Molded body for communication equipment and polycyanurate

Abstract

Provided is a molded body for communication equipment having a built-in microwave and / or milliwave antenna, the molded body being obtained using a thermoplastic resin composition. The thermoplastic resin composition contains a polycyanurate including repeating units represented by formula (1). (Y1 is a divalent organic group. Z1 is a hydrogen atom, a substituted or unsubstituted C1-20 linear or branched chain alkyl group, a substituted or unsubstituted C5-20 cycloalkyl group, a substituted or unsubstituted C6-20 aryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted C1-20 linear or branched chain alkoxy group, or a substituted or unsubstituted C6-20 aryloxy group.)

Description

[Technical Field]

[0001] The present invention relates to a molded article for a communication device that has a built-in microwave and / or millimeter wave antenna and that has excellent radio wave transmittance in the microwave and / or millimeter wave bands, excellent heat resistance, and a low coefficient of linear expansion. The present invention also relates to a polycyanurate for use in the molded article for the communication device and a thermoplastic resin composition containing the polycyanurate. The present invention also relates to a communication device that uses the molded article for the communication device. [Background technology]

[0002] In recent years, high-frequency radio waves such as microwaves and millimeter waves have come into use in the electrical and electronic equipment and automotive fields, and this has led to a demand for materials that have both a low dielectric constant and a low dielectric loss tangent. In particular, in the electrical and electronic fields, in addition to low dielectric constant and low dielectric loss tangent, high heat resistance and low thermal expansion are required.

[0003] Polycyanurates are known to have characteristics such as a high glass transition temperature (Tg), a high refractive index, and excellent chemical resistance and heat resistance. However, there have been no reports on their dielectric properties, and no cases of their use in communication devices using molded articles for communication devices.

[0004] Patent Document 1 discloses various polycyanurates having a bifunctional phenol structure and shows excellent heat resistance and flame retardancy, but makes no mention of dielectric properties.

[0005] Non-Patent Documents 1 to 4 disclose various polycyanurates having a bifunctional phenol structure, but make no mention of their dielectric properties.

[0006] Polycarbonate has excellent mechanical strength, electrical properties, and transparency, and is widely used as an engineering plastic in various fields, including electrical and electronic equipment and automobiles.

[0007] Patent Document 2 proposes a millimeter-wave radar cover that uses a polycarbonate made from a bisphenol having a specific substituent, thereby lowering the dielectric tangent and improving millimeter-wave transmittance. However, the thermoplastic resin composition described therein has insufficient heat resistance for use in information and communication devices such as laptop computers, tablet terminals, smartphones, and router devices.

[0008] Patent Document 3 discloses polycarbonate compositions and copolycarbonates that are produced using two specific types of bisphenols as raw materials and have excellent heat resistance and fire resistance, but does not mention anything about their dielectric properties.

[0009] [Patent Document 1] Japanese Unexamined Patent Publication No. 56-24423 [Patent Document 2] Japanese Patent Application Publication No. 2019-197048 [Patent Document 3] Japanese Unexamined Patent Publication No. 49-73455

[0010] [Non-Patent Document 1] Journal of Industrial Science, Vol. 70, No. 11, 1967, pp. 2066-2068 [Non-patent document 2] Journal of Industrial Science, Vol. 70, No. 4, 1967, pp. 588-593 [Non-patent document 3] European Polymer Journal, 1992, Vol. 28, No. 4, pp. 435-437 [Non-patent document 4] Journal of Polymer Science A-1:Polymer Chemistry 1969, Vol. 7, No. 11, pp. 3089-3100

[0011] In recent years, with the increase in the volume of information and communication traffic, there has been a strong demand for faster communication speeds in information and communication devices such as laptops, tablets, smartphones, and routers. High-speed communication is best achieved by using radio waves in higher frequency bands, and recently, radio waves above 3 GHz, which are classified as the microwave band, have been used. For the next-generation, fifth-generation mobile communication system (5G), the market is expected to take off in the 28 GHz band, which is a higher frequency in the microwave band. Furthermore, it is expected that next-generation communications will also use radio waves in the millimeter wave band.

[0012] Accordingly, there is an increasing demand for higher performance in molded articles for communication devices, such as sheets, films, coatings, and multilayer films that are built into information and communication devices that are expected to use microwave and / or millimeter wave bands. Radio waves in such high frequency bands are characterized by greater transmission loss and poorer permeability through materials than radio waves in lower frequency bands. Therefore, molded articles for communication devices used in microwave and / or millimeter wave communication are desired to have even better radio wave permeability than before.

[0013] The transmission loss is determined by the relative permittivity (ε r ) and the dielectric loss tangent (tanδ) of the dielectric. Therefore, in order to increase the radio wave permeability of the compact for communication devices, the relative dielectric constant ε of the material used for the compact for communication devices must be increased. r , and the dielectric tangent tanδ must be small.

[0014] Information and communication devices that transmit and receive high-frequency radio waves, such as microwaves and / or millimeter waves, tend to generate heat. Furthermore, in environments with large temperature changes, cracks occur at solder joints due to the difference in the linear expansion coefficient between the molded resin and the copper foil, resulting in a decrease in connection reliability. For this reason, materials used in such fields are required to have not only a low dielectric constant and a low dielectric loss tangent, but also adequate heat resistance and low thermal expansion, and there is a strong demand for materials that meet these requirements. However, conventional materials have not been able to meet all of these requirements. Summary of the Invention

[0015] An object of the present invention is to provide a molded article for a communication device having a built-in microwave and / or millimeter wave antenna, which has excellent radio wave transmittance in the microwave and / or millimeter wave bands, excellent heat resistance, and a low coefficient of linear expansion, and to provide the communication device.

[0016] The present inventors have found that the above-mentioned problems can be solved by forming a molded article for a communication device having a built-in microwave and / or millimeter wave antenna, the molded article comprising a specific polycyanurate and a thermoplastic resin composition containing the polycyanurate.

[0017] The gist of the present invention is as follows.

[0018] [1] A molded article for a communication device having a built-in microwave and / or millimeter wave antenna, obtained using a thermoplastic resin composition, wherein the thermoplastic resin composition contains a polycyanurate having a repeating unit represented by the following formula (1):

[0019] [ka]

[0020] (In formula (1), Y 1 represents a divalent organic group. 1 is a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0021] [2] Z above 1is a group selected from the group consisting of a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0022] [3] Y 1 The molded article for a communication device according to [1] or [2], wherein is a divalent organic group having an aliphatic ring or an aromatic ring.

[0023] [4] The molded article for a communication device according to any one of [1] to [3], wherein the thermoplastic resin composition further contains a repeating unit represented by the following formula (2):

[0024] [ka]

[0025] (In formula (2), Y 2 is a divalent organic group having an alicyclic ring or an aromatic ring.

[0026] [5] Y 1 and Y 2 The molded article for a communication device according to [4], wherein

[0027] [6] Y 1 and Y 2 The molded article for a communication device according to [4], wherein:

[0028] [7] Y 1 and Y 2 is a divalent organic group having an aromatic ring.

[0029] [8] Y 1 and Y 2 is a divalent organic group represented by the following formula (3):

[0030] [ka]

[0031] (In formula (3), X 1 represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. 1 ~R 4 each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or a substituted or unsubstituted aryl group, provided that R 1 and R 3 , or R 2 and R 4 may be bonded to each other to form a ring.

[0032] [9] Y 1 and Y 2 is a divalent organic group represented by the following formula (4):

[0033] [ka]

[0034] (In formula (4), X 1 , R 1 ~R 4 are the X in the formula (3), respectively. 1 , R 1 ~R 4 is equivalent to

[0035]

[10] Y 1 and Y 2 is a divalent organic group represented by the following formula (5):

[0036] [ka]

[0037] (In formula (5), X 1, R 1 ~R 4 are the same as in the formula (3), but R 1 and R 3 , R 2 and R 4 do not bond to each other to form a ring.)

[0038]

[11] X 1 is a divalent organic group represented by the following formula (6):

[0039] [ka]

[0040] (In formula (6), R 9 , R 10 R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 9 and R 10 may be bonded to each other to form a ring which may have a substituent.

[0041]

[12] The molded article for a communication device according to any one of [9] to

[11] , wherein the divalent organic group represented by the formula (4) is a divalent organic group selected from the group consisting of the following formulae (7a) to (7r):

[0042] [ka]

[0043]

[13] The dielectric loss tangent of the polycyanurate is 4.5 × 10 -3 The molded article for a communication device according to any one of [1] to

[12] below.

[0044]

[14] The dielectric loss tangent of the polycyanurate is 3.0 × 10 -3The molded article for a communication device according to

[13] , which is:

[0045]

[15] The dielectric loss tangent of the polycyanurate is 1.5 × 10 -3 The molded article for a communication device according to

[14] , which is:

[0046]

[16] The polycyanurate has an average linear expansion coefficient of 7.3 × 10 -5 / °C or less.

[0047]

[17] The polycyanurate has an average linear expansion coefficient of 7.0 × 10 -5 / °C or less.

[0048]

[18] The polycyanurate has an average linear expansion coefficient of 6.4 × 10 -5 / °C or less.

[0049]

[19] The polycyanurate has an average linear expansion coefficient of 5.5 × 10 -5 / °C or less.

[0050]

[20] The molded article for a communication device according to any one of [1] to

[19] , wherein the thermoplastic resin has a relative dielectric constant of 2.6 or less.

[0051]

[21] The molded article for a communication device according to

[20] , wherein the thermoplastic resin has a relative dielectric constant of 2.5 or less.

[0052]

[22] The molded article for a communication device according to any one of [1] to

[21] , wherein the thermoplastic resin composition contains one or more additives selected from the group consisting of a crosslinking agent, an ultraviolet absorber, an antistatic agent, an antioxidant, a coupling agent, a plasticizer, a flame retardant, a colorant, a dispersant, an emulsifier, an elasticity reducing agent, a diluent, an antifoaming agent, an ion trapping agent, a thickener, a leveling agent, inorganic particles, and organic particles.

[0053]

[23] The molded article for a communication device according to any one of [1] to

[22] , which is molded by extrusion molding, injection molding, blow molding, vacuum molding, pressure molding, press molding or film casting of the thermoplastic resin composition.

[0054]

[24] The molded article for a communication device according to any one of [1] to

[23] , which is any one selected from the group consisting of a sheet, a film, a printed wiring board, a coating, and a multilayer film to be built into the communication device.

[0055]

[25] The molded article for a communication device according to any one of [1] to

[23] , wherein the molded article for a communication device is a thin film transistor in which an insulating film, a sealing material, and a gate electrode layer are laminated in this order.

[0056]

[26] The molded article for a communications device according to any one of [1] to

[23] , which is a housing for a communications device or a cover for a housing for a communications device.

[0057]

[27] The molded article for a communication device according to any one of [1] to

[26] , wherein the communication device is a notebook computer, a tablet terminal, a smartphone, or a router device.

[0058]

[28] A communication device having a built-in microwave and / or millimeter wave antenna, obtained by using the molded article for a communication device according to any one of [1] to

[27] .

[0059]

[29] A metal-clad laminate in which a film layer and a metal foil layer are laminated, The film layer is a metal-clad laminate that is the molded article for a communication device according to any one of [1] to

[27] .

[0060]

[30] A polycyanurate containing a repeating unit represented by the following formula (1), in which the total content of a cyclic oligomer represented by the following formula (51) and a cyclic oligomer represented by the following formula (52) is less than 5% by weight.

[0061] [ka]

[0062] [ka]

[0063] (In formulas (51), (52), (1), Y 1 represents a divalent organic group. 1 is a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. In formula (52), Y2 is a divalent organic group having an alicyclic ring or an aromatic ring.

[0064]

[31] Polycyanurate consisting of a repeating unit represented by the following formula (8):

[0065] [ka]

[0066] (In formula (8), Y 3 represents a divalent organic group having an aliphatic ring, or a divalent organic group represented by the following formula (9): 2 is a group selected from the group consisting of a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0067] [ka]

[0068] (In formula (9), X 2 R represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group represented by the following formula (10): 11 ~R 14 each independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0069] [ka]

[0070] (In formula (10), R 15 , R 16 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0071]

[32] The polycyanurate according to

[30] or

[31] , wherein the glass transition temperature of the polycyanurate is 150°C or higher.

[0072]

[33] The dielectric loss tangent of the polycyanurate is 4.5 × 10 -3 The polycyanurate according to any one of

[30] to

[32] , which is:

[0073]

[34] The polycyanurate has an average linear expansion coefficient of 7.5 × 10 -5 / °C or less.

[0074]

[35] A thermoplastic resin composition containing the polycyanurate according to any one of

[30] to

[34] , wherein the thermoplastic resin composition contains a repeating unit represented by the formula (1) or the formula (8): The thermoplastic resin composition has a content of 10% by weight or more in the thermoplastic resin composition.

[0075]

[36] A molded article for a communication device having a built-in microwave and / or millimeter wave antenna, obtained using the polycyanurate according to any one of

[30] to

[34] or the thermoplastic resin composition according to

[35] . [Effects of the Invention]

[0076] The molded article for a communication device provided by the present invention has excellent radio wave transmittance in the microwave and / or millimeter wave bands, excellent heat resistance, and a low coefficient of linear expansion. Therefore, the molded article for a communication device of the present invention can be widely used as a sheet, film, coating, printed wiring board, or multilayer film built into a communication device having a built-in microwave and / or millimeter wave antenna, such as a notebook computer, a tablet terminal, a smartphone, or a router device; a thin-film transistor having an insulating film, a sealant, and a gate electrode layer stacked in this order; a housing for a communication device; and a cover for a housing for a communication device. DETAILED DESCRIPTION OF THE INVENTION

[0077] The present invention will be described in detail below with reference to embodiments and examples, but the present invention should not be construed as being limited to the embodiments and examples shown below. In this specification, unless otherwise specified, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit. The term "independently" when used to describe two or more objects together means that the two or more objects may be the same or different.

