manufactured by Thermo Fisher). The results obtained are shown below. [Measurement result of infrared absorption spectrum of thermoplastic copolymer] IR (cm ^-1 ): 3024, 2916, 1595, 1583, 1510, 1493, 1476, 1447, 1430, 1237, 1204, 1147, 1117, 1082, 1044, 906 , 840, 750, 715, 700, 615, 595, 515, 483, 429.

According to ^{the results of 1} H-NMR measurement (Figure 1) and IR measurement, it can be seen that the disappearance of the olefin part and the peak of the phosphorus compound are confirmed, so the obtained thermoplastic copolymer is a copolymer of HCA-MS and St. (polymer). Furthermore, gel permeation chromatography analysis (GPC analysis: furthermore, the measurement device (high-speed GPC device) used for the measurement) was performed on the reaction solution obtained in the same manner as in the first step above: a product manufactured by Tosoh Co., Ltd. Name "HLC-8420GPC", eluate: THF, detector: differential refractive index detector and UV (ultraviolet) detector), the result shows that the conversion rate of HCA-MS is 87%. In addition, the obtained thermoplastic copolymer was dissolved in DMAc and subjected to gel permeation chromatography analysis (GPC analysis: In addition, the measurement device (high-speed GPC device) was used for the measurement: the product name "HLC-8320GPC" manufactured by Tosoh Co., Ltd. "Leaching solution: DMAc solution containing LiBr at a concentration of 0.1 mM, detector: differential refractive index detector), the result confirmed that the number average molecular weight (Mn) of the obtained thermoplastic copolymer was 88,400.

(Examples 2-7) The type of monomer (II) in the first step was changed from St to the compound shown in Table 2 (indicated by abbreviations), and the amount of monomer (I) used in the first step and the amount of monomer (II) The usage amount, the usage amount of AIBN (radical polymerization initiator), the first reaction temperature, the holding time at the first reaction temperature, and the conditions related to the usage amount of dehydrated DMAc (reaction solvent) are changed to those shown in Table 2. Except for the conditions, thermoplastic copolymers were obtained in the same manner as in Example 1, respectively. Furthermore, in Examples 2-7, the conversion rate of HCA-MS and the number average molecular weight (Mn) of the thermoplastic copolymer were measured by the same method as that used in Example 1, and the obtained results are shown in Table 2.

(Comparative example 1) Using only monomer (I) instead of monomer (II), the amount of monomer (I) used in the first step, the amount of AIBN (radical polymerization initiator) used, the first reaction temperature, and the The conditions related to the retention time at a reaction temperature and the amount of dehydrated DMAc (reaction solvent) used were changed to the conditions shown in Table 2. Except for this, the homopolymer of HCA-MS was obtained in the same manner as in Example 1. (homopolymer).

[Table 2] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative example 1 Type of monomer (I) HCA-MS HCA-MS HCA-MS HCA-MS HCA-MS HCA-MS HCA-MS HCA-MS Type of monomer (II) St St HEMA AN BA N-VPy MMA - Monomer (I) consumption g 100 120 134 150 150 150 150 150 mol 0.30 0.36 0.40 0.45 0.45 0.45 0.45 0.45 Monomer (II) consumption g 31 13 52 twenty four 19 50 45 - mol 0.30 0.13 0.40 0.45 0.15 0.45 0.45 - Usage amount of dehydrated DMAc g 86 88 124 116 113 134 130 130 AIBN usage mg 47 35 63 65 45 65 65 31 First reaction temperature °C 90 90 90 70 90 90 80 90 Holding time at the first reaction temperature Hour 13 13 9 5 9 12 18 13 The molar ratio of monomer (I) to monomer (II) (monomer (I)/monomer (II)) 1/1 3/1 1/1 1/1 3/1 1/1 1/1 - The mass ratio of monomer (I) relative to the total amount of monomer [mass%] 76 90 72 86 89 75 77 100 Conversion rate of HCA-MS [%] 87 92 95 96 89 96 99 95 Mn 88400 97200 97700 76200 46900 55500 86900 68000

(Examples 8-14 and Comparative Example 2) Using the thermoplastic copolymer obtained in Examples 1-7 and the homopolymer obtained in Comparative Example 1 as raw materials (materials), a vacuum heating press was used and the following pressure molding conditions were used In this way, press molding is performed to prepare resin plates (plate-shaped resin molded bodies). In addition, the types of raw materials (materials) used in Examples 8 to 14 and Comparative Example 2 are shown in Table 3. [Conditions for pressure forming] The amount of material used (the amount of polymer (powder) used): 20 g Forming conditions: temperature 200℃, forming pressure 5 MPa, forming time: 20 minutes The size of the mold used: length 130 mm, width 90 mm, thickness 1.5 mm.

[Evaluation of the characteristics of the resin molded bodies obtained in Examples 8-14 and Comparative Example 2] (Determination of total light transmittance) The resin plate (plate-shaped resin molded body) obtained in each example was directly used as the measurement sample, and the "turbidity meter NDH-2000" manufactured by Nippon Denshoku Industry Co., Ltd. was used as the measurement device. JIS K7361-1 (issued in 1997) was measured to obtain the total light transmittance (unit: %). The results obtained are shown in Table 3.