[0078] [overview] The molded article for a communication device of the present invention, which has a built-in microwave and / or millimeter wave antenna, is characterized by comprising a thermoplastic resin composition (hereinafter sometimes referred to as the "thermoplastic resin composition of the present invention") containing a polycyanurate containing a repeating unit represented by the following formula (1) (hereinafter sometimes referred to as the "polycyanurate of the present invention"). The communication device of the present invention is a communication device with a built-in microwave and / or millimeter wave antenna obtained by using the molded article for a communication device.

[0079] Hereinafter, the polycyanurate of the present invention and each component constituting the thermoplastic resin composition of the present invention containing the polycyanurate of the present invention will be described in detail.

[0080] <Polycyanurate> The polycyanurate of the present invention is characterized by containing a repeating unit represented by the following formula (1): The polycyanurate of the present invention may be composed of a repeating unit represented by the following formula (1), or may be a copolymerized polycyanurate containing a repeating unit represented by the following formula (1) and other repeating units. By using a thermoplastic resin composition containing a polycyanurate having a repeating unit represented by the following formula (1), the molded article for a communication device of the present invention can be made to have excellent radio wave transmittance in the microwave and / or millimeter wave bands, heat resistance, and low thermal expansion.

[0081] [ka]

[0082] (In formula (1), Y 1 represents a divalent organic group. 1 is a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0083] In formula (1), Z 1is a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0084] The above Z 1 Examples of the substituent corresponding to "substituted" in each functional group include alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl groups, aryl groups such as phenyl, tolyl, and naphthyl groups, aralkyl groups such as benzyl groups, alkoxy groups such as methoxy groups, amino groups such as diethylamino groups, and halogen atoms such as F, Cl, and Br.

[0085] Z 1 Specific examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms in the above formula include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; Methylethyl group, methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group, methyldodecyl group, methyltridecyl group, methyltetradecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl group, methyloctadecyl group, methylnonadecyl group; Dimethylethyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethylhexadecyl group, dimethylheptadecyl group, dimethyloctadecyl group; Trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group; Ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl group, ethyloctadecyl group; Propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, propylheptadecyl group; butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group; etc.

[0086] Of these, methyl and ethyl groups are preferred because they are more likely to exhibit the properties, such as heat resistance and dielectric properties, inherent to the compound when made into a polycyanurate.

[0087] Z 1Specific examples of the substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms in the above formula include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a bicyclo[2,2,1]heptyl group, a cyclooctyl group, and an adamantyl group.

[0088] Z 1 Specific examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms in the formula (I) include a phenyl group, a 2-methylphenyltolyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 4-ethylphenyl group, a 2-ethylphenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,3-dimethylphenyl group, a 3,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 4-butylphenyl group, a 2-tert-butylphenyl group, a 4-tert-butylphenyl group, a 3-tert-butylphenyl group, a 4-sec-butylphenyl group, a 4-isopropylphenyl group, a 2-isopropylphenyl group, a 4-amylphenyl group, a 4-tert-amylphenyl group, a 4-hexylphenyl group, Examples thereof include a 4-methoxyphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a 2,6-dimethoxyphenyl group, a 3,4-dimethoxyphenyl group, a 4-ethoxyphenyl group, a 4-(N,N-dimethylamino)phenyl group, a 4-(N,N-diethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 3-(N,N-dimethylamino)phenyl group, a 3-(N,N-diethylamino)phenyl group, a 4-(methylthio)phenyl group, a benzylphenyl group, a 4-(trifluoromethoxy)phenyl group, a 4-α-cumylphenyl group, a 4-acetylphenyl group, a 4-fluorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-phenoxyphenyl group, and a naphthyl group.

[0089] Among these, phenyl groups, methylphenyl groups such as 2-methylphenyl groups, methoxyphenyl groups such as 2-methoxyphenyl groups, and naphthyl groups are preferred, as they are more likely to exhibit the various properties, such as heat resistance and dielectric properties, inherent to the present compound when made into a polycyanurate.

[0090] Z 1 Specific examples of the substituted or unsubstituted aralkyl group in the above formula include a benzyl group and a phenylethyl group.

[0091] Z 1 Specific examples of the amino group in the formula (15) include the amino group represented by the following formula (15).

[0092] [ka]

[0093] In the above formula (15), R 38 and R 39 R each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. These organic groups may have any substituent. 38 and R 39 may be bonded to each other to form a ring. The * symbol in the above formula (15) and the substituent group (16) and formula (17) described below indicates the bonding site with the triazine ring in formula (1).

[0094] R 38 and R 39 Examples of the organic group having 1 to 20 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. 1 These are the same as the specific examples of the alkyl group, cycloalkyl group, aryl group and aralkyl group in the above.

[0095] R 38 and R 39 Specific examples of the amino group when they are bonded to each other to form a ring include those represented by the following substituent group (16).

[0096] [ka]

[0097] Among these, Z is preferred because it is easier to exhibit the properties derived from this compound, such as heat resistance and dielectric properties, when it is made into a polycyanurate. 1 As the amino group in 38 and R 39 is a methyl group, R 38 and R 39 is an ethyl group, R 38 is a methyl group and R 39 is a combination of phenyl groups, R 38 is an ethyl group and R 39 is a combination of phenyl groups, R 38 and R 39 An amino group of formula (15) is preferred, which is a piperidinyl group in which the groups are bonded to each other to form a six-membered ring.

[0098] Z 1 Specific examples of the alkoxy group in the formula (17) include alkoxy groups represented by the following formula (17).

[0099] [ka]

[0100] In the above formula (17), R 50 is selected from the group consisting of a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted or unsubstituted aralkyl group. R 50 is an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group, 50 Specific examples of Z 1 The specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group are the same as those in the above.

[0101] Z 1Specific examples of the substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms in the above formula include a phenoxy group, a 2-methylphenoxy group, a 4-methylphenoxy group, a 3-methylphenoxy group, a 4-ethylphenoxy group, a 2-ethylphenoxy group, a 2,6-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,3-dimethylphenoxy group, a 3,4-dimethylphenoxy group, a 2,5-dimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 2,3,6-trimethylphenoxy group, a 4-butylphenoxy group, a 2-tert-butylphenoxy group, a 4-tert-butylphenoxy group, a 3-tert-butylphenoxy group, a 4-sec-butylphenoxy group, a 4-isopropylphenoxy group, a 2-isopropylphenoxy group, a 4-amylphenoxy group, a 4-tert-amylphenoxy group, a 4-hexylphenoxy group, 4-Methoxyphenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 3,5-dimethoxyphenoxy group, 2,6-dimethoxyphenoxy group, 3,4-dimethoxyphenoxy group, 4-ethoxyphenoxy group, 4-(N,N-dimethylamino)phenoxy group, 4-(N,N-diethylamino)phenoxy group, 2-(N,N-dimethylamino)phenoxy group, 2-(N,N-dimethylamino)phenoxy group group, 3-(N,N-dimethylamino)phenoxy group, 3-(N,N-diethylamino)phenoxy group, 4-(methylthio)phenoxy group, benzylphenoxy group, 4-(trifluoromethoxy)phenoxy group, 4-α-cumylphenoxy group, 4-acetylphenoxy group, 4-fluorophenoxy group, 2-fluorophenoxy group, 3-fluorophenoxy group, 4-phenoxyphenoxy group, and naphthoxy group.

[0102] Among these, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-methoxyphenoxy, and naphthoxy groups are preferred, as they are more likely to exhibit the various properties, such as heat resistance and dielectric properties, inherent to the compound when made into a polycyanurate.

[0103] When made into a polycyanurate, the properties inherent to this compound, such as heat resistance and dielectric properties, are more readily exhibited, and from the standpoint of thermal stability, Z 1 is preferably selected from the group consisting of a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms, and more preferably selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and a substituted amino group.

[0104] In the formula (1), Y 1 is a divalent organic group selected from aliphatic groups and aromatic groups. When the compound is made into a polycyanurate, Y 1 The organic group is preferably a divalent organic group having an alicyclic ring or an aromatic ring, and more preferably a divalent organic group having an aromatic ring.

[0105] <Repeating unit represented by formula (2)> The thermoplastic resin composition of the present invention may contain a repeating unit of a carbonate bond represented by the following formula (2): In this case, the repeating unit represented by the following formula (2) may be contained in the polycyanurate of the present invention together with the repeating unit represented by the formula (1), or may be contained as a resin separate from the polycyanurate of the present invention, for example, as a polycarbonate resin. That is, the thermoplastic resin composition of the present invention may contain a polyisocyanurate-polycarbonate copolymer resin, which is the polycyanurate of the present invention, or may contain the polycyanurate of the present invention and a polycarbonate.

[0106] Even when the thermoplastic resin composition of the present invention contains a repeating unit represented by the following formula (2), the excellent heat resistance and dielectric properties owing to the polycyanurate of the present invention can be exhibited. In other words, by adding the polycyanurate of the present invention to a polycarbonate made from an existing bisphenol as a raw material, excellent heat resistance and dielectric properties can be imparted to the polycarbonate.

[0107] [ka]

[0108] (In formula (2), Y 2 is a divalent organic group having an alicyclic ring or an aromatic ring.

[0109] In this case, the divalent organic group Y in (1) 1 and Y in equation (2) 2 Whether the materials are the same or different, they exhibit excellent heat resistance and dielectric properties. 1 and Y 2 By freely selecting the above, it is possible to adjust the heat resistance and dielectric properties of the thermoplastic resin composition of the present invention, as well as the flowability and surface hardness according to the processability and application.

[0110] When the thermoplastic resin composition of the present invention contains a repeating unit represented by the above formula (2), it is preferable that the content ratio of the repeating unit represented by the above formula (1) (corresponding to the repeating unit (A) described below) to the repeating unit represented by the above formula (2) (corresponding to the repeating unit (B) described below) in the thermoplastic resin composition of the present invention satisfies the mass ratio of repeating unit (A) / repeating unit (B) described below.

[0111] <Y 1 , Y 2 Detailed explanation > Y 1 is a divalent organic group, and Y 2 is not particularly limited as long as it is a divalent organic group having an aliphatic ring or an aromatic ring. 1 and Y 2 The preferred structure is a divalent organic group having an alicyclic ring or an aromatic ring.

[0112] Specific examples of organic groups having a divalent aliphatic ring include those represented by the following formulae (12a) to (12g) and divalent aliphatic groups having a substituted aromatic ring structure, such as those represented by the following formulae (13) and (14).

[0113] [ka]

[0114] (In formula (13), R 17 ~R 19 are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent. 20 ~R 25 are each independently a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 4 to 10 carbon atoms which may have a substituent, an acyl group of 1 to 10 carbon atoms which may have a substituent, an alkoxy group of 1 to 10 carbon atoms which may have a substituent, an aryloxy group of 4 to 10 carbon atoms which may have a substituent, an acyloxy group of 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, an alkenyl group of 2 to 10 carbon atoms which may have a substituent, an alkynyl group of 2 to 10 carbon atoms which may have a substituent, a sulfur atom which has a substituent, a silicon atom which has a substituent, a halogen atom, a nitro group, or a cyano group. 20 ~R 25 At least two adjacent groups among these may be bonded to each other to form a ring. In formula (14), R 26 ~R 29 represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. 30 ~R 37 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. m and n each independently represent an integer of 0 to 5.

[0115] Y 1 , Y 2 Specific examples of the divalent organic group having an aromatic ring include the following examples of divalent organic groups Y-1 to Y-20 containing an aromatic ring.1 , Y 2 The organic group is not limited to these.

[0116] [ka]

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] [ka]

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] As mentioned above, Y 1 and Y 2may be the same or different, but Y is preferably the same in terms of ease of synthesis. 1 and Y 2 is preferably a divalent organic group having an aromatic ring.

[0137] Furthermore, Y 1 and Y 2 is preferably a structure represented by the following formula (3).

[0138] [ka]

[0139] (In formula (3), X 1 represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. 1 ~R 4 R each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 1 and R 3 , or R 2 and R 4 may be bonded to each other to form a ring.

[0140] X in the above formula (3) 1 represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. 1 When represents a sulfur atom, it represents a sulfide group, a sulfoxide group, or a sulfone group.

[0141] R in the above formula (3) 1 ~R 4is an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, specific examples thereof include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; Methylethyl group, methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group, methyldodecyl group, methyltridecyl group, methyltetradecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl group, methyloctadecyl group, methylnonadecyl group; Dimethylethyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethylhexadecyl group, dimethylheptadecyl group, dimethyloctadecyl group; Trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group; Ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl group, ethyloctadecyl group; Propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, propylheptadecyl group; butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group; etc.

[0142] R 1 ~R 4Specific examples of the substituted or unsubstituted aryl group include a phenyl group, a tolyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 4-ethylphenyl group, a 2-ethylphenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,3-dimethylphenyl group, a 3,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 4-butylphenyl group, a 2-tert-butylphenyl group, a 4-tert-butylphenyl group, a 3-tert-butylphenyl group, a 4-sec-butylphenyl group, a 4-isopropylphenyl group, a 2-isopropylphenyl group, a 4-amylphenyl group, a 4-tert-amylphenyl group, a 4-hexylphenyl group, and a 4-methoxyphenyl group. Examples thereof include a phenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a 2,6-dimethoxyphenyl group, a 3,4-dimethoxyphenyl group, a 4-ethoxyphenyl group, a 4-(N,N-dimethylamino)phenyl group, a 4-(N,N-diethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 3-(N,N-dimethylamino)phenyl group, a 3-(N,N-diethylamino)phenyl group, a 4-(methylthio)phenyl group, a benzylphenyl group, a 4-(trifluoromethoxy)phenyl group, a 4-α-cumylphenyl group, a 4-acetylphenyl group, a 4-fluorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-phenoxyphenyl group, and a naphthyl group.

[0143] When made into a polycyanurate, this compound is more likely to exhibit its inherent properties, such as heat resistance, low linear expansion coefficient, and low dielectric properties. 1 ~R 4 is preferably a methyl group, a phenyl group, or a naphthyl group, and particularly preferably a methyl group or a phenyl group.

[0144] Specific examples of the structure represented by the formula (3) include the above-mentioned examples of divalent organic groups Y-3 to Y-20 containing an aromatic ring.

[0145] The structure represented by the formula (3) is preferably a structure represented by the following formula (4) in terms of solubility, processability, etc.

[0146] [ka]

[0147] (In formula (4), X 1 , R 1 ~R 4 are the X in the formula (3), respectively. 1 , R 1 ~R 4 is equivalent to

[0148] Specific examples of the structure represented by formula (4) are the above-mentioned divalent organic groups containing an aromatic ring, Y-3, Y-5, Y-7, Y-9, Y-11, Y-13, Y-15, Y-16, Y-18, Y-19, and Y-20. Among these, the structure represented by the following formula (5) is preferred in that it is easier to exhibit various properties such as low dielectric properties of polycyanurate.

[0149] [ka]

[0150] (In formula (5), X 1 , R 1 ~R 4 are the same as in the formula (3), but R 1 and R 3 , R 2 and R 4 do not bond to each other to form a ring.)

[0151] Furthermore, among these, from the viewpoint of impact resistance and heat resistance of polycyanurate, X 1 is preferably a structure represented by the following formula (6).

[0152] [ka]

[0153] (In formula (6), R 9 , R 10 R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group. 9 , R 10 may be bonded to each other to form a ring which may have a substituent.

[0154] X 1 When R is a divalent organic group represented by the above formula (6), 9 , R 10 represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0155] R 9 , R 10 Specific examples of when is an unsubstituted alkyl group having 1 to 20 carbon atoms include, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-icosyl group; Methylethyl group, methylpropyl group, methylbutyl group, methylpentyl group, methylhexyl group, methylheptyl group, methyloctyl group, methylnonyl group, methyldecyl group, methylundecyl group, methyldodecyl group, methyltridecyl group, methyltetradecyl group, methylpentadecyl group, methylhexadecyl group, methylheptadecyl group, methyloctadecyl group, methylnonadecyl group; Dimethylethyl group, dimethylpropyl group, dimethylbutyl group, dimethylpentyl group, dimethylhexyl group, dimethylheptyl group, dimethyloctyl group, dimethylnonyl group, dimethyldecyl group, dimethylundecyl group, dimethyldodecyl group, dimethyltridecyl group, dimethyltetradecyl group, dimethylpentadecyl group, dimethylhexadecyl group, dimethylheptadecyl group, dimethyloctadecyl group; Trimethylbutyl group, trimethylpentyl group, trimethylhexyl group, trimethylheptyl group, trimethyloctyl group, trimethylnonyl group, trimethyldecyl group, trimethylundecyl group, trimethyldodecyl group, trimethyltridecyl group, trimethyltetradecyl group, trimethylpentadecyl group, trimethylhexadecyl group, trimethylheptadecyl group; Ethylpentyl group, ethylhexyl group, ethylheptyl group, ethyloctyl group, ethylnonyl group, ethyldecyl group, ethylundecyl group, ethyldodecyl group, ethyltridecyl group, ethyltetradecyl group, ethylpentadecyl group, ethylhexadecyl group, ethylheptadecyl group, ethyloctadecyl group; Propylhexyl group, propylheptyl group, propyloctyl group, propylnonyl group, propyldecyl group, propylundecyl group, propyldodecyl group, propyltridecyl group, propyltetradecyl group, propylpentadecyl group, propylhexadecyl group, propylheptadecyl group; butylhexyl group, butylheptyl group, butyloctyl group, butylnonyl group, butyldecyl group, butylundecyl group, butyldodecyl group, butyltridecyl group, butyltetradecyl group, butylpentadecyl group, butylhexadecyl group; etc.

[0156] R 9 , R 10Specific examples of the substituted or unsubstituted aryl group include a phenyl group, a tolyl group, a 4-methylphenyl group, a 3-methylphenyl group, a 4-ethylphenyl group, a 2-ethylphenyl group, a 2,6-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,3-dimethylphenyl group, a 3,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 4-butylphenyl group, a 2-tert-butylphenyl group, a 4-tert-butylphenyl group, a 3-tert-butylphenyl group, a 4-sec-butylphenyl group, a 4-isopropylphenyl group, a 2-isopropylphenyl group, a 4-amylphenyl group, a 4-tert-amylphenyl group, a 4-hexylphenyl group, and a 4-methoxyphenyl group. Examples thereof include a phenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 3,5-dimethoxyphenyl group, a 2,6-dimethoxyphenyl group, a 3,4-dimethoxyphenyl group, a 4-ethoxyphenyl group, a 4-(N,N-dimethylamino)phenyl group, a 4-(N,N-diethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 2-(N,N-dimethylamino)phenyl group, a 3-(N,N-dimethylamino)phenyl group, a 3-(N,N-diethylamino)phenyl group, a 4-(methylthio)phenyl group, a benzylphenyl group, a 4-(trifluoromethoxy)phenyl group, a 4-α-cumylphenyl group, a 4-acetylphenyl group, a 4-fluorophenyl group, a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-phenoxyphenyl group, and a naphthyl group.

[0157] R 9 and R 10When these are bonded to each other to form a ring which may have a substituent, examples of the ring-forming groups include a cyclohexylidene group, a 2-methylcyclohexylidene group, a 2-ethylcyclohexylidene group, a 3-methylcyclohexylidene group, a 3-propylcyclohexylidene group, a 4-methylcyclohexylidene group, a 4-butylcyclohexylidene group, a 2,6-dimethylcyclohexylidene group, a 3,5-dimethylcyclohexylidene group, a 3,3,5-trimethylcyclohexylidene group, Examples of such groups include a cyclohexylidene group, a 3-methyl-5-ethylcyclohexylidene group, a 3,3,5,5-tetramethylcyclohexylidene group, a cyclopentylidene group, a 2-methylcyclopentylidene group, a 3,5-dimethylcyclopentylidene group, a cycloheptylidene group, a cyclooctylidene group, a cyclononylidene group, a cyclodecylidene group, a cycloundecylidene group, a cyclododecylidene group, a fluorenylidene group, and a xanthonylidene group.

[0158] Among these, the structures represented by the following formulas (7a) to (7r) are more preferred in that when the compound is made into a polycyanurate, it is easier to exhibit the various properties derived from the compound, such as heat resistance and dielectric properties. In particular, structures such as (7c), (7d), (7e), (7f), (7g), (7h), (7i), (7j), (7k), (7l), (7m), (7n), (7o), (7p), (7q), and (7r) are more preferred because the introduction of a methyl group, a phenyl group, a cycloalkyl group, or the like into the monomer suppresses the movement of the molecular chain. Among these, structures (7d), (7k), (7l), (7p), and (7r) are particularly preferred because the monomers are easily available.

[0159] [ka]

[0160] These aliphatic groups and aromatic groups can be used either alone or as a mixture of two or more kinds in any combination and ratio.

[0161] <Polycyanurate containing a repeating unit represented by formula (8)> The polycyanurate of the present invention contains a repeating unit represented by the above formula (1). The polycyanurate of the present invention may be a polycyanurate containing a repeating unit represented by the following formula (8) (hereinafter, sometimes referred to as "repeating unit (A)").

[0162] [ka]

[0163] (In formula (8), Y 3 represents a divalent organic group having an aliphatic ring, or a divalent organic group represented by the following formula (9): 2 is a group selected from the group consisting of a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0164] [ka]

[0165] (In formula (9), X 2 R represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group represented by the following formula (10): 11 ~R 14 each independently represents a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0166] [ka]

[0167] (In formula (10), R 15 , R 16 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group.

[0168] In equation (8), Z 2 is selected from the group consisting of a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. Z 2 Specific examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms in 1 Similarly, Z 2 Specific examples of the substituted or unsubstituted aryl group having 6 to 20 carbon atoms, the substituted or unsubstituted amino group, and the substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms in the above formula are also given in Z 1 It is synonymous with that in.

[0169] Y 3 represents a divalent organic group having an aliphatic ring or a divalent organic group represented by formula (9). 3 When Y is a divalent organic group having an aliphatic ring, 3 is Y in equation (1). 1 It is synonymous with Y. 3 When R is a divalent organic group represented by formula (9), 11 ~R 14 is R in Equation (3). 1 ~R 4 is synonymous with.

[0170] Among these, R is the most preferred in that it is easier to exhibit the properties derived from this compound, such as heat resistance and dielectric properties, when made into a polycyanurate. 11 ~R 14 is preferably a methyl group, a phenyl group, or a naphthyl group, and particularly preferably a methyl group.

[0171] X 2 represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group represented by formula (10). 2 When represents a sulfur atom, it represents a sulfide group, a sulfoxide group, or a sulfone group. X 2 is a divalent organic group represented by formula (10), R in formula (10)15 , R 16 The hydrogen atom, the substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or the substituted or unsubstituted aryl group is R 9 , R 10 is synonymous with.

[0172] <Polycyanurate and polycarbonate resin composition> Even when the polycyanurate contains a polycarbonate repeating unit represented by the following formula (11) (hereinafter, sometimes referred to as "repeating unit (B)"), it can exhibit excellent heat resistance and dielectric properties. In other words, by adding the polycyanurate of the present invention to a polycarbonate made from an existing bisphenol as a raw material, it is possible to impart excellent heat resistance and dielectric properties to the polycyanurate.

[0173] [ka]

[0174] (In formula (11), Y 4 is Y in the above formula (8) 3 is equivalent to

[0175] Y in equation (8) 3 and Y in equation (11) 4 may be the same or different, but Y is preferably the same in terms of ease of synthesis. 3 and Y 4 is preferably a divalent organic group having an aromatic ring.

[0176] <Repeating unit (A) / Repeating unit (B)> As described above, the thermoplastic resin composition of the present invention may contain a polycyanurate containing the repeating unit (A) and a polycarbonate containing the repeating unit (B), or the polycyanurate of the present invention itself may be a polycyanurate-polycarbonate copolymer resin containing the repeating unit (A) and the repeating unit (B).

[0177] The content ratio of repeating units (A) to repeating units (B) in the polycyanurate-polycarbonate copolymer resin of the present invention or the thermoplastic resin composition of the present invention is not particularly limited, but the repeating unit (A) / repeating unit (B) (molar ratio) is preferably 1:99 to 99:1, particularly 10:80 to 60:40, especially 20:80 to 55:45, and of these, 35:65 to 50:50.

[0178] <Reduced viscosity> The reduced viscosity (ηSP / c) of the polycyanurate of the present invention is not particularly limited, but from the viewpoints of impact resistance, heat resistance, and processability, it is usually 0.1 dL / g or more, preferably 0.2 dL / g or more, and 0.4 dL / g or more, and usually 3.0 dL / g or less, preferably 2.0 dL / g or less, and more preferably 1.0 dL / g or less. The reduced viscosity is measured by the method described in the Examples.

[0179] <Glass transition temperature (Tg)> The glass transition temperature of the polycyanurate of the present invention is not particularly limited, but from the viewpoints of heat resistance and processability, it is usually 100°C or higher, preferably 140°C or higher, more preferably 150°C or higher, even more preferably 160°C or higher, and particularly preferably 180°C or higher, and is usually 350°C or lower, preferably 330°C or lower, and more preferably 280°C or lower.

[0180] The polycyanurate of the present invention has a triazine ring in the molecular chain, and thus has a large dipole, which allows it to have a high glass transition temperature. Furthermore, the polycyanurate of the present invention has a wide range of substituent options, and by appropriately adjusting the size of the substituent, the internal rotation potential in the molecular chain can be adjusted, thereby allowing the glass transition temperature to fall within a desired range. By adjusting the glass transition temperature to a preferred range using this method, good heat resistance and processability can be obtained when producing a molded product. The glass transition temperature is measured by the method described in the Examples.

[0181] <Relative permittivity (εr), dielectric loss tangent (tanδ)> The relative dielectric constant (εr) of the polycyanurate of the present invention, measured at a temperature of 23° C. and a frequency of 10 GHz, is preferably 2.6 or less, more preferably 2.55 or less, and particularly preferably 2.5 or less. The polycyanurate of the present invention has a dielectric loss tangent (tanδ) of 4.5×10 measured at a temperature of 23° C. and a frequency of 10 GHz. -3 Preferably, it is 4.0 x 10 or less. -3 More preferably, it is 3.0×10 or less. -3 More preferably, it is 2.5×10 or less. -3 It is particularly preferable that the value is 1.5×10 or less. -3 It is particularly preferred that:

[0182] When the dielectric constant and the dielectric loss tangent are equal to or less than the upper limit, the transmittance of microwaves and / or millimeter waves is good. The dielectric constant and the dielectric loss tangent are measured by the method described in the examples.