(Measurement of refractive index) The resin plate (plate-shaped resin molded body) obtained in each example was used directly as the measurement sample, and the "Multiwavelength Abbe Refractometer DR-M2" manufactured by Atago Co., Ltd. was used as the measurement device. Under the temperature condition of ℃, the refractive index (nD) for light (D-ray) with a wavelength of 589 nm is measured to obtain the refractive index. The results obtained are shown in Table 3.

(Evaluation test of flame retardancy) A test piece (length: 120 mm, width: 13 mm, thickness: 1.5 mm) was prepared using the resin plate (plate-shaped resin molded body) obtained in each example, etc., and was carried out in accordance with the UL94 standard (Underwriters Laboratories (Underwriters Laboratories)). The flame retardancy evaluation test (UL94V test) of the vertical burning test (V test) specified by Laboratories Inc.). Furthermore, in this test, the size of the flame was set to 20 mm. After the first flame contact was performed on the test piece for 10 seconds, the second flame contact was performed for 10 seconds while the fire disappeared. Then, the state of the test piece after the second flame contact or the influence caused by drips from the test piece were confirmed, and the flame retardancy of each resin board was evaluated according to the following evaluation criteria. The results obtained are shown in Table 3. [Evaluation criteria for flame retardancy] A: The test piece is not ignited, and it meets the UL94 standard "V-0". B: Although the test piece was not ignited, the cotton ignited due to molten dripping, which is equivalent to the UL94 standard "V-2".

[table 3] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative example 2 About the material of the resin film Type of material (polymer) Copolymer (Example 1) Copolymer (Example 2) Copolymer (Example 3) Copolymer (Example 4) Copolymer (Example 5) Copolymer (Example 6) Copolymer (Example 7) Homopolymer (Comparative Example 1) Monomers used to prepare the polymer (molar ratio in parentheses) HCA-MS/St (1/1) HCA-MS/St (3/1) HCA-MS/HEMA (1/1) HCA-MS/AN (1/1) HCA-MS/BA (3/1) HCA-MS/N-VPy (1/1) HCA-MS/MMA (1/1) Only use HCA-MS Refractive index (nD) 1.64 1.65 1.61 1.63 1.63 1.65 1.62 1.65 Total light transmittance (%) 87.5 86.1 87.7 87.2 86.1 85.1 87.2 86.9 Evaluation of flame retardancy A (V-0) A (V-0) A (V-0) A (V-0) A (V-0) A (V-0) A (V-0) B (equivalent to V-2)

According to the results shown in Table 3, it is also clearly confirmed that the resin plates obtained in Examples 8 to 14 (the copolymers of monomer (I) and monomer (II) obtained in Examples 1 to 7 are molded into Compared with the resin plate obtained in Comparative Example 1 (a molded body formed by molding a homopolymer of HCA-MS), the flame retardancy becomes higher. In addition, the resin plates obtained in Examples 8 to 14 all had a higher total light transmittance and a higher refractive index equivalent to the resin plates obtained in Comparative Example 1. Based on this result, it can be seen that by using the copolymer of HCA-MS (monomer (I)) and the above-mentioned monomer (II) (Examples 1 to 7) to prepare resin moldings, it is combined with the homopolymerization of HCA-MS Compared with the case of preparing a resin molded body, a resin molded body showing higher flame retardancy can be obtained, and a sufficiently high refractive index can be obtained with the same degree as the resin molded body obtained by using the homopolymer of HCA-MS A resin molded body with high efficiency and sufficient transparency (based on total light transmittance). [Industrial availability]

As explained above, according to the present invention, it is possible to provide a thermoplastic copolymer having higher flame retardancy and sufficiently high refractive index and transparency, and a resin molded body formed by molding the thermoplastic copolymer. In this way, the thermoplastic copolymer of the present invention can have sufficiently high flame retardancy and excellent optical properties (higher refractive index, or higher transparency based on total light transmittance), so it is especially useful for It is more useful as a material for resin molded bodies for optical applications such as lenses, building materials, coating materials, and coatings.

^{Figure 1 is the 1} H-NMR spectrum of the thermoplastic copolymer obtained in Example 1.

Claims (4)

A thermoplastic copolymer, which is a polymer of monomer (I) and monomer (II). The above monomer (I) is represented by the following general formula (1): [化1]

It means that the above-mentioned monomer (II) is at least one compound selected from the group consisting of monosubstituted ethylene and 1,1-disubstituted ethylene in addition to the monomer (I). The thermoplastic copolymer of claim 1, wherein the above-mentioned compound selected as the above-mentioned monomer (II) is a compound having a refractive index of 1.35 or more. The thermoplastic copolymer of claim 1 or 2, wherein the above-mentioned monomer (II) is selected from the group consisting of styrenes, acrylates, methacrylates, N-vinylamines and acrylonitrile At least one compound. A resin molded body, which is a molded body of a thermoplastic copolymer according to any one of claims 1 to 3.

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