[0183] Generally, the chemical structural approach to lowering the dielectric constant of polymers is to suppress the ease of molecular polarization, and to lower the dielectric loss tangent, it is necessary to suppress the rotation of the molecular dipole. The polycyanurate of the present invention has a triazine ring with a large dipole in the molecular chain, and the dipole moment of the triazine ring is 0, which contributes to achieving a low dielectric constant and a low dielectric loss tangent. Furthermore, the dielectric loss tangent depends on the molecular mobility when an electric field is applied to the dielectric, and in order to achieve a lower dielectric loss tangent, it is necessary to reduce the substituent Z in formula (1). 1 and organic group Y 1 The selection of the preferred substituent Z is also important. 1 is explained in <Polycyanurate>, but the most preferred substituent Z 1Examples of the most preferred alkyl groups include methyl and ethyl groups for chain alkyl groups, and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2.2.1]heptyl, cyclooctyl, and adamantyl groups for cycloalkyl groups. The most preferred aryl groups are phenyl, methylphenyl groups such as 2-methylphenyl, methoxyphenyl groups such as 2-methoxyphenyl, and naphthyl groups. The most preferred amino groups are those represented by the following formula (15): 38 and R 39 is a methyl group, R 38 and R 39 is an ethyl group, R 38 is a methyl group and R 39 is a combination of phenyl groups, R 38 is an ethyl group and R 39 is a combination of phenyl groups, R 38 and R 39 The most preferred is an amino group represented by the following formula (15), which is a piperidinyl group in the following substituent group (16) in which the groups bond to each other to form a 6-membered ring.

[0184] [ka]

[0185] In the above formula (15), R 38 and R 39 R each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. These organic groups may have any substituent. 38 and R 39 may be bonded to each other to form a ring.

[0186] The * symbol in the above formula (15) and the following substituent group (16) indicates the bonding site with the triazine ring in formula (1).

[0187] [ka]

[0188] substituent Z 1When Y is an aryloxy group, the most preferred are phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-methoxyphenoxy, and naphthoxy. 1 The more preferred organic group Y 1 As examples of the above, structures represented by the following formulas (7a) to (7r) are more preferred, and in particular, by introducing a methyl group, a phenyl group, a cycloalkyl group, etc. into the monomer, such as (7c), (7d), (7e), (7f), (7g), (7h), (7i), (7j), (7k), (7l), (7m), (7n), (7o), (7p), (7q), (7r), etc., the movement of the molecular chain is suppressed, resulting in lower dielectric properties. Among these, (7d), (7k), (7l), (7p), and (7r) are particularly preferred because the monomers are easily available. As mentioned above, the substituent Z 1 and organic group Y 1 By adjusting the above, the movement of polymer chains when an AC electric field is applied to the dielectric can be suppressed, thereby making it possible to achieve a lower dielectric constant and dielectric loss tangent.

[0189] [ka]

[0190] <Average coefficient of linear expansion (CTE)> In the present invention, the reliability of the resin used in the molded article for communication devices was evaluated by measuring the CTE by the method described in (4) of the "Method for measuring and evaluating physical properties" section of the Examples section described later. The CTE of the polycyanurate of the present invention is preferably 7.5 × 10 as the average coefficient of linear expansion in this measurement method. -5 / °C or less, more preferably 7.3 × 10 -5 / °C or less, more preferably 7.0 × 10 -5 / °C or less, particularly preferably 6.4 × 10 -5 / °C or less, particularly preferably 5.5 × 10 -5 It exhibits a low CTE of less than / ℃.

[0191] Generally, the chemical structural factors that govern the thermal expansion behavior of polymers are that a polymer with a linear and rigid structure can have a smaller linear expansion coefficient than a polymer with a structure in which the polymer chain is nonlinear and flexible and can take various conformations. The molecular chain structure of the polycyanurate of the present invention is linear and rigid, so it exhibits a low linear expansion coefficient. In addition, in order to achieve a lower linear expansion coefficient, the substituent Z in formula (1) can be 1 and organic group Y 1 The selection of the preferred substituent Z is also important. 1 is explained in <Polycyanurate>, but the most preferred substituent Z 1 Examples of the most preferred alkyl groups include methyl and ethyl groups for chain alkyl groups, and cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, bicyclo[2,2,1]heptyl, cyclooctyl, and adamantyl groups for cycloalkyl groups. The most preferred aryl groups are phenyl, methylphenyl groups such as 2-methylphenyl, methoxyphenyl groups such as 2-methoxyphenyl, and naphthyl groups. The most preferred amino groups are those represented by the following formula (15): 38 and R 39 is a methyl group, R 38 and R 39 is an ethyl group, R 38 is a methyl group and R 39 is a combination of phenyl groups, R 38 is an ethyl group and R 39 is a combination of phenyl groups, R 38 and R 39 The most preferred is an amino group represented by the following formula (15), which is a piperidinyl group in the following substituent group (16) in which the groups bond to each other to form a 6-membered ring.

[0192] [ka]

[0193] In the above formula (15), R 38 and R 39 R each independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. These organic groups may have any substituent. 38 and R39 may be bonded to each other to form a ring. The * symbol in the above formula (15) and the following substituent group (16) indicates the bonding site with the triazine ring in formula (1).

[0194] [ka]

[0195] substituent Z 1 When Y is an aryloxy group, the most preferred are phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-methoxyphenoxy, and naphthoxy. 1 The more preferred organic group Y 1 As examples of the above, structures represented by the following formulas (7a) to (7r) are more preferred, and in particular, by introducing a methyl group, a phenyl group, a cycloalkyl group, etc. into the monomer, such as (7c), (7d), (7e), (7f), (7g), (7h), (7i), (7j), (7k), (7l), (7m), (7n), (7o), (7p), (7q), (7r), etc., the movement of the molecular chain is suppressed, resulting in lower dielectric properties. Among these, (7d), (7k), (7l), (7p), and (7r) are particularly preferred because the monomers are easily available. As mentioned above, the substituent Z 1 and organic group Y 1 By adjusting the coefficient of linear expansion, the movement of polymer chains can be suppressed, resulting in a lower coefficient of linear expansion. In environments with large temperature changes, the difference in the coefficient of linear expansion between the molded resin and the copper foil can cause cracks in the solder joint, reducing the reliability of the connection. Therefore, by adjusting the coefficient of linear expansion, the reliability can be improved.

[0196] [ka]

[0197] <Method of producing polycyanurate> The polycyanurate of the present invention can be produced by a conventionally known polymerization method. The polymerization method is not particularly limited. Examples of the polymerization method include an interfacial polymerization method and a melt transesterification method.

[0198] (interfacial polymerization method) [Polymerization reaction] In the interfacial polymerization method, polycyanurate is obtained by interfacially polymerizing a starting dihydroxy compound and a 2,6-dihalogeno-1,3,5-triazine compound represented by the following formula (41) in the presence of a polymerization catalyst, usually at a pH of 9 or higher, in the presence of an organic solvent inert to the reaction and an alkaline aqueous solution. A molecular weight modifier (terminal terminator) may be present in the reaction system as needed. An antioxidant may also be present to prevent oxidation of the starting dihydroxy compound.

[0199] [ka]

[0200] (In formula (41), Hal 1 , Hal 2 represents a halogen atom. Z 1 is Z in the formula (1). 1 is equivalent to

[0201] As the starting material 2,6-dihalogeno-1,3,5-triazine compound, a 2,6-dichloro-1,3,5-triazine compound is preferred because it can be easily derived from cyanuric chloride. The 2,6-dihalogeno-1,3,5-triazine compounds may be used alone or in any combination of two or more in any ratio.

[0202] As the starting dihydroxy compound, at least a dihydroxy compound capable of producing the polycyanurate of the present invention by reaction with a 2,6-halogeno-1,3,5-triazine compound is used.

[0203] The starting dihydroxy compound used in the production of the polycyanurate of the present invention includes a dihydroxy compound represented by the following formula (X). HO-Y 1 -OH (X) In formula (1), Y 1 is Y in the formula (1). 1 and preferably, Y in formula (2) 2 Y is more preferably represented by the formula (3), even more preferably represented by the formula (4), and particularly preferably represented by the formula (5). 1 More specifically, the compounds include those represented by the formulas (7a) to (7r).

[0204] Specific examples of such dihydroxy compounds include bisphenols such as bis(4-hydroxydiphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, and 1,1-bis(4-hydroxyphenyl)cyclohexane; biphenols such as 4,4'-dihydroxybiphenyl and 3,3',5,5'-tetramethyl-4,4'-dihydroxybiphenyl; bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ether, and bis(4-hydroxyphenyl)ketone. Among these, bisphenols are preferred from the viewpoint of the color, impact resistance, and heat resistance of the resulting polycyanurate, and structures represented by the following formulas (7a) to (7r) are particularly preferred from the viewpoint of dielectric properties.

[0205] [ka]

[0206] These dihydroxy compounds may be used alone or in any combination of two or more in any ratio.

[0207] The organic solvent inert to the reaction is not particularly limited, and examples thereof include chlorinated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, monochlorobenzene, and dichlorobenzene; aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, and nitrobenzene; etc. One type of organic solvent may be used, or two or more types may be used in any combination and ratio.

[0208] The alkaline compound contained in the alkaline aqueous solution is not particularly limited, but examples thereof include alkali metal compounds and alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium bicarbonate. Of these, sodium hydroxide and potassium hydroxide are preferred. One type of alkaline compound may be used, or two or more types may be used in any combination and ratio.

[0209] There is no limitation on the concentration of the alkaline compound in the alkaline aqueous solution, but in general, in order to control the pH of the alkaline aqueous solution to 10-12, the alkaline compound concentration is used at 5-10 wt %.

[0210] Since residual alkali compounds in the polycyanurate deteriorate the thermal stability of the polycyanurate, it is preferable to include a step of removing the alkali compounds used after polymerization of the polycyanurate of the present invention. Specific examples of the alkali compound removal step include a neutralization step with acid and washing with distilled water or ion-exchanged water. Among these, including a neutralization step with acid tends to efficiently remove the alkali compounds, making it preferable. These alkali compound removal steps may generally involve the above operations alone or in combination of two or more. It is desirable to remove as much of the alkali compounds and the acid used for neutralization as possible by washing with distilled water or ion-exchanged water. The acid used in the neutralization step is preferably dilute hydrochloric acid, but organic acids such as acetic acid, citric acid, succinic acid, and malic acid, phosphoric acid, phosphoric acid with sodium hydrogen, phosphoric acid with potassium hydrogen, ammonium chloride, and acids containing heteroatoms other than oxygen, such as monosodium citrate, may also be used.

[0211] The polymerization catalyst is not particularly limited, but examples thereof include aliphatic tertiary amines such as trimethylamine, triethylamine, tributylamine, tripropylamine, and trihexylamine; alicyclic tertiary amines such as N,N'-dimethylcyclohexylamine and N,N'-diethylcyclohexylamine; aromatic tertiary amines such as N,N'-dimethylaniline and N,N'-diethylaniline; quaternary ammonium salts such as trimethylbenzylammonium chloride, tetramethylammonium chloride, and triethylbenzylammonium chloride; pyridine; guanine; guanidine salts; etc. One type of polymerization catalyst may be used, or two or more types may be used in any combination and ratio.

[0212] The molecular weight modifier is not particularly limited, and examples thereof include aromatic phenols having a monovalent phenolic hydroxyl group, aliphatic alcohols such as methanol and butanol, mercaptans, and phthalimide, among which aromatic phenols are preferred. Specific examples of such aromatic phenols include phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot-butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol, mn-nonylphenol, and pn-nonylphenol. Examples of suitable phenols include phenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol, 2,5-di-t-butylphenol, 2,4-di-t-butylphenol, 3,5-di-t-butylphenol, 2,5-dicumylphenol, 3,5-dicumylphenol, p-cresol, bromophenol, tribromophenol, monoalkylphenols having a linear or branched alkyl group having an average of 12 to 35 carbon atoms at the ortho, meta, or para position, 9-(4-hydroxyphenyl)-9-(4-methoxyphenyl)fluorene, 9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene, and 4-(1-adamantyl)phenol. Among these, phenol, pt-butylphenol, p-phenylphenol, and p-cumylphenol are preferably used. The molecular weight modifier may be used alone or in any combination of two or more kinds in any ratio.

[0213] The amount of molecular weight modifier used is not particularly limited, but is, for example, usually 0.5 moles or more, preferably 1 mole or more, and usually 50 moles or less, preferably 30 moles or less, per 100 moles of the raw material dihydroxy compound.

[0214] The antioxidant is not particularly limited, but examples thereof include hindered phenol-based antioxidants. Specific examples thereof include pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 2,4-dimethyl-6-(1-methylpentadecyl)phenol, diethyl[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]phosphate, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6- triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylene bis(oxyethylene) bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, and the like.

[0215] Among these, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] and octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate are preferred. Commercially available phenolic antioxidants include "Irganox 1010" and "Irganox 1076" manufactured by BASF, and "Adekastab AO-50" and "Adekastab AO-60" manufactured by ADEKA.

[0216] The antioxidants may be used alone or in any combination of two or more in any ratio.

[0217] The amount of antioxidant used is not particularly limited, but is preferably 0.001 part by weight or more, more preferably 0.01 part by weight or more, and even more preferably 0.1 part by weight or more, relative to 100 parts by weight of the starting dihydroxy compound. By using an amount of antioxidant that is equal to or greater than the above-mentioned lower limit, the antioxidant's effect is sufficient. The amount of antioxidant used is preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, relative to 100 parts by weight of the starting dihydroxy compound. By using an amount of antioxidant that is equal to or less than the above-mentioned upper limit, gas generation during injection molding can be suppressed.

[0218] During the reaction, the order in which the reaction substrates (reaction raw materials), reaction solvent (organic solvent), catalyst, additives, etc. are mixed is arbitrary as long as the desired polycyanurate is obtained, and an appropriate order may be arbitrarily set.

[0219] As a method for synthesizing a copolymer resin of polycyanurate repeating units (A) and polycarbonate repeating units (B), a polycyanurate-polycarbonate copolymer resin can be obtained by using 2,6-dihalogeno-1,3,5-triazine, a dihydroxy compound, and a carbonate-forming compound as raw materials and carrying out interfacial polymerization in the presence of a polymerization catalyst.

[0220] In the above case, the 2,6-dihalogeno-1,3,5-triazine, dihydroxy compound, organic solvent inert to the reaction, alkali compound contained in the alkaline aqueous solution, polymerization catalyst, molecular weight modifier, and antioxidant can be used in the same specifications and amounts as in the above-mentioned synthesis of polycyanurate.

[0221] Carbonyl halides are preferably used as carbonate-forming compounds, and phosgene is particularly preferred. The method using phosgene is particularly called the phosgene method. Alternatively, a carbonate oligomer compound having an average molecular weight of several hundred to several thousand of a dihydroxy compound can be prepared in advance and used instead of the dihydroxy compound. The carbonate oligomer compound can be synthesized by an interfacial polymerization method or the melt transesterification method described below.

[0222] During the reaction, the order in which the reaction substrates (reaction raw materials), reaction solvent (organic solvent), catalyst, additives, etc. are mixed may be any order as long as the desired polycyanurate is obtained, and an appropriate order may be set as desired. The molecular weight modifier may be mixed at any time between the initial stage of the reaction and the start of the polymerization reaction.

[0223] The reaction temperature is not particularly limited, but is preferably 0 to 40° C. The reaction time is not particularly limited, but is preferably several minutes (for example, 10 minutes) to several hours (for example, 6 hours).

[0224] [Alkaline compound removal process] Since residual alkali compounds in the polycyanurate deteriorate the thermal stability of the polycyanurate, it is preferable to include a step of removing the alkali compounds used after polymerization of the polycyanurate of the present invention. Specific examples of the alkali compound removal step include a neutralization step with an acid and washing with distilled water or ion-exchanged water. Among these, including a neutralization step with an acid tends to efficiently remove the alkali compounds, making it preferable. These alkali compound removal steps may generally involve the above operations alone or in combination of two or more. It is desirable to remove as much of the alkali compounds and the acid used for neutralization as possible by washing with distilled water or ion-exchanged water. The acid used in the neutralization step is preferably dilute hydrochloric acid, but organic acids such as acetic acid, citric acid, succinic acid, and malic acid, phosphoric acid, phosphoric acid with sodium hydrogen, phosphoric acid with potassium hydrogen, ammonium chloride, and acids containing heteroatoms other than oxygen, such as monosodium citrate, may also be used.

[0225] The residual alkali content in the polycyanurate of the present invention is preferably less than 50 ppm. If the residual alkali metal content is 50 ppm or more, the moldability of the polycyanurate tends to deteriorate, which is undesirable. The residual alkali content in the polycyanurate can be determined using known methods such as ion chromatography, atomic absorption spectrometry, and inductively coupled plasma mass spectrometry. The amount of catalyst remaining in the polycyanurate of the present invention is preferably less than 200 ppm, more preferably less than 100 ppm. If the amount of catalyst remaining is 200 ppm or more, the dielectric properties tend to deteriorate, which is undesirable. The amount of catalyst remaining in the polycyanurate can be determined using gas chromatography.

[0226] [Obtaining Polycyanurate] The polycyanurate solid can be obtained from a reaction mixture containing the polycyanurate of the present invention that has undergone the polymerization reaction step and the alkali compound removal step by evaporating the organic solvent to obtain a solid, spraying the polycyanurate solution and instantly drying it to obtain granules or fine particles, adding the polycyanurate to warm water and evaporating the solvent to obtain a solid, or adding the polycyanurate solution after alkali compound removal dropwise to an organic solvent in which the polycyanurate is poorly soluble to obtain a solid. However, in the interfacial polymerization method, in addition to the polycyanurate of the present invention, a cyclic oligomer represented by the following formula (51) or (52) is produced in an amount of about 5 to 20% by weight based on the amount of the polycyanurate of the present invention produced. The reason for the difference in the amount of cyclic oligomer produced is that the substituent Z of the polycyanurate 1 and organic group Y 1 This is because the ease of cyclization varies depending on the substitution position and size of the , and the amount produced also varies.

[0227] [ka]

[0228] (In formulas (51) and (52), Z 1 ,Y 1 is the same as in the formula (1), and Y in the formula (52) 2 has the same meaning as in the above formula (2).

[0229] If a large amount of cyclic oligomers remain in the polycyanurate of the present invention, the thermal stability of the polycyanurate will deteriorate and surface defects, as described below, will occur, so it is preferable to reduce the cyclic oligomer content in the polycyanurate. The most preferred method for obtaining polycyanurate in high yield while reducing the cyclic oligomer content is to add a polycyanurate solution to an organic solvent in which the polycyanurate is poorly soluble and which dissolves the cyclic oligomers, and obtain the polycyanurate as a solid from which the cyclic oligomers have been removed. Specific examples of organic solvents used in this case include ester solvents such as ethyl acetate, methyl acetate, and butyl acetate; aromatic hydrocarbon solvents such as toluene and xylene; alcohol solvents such as methanol, ethanol, and isopropanol; and nitrile solvents such as acetonitrile. Ester solvents that have high solubility in cyclic oligomers and low solubility in polycyanurate are more preferred, and ethyl acetate is the most preferred.

[0230] When selecting a method of adding a polycyanurate solution to an organic solvent in which polycyanurate is poorly soluble to obtain a solid, commonly used alcohol solvents such as methanol, ethanol, and isopropanol have low solubility in polycyanurate and are suitable for extraction, but they also have low solubility in cyclic oligomers. Therefore, when a large amount of cyclic oligomers is purified in the polymerization reaction, a large amount of solvent must be used to remove the cyclic oligomers from the polycyanurate, which is not preferred.

[0231] The amount of residual cyclic oligomer in the polycyanurate of the present invention, as the total content of the cyclic oligomer represented by the formula (51) and the cyclic oligomer represented by the formula (52), is preferably less than 5% by weight, more preferably less than 3% by weight, and most preferably less than 1% by weight. When the polycyanurate is used as a sheet, film, coating, or molded article for communication devices, such as a multilayer film, to be incorporated into information and communication devices that are expected to use microwave and / or millimeter wave bands, if low molecular weight components such as monomers and oligomers are contained, these low molecular weight components may bleed out to the surface over time, causing surface defects that result in transmission loss, or may be transferred to rolls or the like, resulting in process defects. Furthermore, a high amount of residual cyclic oligomer is undesirable because it deteriorates the thermal stability of the polycyanurate, as shown in Table 3 below. The amount of residual cyclic oligomer in the polycyanurate can be measured by gel permeation chromatography (GPC), proton nuclear magnetic resonance (NPR), or the like. 1 In consideration of the necessity of removing cyclic oligomers from the polycyanurate, the amount of residual cyclic oligomers in the polycyanurate of the present invention, expressed as the total content of the cyclic oligomer represented by the formula (51) and the cyclic oligomer represented by the formula (52), is preferably 100 ppb by weight or more, more preferably 1 ppm by weight or more.

[0232] (melt transesterification method) The melt transesterification method is a method for producing polycyanurate by carrying out a transesterification reaction by polycondensation of a raw material containing, for example, a bifunctional triazine compound represented by the following formula (42), a raw material dihydroxy compound, and a catalyst. The raw material dihydroxy compound is not only an aromatic dihydroxy compound similar to that used in the interfacial polymerization method, but also a divalent aliphatic diol having a substituted aromatic ring structure, such as those represented by the following formulae (12a) to (12g) or the following formulae (13) and (14).

[0233] [ka]

[0234] (In formula (13), R 17 ~R 19 are each independently a direct bond or an alkylene group having 1 to 4 carbon atoms which may have a substituent. 20 ~R 25 are each independently a hydrogen atom, an alkyl group of 1 to 10 carbon atoms which may have a substituent, an aryl group of 4 to 10 carbon atoms which may have a substituent, an acyl group of 1 to 10 carbon atoms which may have a substituent, an alkoxy group of 1 to 10 carbon atoms which may have a substituent, an aryloxy group of 4 to 10 carbon atoms which may have a substituent, an acyloxy group of 1 to 10 carbon atoms which may have a substituent, an amino group which may have a substituent, an alkenyl group of 2 to 10 carbon atoms which may have a substituent, an alkynyl group of 2 to 10 carbon atoms which may have a substituent, a sulfur atom which has a substituent, a silicon atom which has a substituent, a halogen atom, a nitro group, or a cyano group. 20 ~R 25 At least two adjacent groups among these may be bonded to each other to form a ring. In formula (14), R 26 ~R 29 represents a substituted or unsubstituted alkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 6 to 20 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. 30 ~R 37 each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 6 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. m and n each independently represent an integer of 0 to 5.

[0235] [ka]

[0236] (In formula (42), L 1 , L 2 are each independently an aryloxy group; Z 1 is Z in the formula (1). 1is equivalent to

[0237] In equation (42), L 1 and L 2 are each independently an aryloxy group and may be the same or different. 1 and L 2 In the production of polycyanurate, a phenoxy group is preferred because of the ease with which the polycondensation reaction proceeds. 1 and L 2 When is a phenoxy group, phenol is produced as a by-product in the polycondensation reaction, but the phenol can be easily removed from the system by distillation.

[0238] When producing polycyanurate by the melt transesterification method, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and conventionally known catalysts can be used. For example, it is preferable to use an alkali metal compound and / or an alkaline earth metal compound. A basic compound such as a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound may be used in combination as an auxiliary. One type of transesterification catalyst may be used, or two or more types may be used in any combination and ratio.

[0239] In the melt transesterification method, the reaction temperature is not particularly limited, but is usually 100 to 320°C. The pressure during the reaction is not particularly limited, but is usually a reduced pressure of 2 mmHg or less. As a specific operation, a melt polycondensation reaction may be carried out under the above conditions while removing by-products.

[0240] In the presence of an alkali catalyst, the polycyanurate of the present invention is significantly affected by thermal history and oxidation, which may lead to a deterioration in color. Therefore, the reaction temperature is preferably 320°C or lower. In addition, to prevent oxygen leakage from the equipment due to excessive pressure reduction, it is preferable to select reduced pressure conditions with a lower limit of about 0.05 mmHg.

[0241] The reaction can be carried out in either a batch or continuous manner. In the case of a batch method, the order of mixing the reaction substrate, reaction solvent, catalyst, additives, etc. is arbitrary as long as the desired polycyanurate is obtained, and an appropriate order may be arbitrarily set.

[0242] In the melt transesterification method, a catalyst deactivator may be used as needed. Any compound that neutralizes the transesterification catalyst can be used as the catalyst deactivator. Examples include sulfur-containing acidic compounds and their derivatives, phosphorus-containing acidic compounds and their derivatives, etc. One type of catalyst deactivator may be used, or two or more types may be used in any combination and ratio.

[0243] The amount of the catalyst deactivator used is not particularly limited, but is usually 0.5 equivalents or more, preferably 1 equivalent or more, more preferably 3 equivalents or more, relative to the transesterification catalyst, and usually 50 equivalents or less, preferably 10 equivalents or less, more preferably 8 equivalents or less. The amount of the catalyst deactivator used is usually 1 ppm or more and 100 ppm or less, preferably 50 ppm or less, relative to the polycyanurate.

[0244] As a method for synthesizing a copolymer resin of polycyanurate repeating units (A) and polycarbonate repeating units (B), a polycyanurate-polycarbonate copolymer resin can be obtained by melt transesterification in the presence of a polymerization catalyst using a carbonate ester as a raw material in addition to the bifunctional triazine compound and raw material dihydroxy compound represented by the formula (42).

[0245] The carbonate ester may be, for example, a compound represented by the following formula (44): Examples of the carbonate ester include aryl carbonates, dialkyl carbonates, biscarbonates of dihydroxy compounds, monocarbonates of dihydroxy compounds, and carbonates of dihydroxy compounds such as cyclic carbonates.

[0246] [ka]

[0247] (In the above formula (44), R 38 and R 39 each independently represents an alkyl group, an aryl group, or an arylalkyl group having 1 to 20 carbon atoms.)

[0248] Below, R 38 and R 39 When the alkyl group is an alkyl or arylalkyl group, it is called a dialkyl carbonate, and when the aryl group is an aryl carbonate, it is called a diaryl carbonate. 38 and R 39 are preferably both aryl groups, and more preferably diaryl carbonate represented by the following formula (45).

[0249] [ka]

[0250] (In the above formula (45), R 40 and R 41 are each independently a halogen atom, a nitro group, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and p and q are each independently an integer of 0 to 5.

[0251] Specific examples of such carbonate esters include dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, and di-t-butyl carbonate, diphenyl carbonate (hereinafter sometimes abbreviated as "DPC"), bis(4-methylphenyl)carbonate, bis(4-chlorophenyl)carbonate, bis(4-fluorophenyl)carbonate, bis(2-chlorophenyl)carbonate, bis(2,4-difluorophenyl)carbonate, bis(4-nitrophenyl)carbonate, bis(2-nitrophenyl)carbonate, bis(methylsalicylphenyl)carbonate, and diaryl carbonates (which may have a substituent) such as ditolyl carbonate. Of these carbonate esters, diphenyl carbonate is particularly preferred. These carbonate esters may be used alone or in combination.

[0252] The ratio of the starting bifunctional triazine compound to the starting dihydroxy compound and carbonate ester is optional as long as the desired polycyanurate-carbonate copolymer resin is obtained. When polymerizing with the dihydroxy compound, the total amount of the bifunctional triazine compound and carbonate ester is preferably used in a slight excess relative to the starting dihydroxy compound. The amount of carbonate ester relative to the amount of dihydroxy compound is preferably 1.01 times (molar ratio) or more, more preferably 1.02 times or more. By setting the molar ratio at or above the lower limit, the thermal stability of the resulting polycyanurate-carbonate copolymer resin becomes good. The total amount of the bifunctional triazine compound and carbonate ester relative to the amount of the dihydroxy compound is preferably 1.30 times (molar ratio) or less, more preferably 1.20 times or less. By keeping the molar ratio at or below the upper limit, the reactivity is improved, the productivity of the polycyanurate-carbonate copolymer resin having the desired molecular weight is improved, and the amount of the remaining bifunctional triazine compound and carbonate ester in the resin is reduced, which is advantageous in that it is possible to suppress coloration of the resin during molding or when it is formed into a molded product.

[0253] In addition to the polycyanurate of the present invention, the melt transesterification method also produces a cyclic oligomer represented by the following formula (51) or (52) in an amount of about 1 to 3% by weight based on the amount of polycyanurate of the present invention. The amount of cyclic oligomer produced varies depending on the substituent of the monomer, but the melt transesterification method, unlike the interfacial polymerization method, does not use a solvent, and therefore the movement of polymer chains produced during polymerization is suppressed compared to the interfacial polymerization method, making it less likely to produce cyclic oligomers and making it suitable for polymerizing the polycyanurate of the present invention.

[0254] [ka]

[0255] (In formulas (51) and (52), Z 1 ,Y 1 is the same as in the formula (1), and Y in the formula (52) 2 has the same meaning as in the above formula (2).

[0256] <Thermoplastic resin composition> The thermoplastic resin composition of the present invention may contain other components in addition to the polycyanurate of the present invention (including polycyanurate-polycarbonate copolymer resin) and the polycarbonate described above, as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include resins other than polycarbonate, various resin additives, etc. One type of other component may be contained, or two or more types may be contained in any combination and ratio.

[0257] Examples of resins other than the polycyanurate and polycarbonate of the present invention include thermoplastic polyesters such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT); styrene resins such as polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), acrylonitrile-styrene-acrylic rubber copolymer (ASA), and acrylonitrile-ethylene propylene rubber-styrene copolymer (AES); polyolefins such as polyethylene (PE), polypropylene (PP), and cyclic cycloolefin (COP); polyamide (PA); polyimide (PI); polyetherimide (PEI); polyurethane (PU); polyphenylene ether (PPE); polyphenylene sulfide (PPS); polysulfone (PSU); polymethacrylate (PMMA); liquid crystal polymer (LCP); and polyaryl ether ketone (PAEK).

[0258] The content of the structural unit (A) contained in the thermoplastic resin composition of the present invention, ie, the repeating unit represented by the formula (1) is preferably 10% by weight or more in the thermoplastic resin composition.

[0259] Examples of resin additives include crosslinking agents, heat stabilizers, antioxidants, coupling agents, release agents, ultraviolet absorbers, colorants (dyes and pigments), flame retardants, anti-dripping agents, antistatic agents, preservatives, lubricants, anti-blocking agents, flow improvers, plasticizers, dispersants, emulsifiers, elasticity reducing agents, diluents, antifoaming agents, ion trapping agents, thickeners, leveling agents, inorganic particles, organic particles, antibacterial agents, glass fibers, carbon fibers, inorganic fillers, and organic fibers.

[0260] The thermoplastic resin composition of the present invention may contain one kind of these resin additives, or may contain two or more kinds in any combination and ratio.

[0261] Of these, the thermoplastic resin composition of the present invention preferably contains at least one additive selected from the group consisting of a crosslinking agent, an ultraviolet absorber, an antistatic agent, an antioxidant, a coupling agent, a plasticizer, a flame retardant, a colorant, a dispersant, an emulsifier, an elasticity reducing agent, a diluent, an antifoaming agent, an ion trapping agent, a thickener, a leveling agent, inorganic particles, and organic particles.

[0262] The content of the polycyanurate of the present invention in the thermoplastic resin composition of the present invention, including these other resins and resin additives, is preferably 30% by weight or more, more preferably 40% by weight or more, even more preferably 50% by weight or more, particularly preferably 60% by weight, and most preferably 70 to 100% by weight.

[0263] <Method of producing thermoplastic resin composition> The method for producing the thermoplastic resin composition of the present invention is not limited, and a wide variety of known methods for producing thermoplastic resin compositions can be used.Specific examples include methods of melt-kneading the mixture with a Banbury mixer, roll, single-screw kneading extruder, twin-screw kneading extruder, kneader, etc.

[0264] <Molded body> To produce a molded article using the thermoplastic resin composition of the present invention, the thermoplastic resin composition produced as described above may be pelletized and the pellets may be molded by various molding methods to produce a molded article, or the thermoplastic resin composition of the present invention may be melt-kneaded in an extruder and directly molded into a molded article, without going through the pelletizing step.

[0265] The shape of the molded product is not particularly limited and can be appropriately selected depending on the use and purpose of the molded product. Examples include plate-like, plate-like, rod-like, sheet-like, film-like, cylindrical, ring-like, circular, elliptical, polygonal, irregularly shaped, hollow, frame-like, box-like, and panel-like shapes. The molded article may be a molded article having an uneven surface, or a molded article having a three-dimensional shape with a three-dimensional curved surface. When used in the form of a sheet, film, plate, or the like, it may be laminated with other resin sheets to form a multilayer structure.

[0266] The method for forming the molded article is not particularly limited, and conventionally known molding methods can be used, such as injection molding, injection compression molding, extrusion molding, profile extrusion, transfer molding, blow molding, gas-assisted blow molding, blow molding, extrusion blow molding, IMC (in-mold coating molding), rotational molding, multilayer molding, two-color molding, insert molding, sandwich molding, foam molding, pressure molding, sheet molding, thermoforming, laminate molding, vacuum forming, pressure forming, press molding, and film casting. Of these, extrusion molding, injection molding, blow molding, vacuum forming, pressure forming, press molding, and film casting are preferred, and injection molding and extrusion molding are particularly preferred.

[0267] The molding temperature when molding the thermoplastic resin composition of the present invention is preferably 200°C or higher, more preferably 250°C or higher, and most preferably 280°C or higher. By setting the molding temperature to the above lower limit or higher, fluidity and moldability are improved. The molding temperature when molding the thermoplastic resin composition of the present invention is preferably 350°C or lower, particularly preferably 320°C or lower. By setting the molding temperature to the above upper limit or lower, the color tone of the thermoplastic resin composition can be made good.

[0268] The film may be a uniaxially or biaxially stretched film that has been stretched in one or two directions. Examples of methods for producing a stretched film include a method in which an unstretched film is produced as a precursor by a T-die casting method, a press method, a calendar method, or the like, and then stretched by a roll stretching method, a tenter stretching method, or the like, or a method in which melt extrusion and stretching are carried out in an integrated manner by an inflation method, a tubular method, or the like.

[0269] The molding temperature in the press method or the extrusion casting method using a T-die is adjusted as appropriate depending on the flow characteristics and film-forming properties of the thermoplastic resin composition used, but is generally 280° C. or higher and 370° C. or lower. For melt kneading, a commonly used single-screw extruder, twin-screw extruder, kneader, mixer, etc. can be used without any particular limitation.

[0270] When injection molding or extrusion molding is carried out, pigments, dyes, mold release agents, heat stabilizers, etc. may be added to the thermoplastic resin composition of the present invention as appropriate within the range that does not impair the object of the present invention.

[0271] <Injection molded body> The thermoplastic resin composition of the present invention can be suitably used as an injection-molded article by injection molding. The injection molding method is not particularly limited, and any molding method commonly used for thermoplastic resins can be used. Examples include ultra-high speed injection molding, injection compression molding, two-color molding, gas-assisted or other hollow molding methods, molding using an insulated mold, molding using a rapidly heated mold, foam molding (including supercritical fluids), insert molding, and IMC (in-mold coating molding). Molding methods using a hot runner system can also be used.

[0272] When an injection molding machine or the like is used, the mold temperature is preferably 150°C or less, more preferably 120°C or less, and most preferably 100°C or less. By setting the mold temperature at or below the upper limit, the cooling time during molding can be shortened, shortening the production cycle of molded products and improving productivity. When an injection molding machine or the like is used, the mold temperature is preferably 30°C or more, particularly preferably 50°C or more. Setting the mold temperature at or above the lower limit is preferable because it allows for the production of uniform molded products.

[0273] <Extrusion molded body> The thermoplastic resin composition of the present invention can be suitably used as an extrusion molded article by extrusion molding. There are no particular limitations on the method for producing an extrusion molded article from the thermoplastic resin composition of the present invention, but an extrusion molding machine is usually used. The extrusion molding machine is generally equipped with a T-die, a round die, or the like, and extrusion molded articles of various shapes can be obtained. Examples of extrusion molded articles include sheets, films, plates, tubes, pipes, and the like. Among these, sheets or films are preferred.

[0274] <Application> The molded article of the thermoplastic resin composition of the present invention can be used, for example, as parts for various automobile components, electrical and electronic devices, information terminal devices, office automation equipment, machine parts, home appliances, vehicle parts, building materials, various containers, leisure goods and miscellaneous goods, lighting equipment, etc., particularly housings for electronic devices such as smartphones and computers, antenna covers, covers for wired communication devices such as routers and switches, covers for millimeter-wave radar, thin-film transistors in which a multilayer film, an insulating film, an encapsulant, and a gate electrode layer are laminated in this order, and printed wiring boards.

[0275] Among these, the thermoplastic resin composition of the present invention has particularly excellent properties of transmittance for microwave and / or millimeter wave band radio waves, heat resistance, and low linear expansion, and therefore the thermoplastic resin composition of the present invention can be effectively used as a molding material for a communication device housing having a built-in microwave and / or millimeter wave antenna, a cover for the communication device housing, an insulating film, a sealant, a printed wiring board, etc.

[0276] <Thickness of molded body> The thickness of a molded article made from the thermoplastic resin composition of the present invention, particularly a molded article for a communication device incorporating a microwave and / or millimeter wave antenna as described below, is preferably 1.5 mm or less, more preferably 1.2 mm or less, and most preferably 1.0 mm or less. Here, the thickness of the molded article refers to the thickness of a portion occupying 50% or more of the area of ​​the entire molded article, such as the thickness of the main plate surface. When the thickness of the molded article is equal to or less than the upper limit, the transmission loss can be reduced. When the thickness of the molded article is equal to or more than the lower limit, the mechanical strength required to maintain the structure of the molded article can be made sufficient.

[0277] There are no limitations on the shape, pattern, color, dimensions, etc. of the molded article for a communication device having a built-in microwave and / or millimeter wave antenna, and these can be appropriately selected depending on the application of the molded article for a communication device having a built-in microwave and / or millimeter wave antenna.

[0278] In the present invention, microwaves refer to radio waves with a frequency of 3.0 to 30 GHz, and millimeter waves refer to radio waves with a frequency of 30 to 300 GHz. Therefore, microwaves and / or millimeter waves refer to radio waves with a frequency of 3.0 to 300 GHz. In other words, a communication device with a built-in microwave and / or millimeter wave antenna refers to a communication device with a built-in antenna that transmits and receives radio waves with a frequency of 3.0 to 300 GHz. Specific examples of such communication devices include laptop computers, tablet devices, smartphones, and router devices that transmit and receive radio waves with a frequency of 3.0 to 300 GHz.

[0279] In the molded article for a communication device having a built-in microwave and / or millimeter wave antenna of the present invention, the frequency at which the microwave and / or millimeter wave antenna transmits and receives is not particularly limited as long as it is 3.0 to 300 GHz, but is more suitable for radio waves in the frequency band of 3.2 to 250 GHz, and even more suitable for radio waves in the frequency band of 3.4 to 200 GHz.

[0280] In particular, the molded article for a communication device of the present invention having a built-in microwave and / or millimeter wave antenna can be suitably used for radio waves in the frequency band of 3.5 to 30 GHz used in 5G (fifth generation mobile communication system).

[0281] Radio waves in the microwave and / or millimeter wave bands tend to have poor radio wave transmittance, and from this perspective, a molded article for a communication device incorporating an antenna for transmitting and receiving radio waves in the microwave and / or millimeter wave bands is required to have high radio wave transmittance. Communication devices that transmit and receive microwave and / or millimeter wave band radio waves tend to generate heat, and therefore molded articles for communication devices that incorporate antennas that transmit and receive microwave and / or millimeter wave band radio waves are required to have high heat resistance and a low coefficient of linear expansion.

[0282] The polycyanurate of the present invention contained in the thermoplastic resin composition of the present invention used in the molded article for a communication device having a built-in antenna for transmitting and receiving radio waves in the microwave and / or millimeter wave bands of the present invention combines a low dielectric constant, a low dielectric loss tangent, high heat resistance, and a low coefficient of linear expansion. Thus, the thermoplastic resin composition of the present invention containing the polycyanurate of the present invention combines a low dielectric constant, a low dielectric loss tangent, high heat resistance, and a low coefficient of linear expansion, and is suitable for use in the molded article for a communication device that transmits and receives radio waves in the microwave and / or millimeter wave bands.

[0283] Specific examples of molded articles for communication devices having built-in microwave and / or millimeter wave antennas include sheets, films, coatings, and multilayer films to be built into notebook computers, tablet terminals, smartphones, router devices, etc.; housings for communication devices; and thin film transistors and printed wiring boards in which covers, insulating films, sealants, and gate electrode layers for housings for communication devices are laminated in this order. The molded articles for communication devices of the present invention, which are made from the thermoplastic resin composition of the present invention, are particularly suitable for these applications.

[0284] <Applications of resin sheets> Examples of applications of the resin sheet made of the thermoplastic resin composition of the present invention include, but are not limited to, copper foil laminates, flexible printed circuit boards, multilayer printed wiring boards, circuit board materials for electric and electronic devices such as capacitors, underfill materials, interchip fills for 3D-LSI, insulating sheets, and heat dissipation substrates.

[0285] <Circuit board materials> A resin sheet made of the thermoplastic resin composition of the present invention can be used as a circuit board material by laminating it with a conductor. The conductor may be a metal foil made of a conductive metal such as copper or aluminum, or an alloy containing such a metal, or a metal layer formed by plating or sputtering. When used as a circuit board material for electric and electronic devices, the resin sheet preferably has a thickness of 10 μm or more and 200 μm or less, and the conductor preferably has a thickness of 0.2 μm or more and 70 μm or less.

[0286] A circuit board material using the thermoplastic resin composition of the present invention is characterized by a sufficiently low dielectric loss tangent. The dielectric loss tangent of the circuit board material is preferably less than 0.01 at 12 GHz, more preferably less than 0.008. The lower the dielectric loss tangent, the more efficient and faster the electrical signal transmission can be when the circuit board is made. The lower limit of the dielectric loss tangent is not particularly limited, and it is sufficient as long as it is 0 or greater.

[0287] <Method of manufacturing circuit board materials> The circuit board material of the present invention can be produced, for example, by the following method. After laminating a conductor on the resin sheet of the present invention, a circuit is formed using a photoresist or the like, and the required number of such layers are laminated. The lamination of the resin sheet and the conductor may be performed by directly laminating a conductive metal foil on the resin sheet, by bonding the resin sheet and the conductive metal foil with an adhesive, by forming a conductive metal layer by plating or sputtering, or by combining these methods.

[0288] <Metal-clad laminate> The metal-clad laminate of the present invention is a metal-clad laminate in which a film layer and a metal foil layer are laminated together, and the film layer is the metal-clad laminate that is the above-mentioned molded article for a communication device of the present invention.

[0289] The details of the metal-clad laminate of the present invention are the same as those of the circuit board material described above, and the film layer corresponds to a resin sheet made of the thermoplastic resin composition of the present invention, and the metal foil corresponds to the conductor described above. In the metal-clad laminate of the present invention, the metal foil layer is laminated with the film layer, which is the molded article for a communication device of the present invention. [Example]

[0290] The present invention will be described in more detail below with reference to the following examples. It is not limited to:

[0291] <Methods for measuring and evaluating physical properties> The physical properties of the resins (polycyanurate, polycyanurate-polycarbonate copolymer resin, or polycarbonate) obtained in the following Examples and Comparative Examples were measured and evaluated by the following methods.

[0292] (1) Molecular weight measurement: reduced viscosity (ηSP / c) The resin was dissolved in methylene chloride (concentration c = 0.60 g / dL), and the specific viscosity (ηsp) at 20°C was measured using an Ubbelohde viscometer (manufactured by Moritomo Rika Kogyo Co., Ltd.), and the reduced viscosity (ηsp / c) was calculated by dividing by the concentration c.

[0293] (2) Molecular weight measurement: gel permeation chromatography (GPC) The resin was dissolved in tetrahydrofuran, and the weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using Shimadzu Corporation's SCL-10AVP under the following conditions. Column: TSKgel α-3000 (particle diameter 7 μm, inner diameter 7.8 mm, length 30 cm) + TSKgel α-4000 (particle diameter 10 μm, inner diameter 7.8 mm, length 30 cm) Mobile phase: Tetrahydrofuran (containing 0.03% by volume of 2,6-di-t-butyl-4-methylphenol as a stabilizer) Detection wavelength: 254 nm Flow rate: 1.0mL / min Column oven temperature: 40°C

[0294] (3) Heat resistance: Glass transition temperature (Tg) Using a differential scanning calorimeter (DSC7020 AS-3D manufactured by SII), approximately 10 mg of a resin sample was heated at a heating rate of 10°C / min to measure the calorific value, and in accordance with ISO 3146, the extrapolated glass transition onset temperature was determined as the temperature at the intersection of a straight line extending the low-temperature baseline to the high-temperature side and a tangent drawn at the point where the gradient of the curve of the stepwise change in the glass transition is maximum. This extrapolated glass transition temperature was taken as the glass transition temperature (Tg).

[0295] (4) Heat resistance: Simultaneous differential thermogravimetry measurement (Td5) Using a thermogravimetric and differential thermal analyzer (TG-DTA EXTER6000 manufactured by SII), approximately 5 mg of the resin sample was heated at a temperature increase rate of 10°C / min, and the thermal decomposition temperature (5% weight loss temperature, Td5) was measured from the obtained thermal decomposition curve.

[0296] (5) Thermal stability evaluation (340°C, 30 minutes) In order to heat and melt polycyanurate to create molded products such as films, we conducted an accelerated thermal stability test at 340°C, slightly higher than the melting temperature, to simulate a melt-molding state, and evaluated the difference in thermal stability depending on the cyclic oligomer content.The evaluation method was to use a simultaneous differential thermal and thermogravimetric analyzer (SII TG-DTA EXTER6000) to heat approximately 2 mg of resin sample at 340°C for 30 minutes, and calculate the weight loss rate (%) after 30 minutes from the obtained thermal decomposition curve.

[0297] (6) Dielectric properties: relative permittivity (ε r )·Dielectric tangent (tanδ) The resin was vacuum dried at 80°C for 5 hours and then molded into a film using a heat press molding machine to produce a film with a thickness of 200 to 600 μm. The molding conditions for the heat press molding machine were adjusted appropriately between a temperature of 150 to 250°C and a pressure of 10 to 15 MPa. From this film, strips of film measuring 70 mm in length, 1.97 to 1.38 mm in width, and 431 to 624 μm in thickness were cut out. After conditioning for 48 hours at a room temperature of 23°C and a humidity of 50%, the relative permittivity (ε) was measured at a frequency of 10 GHz using a cavity resonator (Kanto Applied Electronics Development Co., Ltd. CP-531) and a series network analyzer (Keysight Technologies E8361A PNA). r ) and dielectric loss tangent (tan δ) were measured.

[0298] (7) Average coefficient of linear expansion (CTE) (3) Dielectric properties: relative permittivity (ε r Films formed in the same manner as in the case of dielectric loss tangent (tanδ) were punched out using a super straight cutter with a width of 4 mm and a length of 40 mm, and measured using a TMA / SS6100 manufactured by SII Nano Technology, Inc. The film sample was held at a chuck distance of 10 mm, and the CTE was measured between -20°C and 80°C when the temperature was increased from -30°C to 100°C at a rate of 10°C / min with 120 mL / min of nitrogen.

[0299] (8) Proton nuclear magnetic resonance ( 1 H NMR) The following equipment and solvents were used: Equipment: JEOL ECZ400S nuclear magnetic resonance spectrometer, 400MHz Solvent: deuterated chloroform containing 0.03% by volume of tetramethylsilane

[0300] (9) Matrix-assisted laser desorption / ionization mass spectrometry Using the following equipment, mass spectrometry was performed on the low molecular weight components removed in the ethyl acetate precipitate recovery treatment in Example 8. As a result, it was confirmed that they were nine types of cyclic oligomers represented by the following formula (50A). Equipment: JEOL JMS-S3000 Ionization method: matrix-assisted laser desorption ionization Measurement mode: Spiral mode Polarity: Positive ion detection Scanning mass range: 50-10,000 (m / z) Sample preparation: A 0.2 μL mixture of equal volumes of a tetrahydrofuran solution of the sample and a 10 mg / mL tetrahydrofuran solution of the matrix substance was applied to a MALDI-MS sample plate to create a dry spot. The dry spot was irradiated with an ultraviolet laser, and the generated ions were observed.

[0301] [ka]

[0302] [Synthesis Example 1: Synthesis of 2,4-dichloro-6-phenyl-1,3,5-triazine [3]]

[0303] [ka]

[0304] Cyanuric chloride [1] (200 g, 1.09 mol) was dissolved in tetrahydrofuran (2 L). Under a nitrogen atmosphere, a 3 mol / L tetrahydrofuran solution of phenylmagnesium bromide [2] (397.66 mL) was added dropwise to this solution at 0°C. After the addition, the mixture was stirred at 30°C for 12 hours under a nitrogen atmosphere. The reaction mixture was then quenched by slowly adding 100 mL of saturated aqueous ammonium chloride at 0°C. After removing the tetrahydrofuran under reduced pressure, the residue was dissolved in ethyl acetate (3 L) and washed with water (2 L, twice). The organic layer was dried over anhydrous sodium sulfate, the sodium sulfate was removed by filtration, and the filtrate was concentrated to obtain the crude product. The crude product was added to a mixture of petroleum ether and ethyl acetate to form a slurry, and the precipitate was filtered and dried to obtain 2,4-dichloro-6-phenyl-1,3,5-triazine [3] (157 g, 694.50 mmol, yield 64.0%, HPLC purity 98.8%) as a light brown solid. 1The 1 H NMR spectrum was consistent with the desired product. 1 H NMR(400MHz,CDCl3) δ=8.52(dd,J=1.2,8.4Hz,6H),7.71-7.62(m,3H),7.58-7.47(m,6H)

[0305] [Synthesis Example 2: Synthesis of 2,4-diphenoxy-6-phenyl-1,3,5-triazine [5]]

[0306] [ka]

[0307] Sodium hydroxide (58.39 g, 1.46 mol) was added to pure water (300 mL) to form a solution, and phenol [4] (134.26 g, 1.43 mol) was added and dissolved at 0 °C. This solution was added dropwise to a mixed solution of 2,4-dichloro-6-phenyl-1,3,5-triazine [3] (150 g, 663.54 mmol) synthesized by the method described in Synthesis Example 1, acetone (1 L), and pure water (1 L) at 0 °C under a nitrogen atmosphere. The mixture was stirred at 0 °C for 1 hour and then at 30 °C for 8 hours. The reaction mixture was filtered, and the collected cake was washed with heptane (200 mL). The filter cake was then concentrated to dryness to obtain crude crystals of 2,4-diphenoxy-6-phenyl-1,3,5-triazine (185 g) as an off-white solid, which was purified by silica gel column chromatography (eluting with a heptane / ethyl acetate ratio gradually changed from 1 / 0 to 10 / 1). The pure fractions were concentrated to dryness to obtain 2,4-diphenoxy-6-phenyl-1,3,5-triazine [5] (155 g, 454 mmol, yield 68.4%, HPLC purity 99.9%) as a white solid. 1 The 1 H NMR spectrum was consistent with the desired product. 1 H NMR(400MHz,CDCl3) δ=8.34-8.25(m,2H),7.58-7.51(m,1H),7.48-7.38(m,6H),7.32-7.21(m,6H)

[0308] [Synthesis Example 3: Synthesis of 4,6-dichloro-N-phenyl-N-methyl-1,3,5-triazin-2-amine [7]]

[0309] [ka]

[0310] Cyanuric chloride [1] (200 g, 1.08 mol) was dissolved in tetrahydrofuran (1 L), potassium carbonate (224.83 g, 1.63 mol) was added, and the mixture was cooled to 0 °C under a nitrogen atmosphere with stirring. Next, a solution of N-methylaniline [6] (118.53 g, 1.11 mol) in THF (1 L) was added dropwise at 0 °C. This mixture was stirred at 25 °C for 3 hours. The reaction mixture was then poured into ice water (2 L) to precipitate crystals. The precipitated crystals were removed by filtration, and ethyl acetate (300 mL) was added to the filtrate, and the product was extracted into the organic layer. This procedure was repeated twice. The resulting organic layer was dried over anhydrous sodium sulfate, the sodium sulfate was removed by filtration, and the solvent was removed under reduced pressure to obtain the crude product. The crude product was purified by silica gel column chromatography (eluting with n-heptane / ethyl acetate at a ratio of 90 / 10). The pure fraction was concentrated to dryness and added to n-heptane / ethyl acetate (5 / 1, 1680 mL). After stirring at 20°C for 12 hours, the crystals were filtered and dried under reduced pressure to give 4,6-dichloro-N-phenyl-N-methyl-1,3,5-triazin-2-amine [7] (132.39 g, 48.3% yield) as a white solid. 1 The 1 H NMR spectrum was consistent with the desired product. 1 H NMR(400MHz,CDCl3) δ=7.39-7.32(m,2H),7.27-7.23(m,1H),7.17-7.12(m,2H),3.45(s,3H)

[0311] [Synthesis Example 4: Synthesis of 4,6-diphenoxy-N-methyl-N-phenyl-1,3,5-triazin-2-amine [8]]

[0312] [ka]

[0313] Sodium hydroxide (34.49 g, 862.40 mmol) was added to pure water (30 mL) to form a solution, and phenol [4] (79.32 g, 842.80 mmol) was added and dissolved at 0 °C. This solution was added dropwise to a mixed solution of 4,6-dichloro-N-phenyl-N-methyl-1,3,5-triazin-2-amine [7] (100 g, 392.00 mmol), synthesized by the method described in Synthesis Example 5, acetone (60 mL), and pure water (60 mL) at 0 °C under a nitrogen atmosphere. The mixture was stirred at 0 °C for 1 hour and then at 25 °C for 12 hours. The precipitated crystals were filtered, and the collected cake was washed with pure water to obtain crude crystals. The crude crystals were purified by silica gel column chromatography (eluting with n-heptane / ethyl acetate at a ratio of 90 / 10). The pure fractions were concentrated to dryness and added to n-heptane (400 mL). After stirring at 20°C for 12 hours, the crystals were filtered and dried under reduced pressure to give 4,6-diphenoxy-N-methyl-N-phenyl-1,3,5-triazin-2-amine [8] (94.25 g, yield 67.2%, HPLC purity 99.9%) as a white solid. 1 The 1 H NMR spectrum was consistent with the desired product. 1 H NMR(400MHz,CDCl3) δ=7.53-7.02(m,15H),3.48(s,3H),7.36-7.18(m,6H),6.95-6.87(m,2H),3.85(s,3H)

[0314] [Synthesis Example 5: Synthesis of polycarbonate oligomer

[11] of 2,2-bis(4-hydroxyphenyl)propane] [ka]

[0315] In a glass reactor equipped with a reactor agitator, a reactor heater, and a reactor pressure regulator, 100 parts by weight of 2,2-bis(4-hydroxyphenyl)propane [9] (hereinafter sometimes abbreviated as "BPA") and 62.9 parts by weight of diphenyl carbonate

[10] (hereinafter sometimes abbreviated as "DPC") were added, and 2.14 × 10 cesium carbonate was added. -3 parts by weight were added to prepare a raw material mixture (the molar ratio of BPA to DPC was 67:100). Next, the pressure inside the glass reactor was reduced to approximately 50 Pa (0.38 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated three times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was raised to 150°C, stirring was performed (100 rpm), and the temperature was raised to 240°C at atmospheric pressure over 60 minutes to dissolve the mixture (dissolution step). After maintaining the temperature at 240°C for 30 minutes as the first stage of the polymerization reaction, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) absolute to 13.3 kPa (100 Torr) over 40 minutes while distilling off phenol, a by-product of the oligomerization reaction occurring inside the reactor.

[0316] The pressure inside the reactor was then maintained at 13.3 kPa, and the reaction was continued for 60 minutes while further distilling off phenol. In the second polymerization stage, the reactor external temperature was raised to 270°C over 20 minutes, and simultaneously the reactor internal pressure was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) absolute over 30 minutes, and the distilled phenol was removed from the system. The absolute pressure inside the reactor was then reduced to 200 Pa or less, and the polycondensation reaction was continued. In the case of oligomers, the stirring power did not increase, so the polycondensation reaction was terminated after a predetermined time (30 minutes). The total polymerization time in this Synthesis Example 5 is the time from the start of the first-stage polymerization reaction to the end of the second-stage reaction.

[0317] Next, the pressure inside the reactor was restored with nitrogen, and the molten oligomer was removed from the reactor and cooled at room temperature to obtain a mixture of 2,2-bis(4-hydroxyphenyl)propane polycarbonate oligomer and unreacted BPA (hereinafter sometimes abbreviated as "BPA polycarbonate oligomer")

[11] as a light orange solid. 1 The number average molecular weight was calculated to be 770 from the integral ratio of the 1 H NMR signals. 1 H NMR(400MHz, CDCl3) δ=7.248-7.227(m,27H),7.165-7.132(m,26H),7.074-7.056(m,12H),6.70 5-6.691(m,12H),4.86(m,6H),1.697(s,27H),1.665(s,27H),1.634(s,6H)

[0318] [Example 1] A raw material mixture was prepared by adding 100 parts by weight of 2,2-bis(4-hydroxyphenyl)propane (hereinafter, sometimes abbreviated as "BPA"), 149.5 parts by weight of 2,4-diphenoxy-6-phenyl-1,3,5-triazine [5] (referred to as "monomer [5]" in Tables 1A, 1B, 2A, and 2B) synthesized by the method described in Synthesis Example 2, and 0.143 parts by weight of cesium carbonate as a catalyst to a glass reactor equipped with a reactor stirrer, a reactor heating device, and a reactor pressure adjusting device.

[0319] Next, the pressure inside the glass reactor was reduced to approximately 50 Pa (0.38 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated three times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was increased to 220°C, and the internal temperature of the reactor was gradually increased to dissolve the mixture. The stirrer was then rotated at 100 rpm. Then, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) absolute over 40 minutes while distilling off phenol, which was a by-product of the oligomerization reaction occurring inside the reactor.

[0320] Next, the pressure inside the reactor was maintained at 13.3 kPa, and the transesterification reaction was carried out for 80 minutes while further distilling off phenol. The temperature outside the reactor was then raised to 290°C, and the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) absolute pressure to 399 Pa (3 Torr) over 40 minutes, and the distilled phenol was removed from the system. The absolute pressure inside the reactor was then reduced to 12 Pa, and the polycondensation reaction was continued. The polycondensation reaction was terminated when the reactor agitator reached a predetermined stirring power. The total polymerization time in this Example 1 refers to the time from the start of pressure reduction from 101.3 kPa (760 Torr) absolute pressure to the end of the polymerization reaction.

[0321] Next, the pressure inside the reactor was restored with nitrogen, and the molten polymer was taken out of the reactor and cooled at room temperature to obtain a polymer. The monomer composition, polymerization conditions, reduced viscosity, molecular weight, and oligomer content were measured, and the results are shown in Table 1A. In addition, the glass transition temperature (Tg), relative dielectric constant (ε r The measurement results of the dielectric loss tangent (tan δ) and coefficient of linear expansion (CTE) are shown in Table 2A together with the monomer composition.

[0322] [Example 2] 90.03 parts by weight of 4,6-dichloro-N-phenyl-N-methyl-1,3,5-triazin-2-amine [7] (referred to as "monomer [7]" in Tables 1A, 1B, 2A, and 2B) was dissolved in 667 parts by weight of nitrobenzene. This solution was designated solution A. 80.0 parts by weight of BPA and 1.43 parts by weight of 2,3,5-trimethylphenol were dissolved in 810 parts by weight of 1N sodium hydroxide. This solution was designated as solution B. Solution B and 11.30 parts by weight of tetrabutylammonium bromide were placed in a glass reactor equipped with a reactor stirrer and a reactor heater, and the mixture was stirred at an external reactor temperature of 20° C. Next, solution A was added and the mixture was stirred for 5 hours. To the reaction mixture, 904 parts by weight of methylene chloride and 600 parts by weight of demineralized water were added to extract the organic layer, which was then washed with 100 parts by weight of 0.1 N hydrochloric acid. The organic layer was then washed with 600 parts by weight of demineralized water. This washing with demineralized water was repeated four times. The washed organic layer was added to 13,300 parts by weight of ethyl acetate, and the precipitated white solid was collected and dried in vacuum at 100°C for 6 hours to obtain the target product in a yield of 77%. The results are shown in Tables 1A and 2A.

[0323] To confirm that the filtrate obtained by this operation contained cyclic oligomers, the filtrate was concentrated to obtain a white solid. The obtained sample was subjected to mass spectrometry using matrix-assisted laser desorption / ionization mass spectrometry, and the molecular weights of nine types of cyclic oligomers represented by the following formula (50B) were confirmed.

[0324] [ka]

[0325] [Example 3] The procedure described in Example 1 was repeated except that the amount of 2,4-diphenoxy-6-phenyl-1,3,5-triazine [5] charged was 74.8 parts by weight, 46.9 parts by weight of diphenyl carbonate (hereinafter sometimes abbreviated as "DPC") was used, the amount of cesium carbonate added was 0.061 parts by weight, and the polymerization conditions were as shown in Table 1A. The results are shown in Tables 1A and 2A.

[0326] [Example 4] The procedure described in Example 1 was repeated except that 81.2 parts by weight of 4,6-diphenoxy-N-methyl-N-phenyl-1,3,5-triazin-2-amine [8] and 51.7 parts by weight of DPC were used instead of 2,4-diphenoxy-6-phenyl-1,3,5-triazine [5], the amount of cesium carbonate added was changed to 0.043 parts by weight, and the polymerization conditions were as shown in Table 1A. The results are shown in Tables 1A and 2A.

[0327] [Example 5] 2.995 parts by weight of BPA polycarbonate oligomer

[11] , 0.8871 parts by weight of 2,4-dichloro-6-phenyl-1,3,5-triazine [3], 0.063 parts by weight of tetrabutylammonium bromide, and 6.8 parts by weight of methylene chloride were added to a glass reactor equipped with a reactor stirrer and a reactor heater. After the external temperature of the reactor was raised to 30°C and the contents were dissolved, 8.454 parts by weight of 1N sodium hydroxide was added and the mixture was stirred for 1.5 hours. The organic layer was extracted with 10 parts by weight of demineralized water and 7.5 parts by weight of methylene chloride, and then washed with 10 parts by weight of 0.1 N hydrochloric acid. The organic layer was then washed with 10 parts by weight of demineralized water. This washing with demineralized water was repeated three times. The washed organic layer was added to 160 parts by weight of ethyl acetate and stirred for 1 hour. The resulting precipitate was removed and dried in vacuum at 80°C for 6 hours. The dried precipitate was redissolved in 19 parts by weight of methylene chloride and added to 190 parts by weight of methanol to cause reprecipitation. The precipitated white solid was collected and dried in vacuum at 90°C for 3 hours, yielding the target product in 51% yield. The results are shown in Tables 1A and 2A.

[0328] [Example 6] A glass reactor equipped with a reactor stirrer and reactor heater was charged with 3.39 parts by weight of BPA polycarbonate oligomer

[11] , 1.18 parts by weight of 2,2-bis(3-methyl-4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as BPC), 2.09 parts by weight of 2,4-dichloro-6-phenyl-1,3,5-triazine [3], 0.223 parts by weight of tetrabutylammonium bromide, and 17.4 parts by weight of methylene chloride. The external temperature of the reactor was raised to 30°C to dissolve the contents, and then 4.347 parts by weight of 1 N sodium hydroxide was added and the mixture was stirred for 1 hour. To the reaction mixture, 20 parts by weight of demineralized water and 25 parts by weight of methylene chloride were added to extract the organic layer, which was then washed with 20 parts by weight of 0.1 N hydrochloric acid. The organic layer was then washed with 20 parts by weight of demineralized water. This washing with demineralized water was repeated three times. The washed organic layer was added to 200 parts by weight of ethyl acetate and stirred for 1 hour. The precipitated white solid was collected and dried in vacuum at 90°C for 2 hours to obtain the target product in a yield of 53%. The results are shown in Tables 1A and 2A.

[0329] [Example 7] In a glass reactor equipped with a reactor stirrer, a reactor heater, and a reactor pressure regulator, 100 parts by weight of BPC, 66.6 parts by weight of 2,4-diphenoxy-6-phenyl-1,3,5-triazine [5], and 47.6 parts by weight of DPC were added, and the amount of cesium carbonate added was 4.24 × 10 -3 Parts by weight were added to prepare a raw material mixture. Next, the pressure inside the glass reactor was reduced to approximately 50 Pa (0.38 Torr), and then the pressure was returned to atmospheric pressure with nitrogen. This operation was repeated three times to purge the inside of the reactor with nitrogen. After nitrogen purge, the external temperature of the reactor was raised to 150°C, and with stirring as necessary, the temperature was raised to 240°C at atmospheric pressure over 60 minutes to dissolve the mixture (dissolution step). After maintaining the temperature at 240°C for 30 minutes as the first stage of the polymerization reaction, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) absolute to 13.3 kPa (100 Torr) over 40 minutes while distilling off phenol, a by-product of the oligomerization reaction taking place inside the reactor. Next, the pressure inside the reactor was maintained at 13.3 kPa, and the reaction was carried out for 60 minutes while further distilling off phenol. In the second stage of polymerization, the temperature outside the reactor was raised to 280°C in 20 minutes, and simultaneously the pressure inside the reactor was reduced from 13.3 kPa (100 Torr) absolute to 399 Pa (3 Torr) over 30 minutes, and the distilled phenol was removed from the system. The absolute pressure inside the reactor was then reduced to 200 Pa or less, and the polycondensation reaction was continued. The polycondensation reaction was terminated when the reactor agitator reached a predetermined stirring power. The total polymerization time in this example was the time from the start of the first stage of polymerization to the end of the second stage. In this example, it was 3 hours and 30 minutes. The reactor was then re-pressurized with nitrogen, and the molten polymer was taken out of the reactor and cooled at room temperature to obtain a polymer. The results are shown in Tables 1B and 2B.

[0330] [Example 8] 2.26 parts by weight of BPC was dissolved in 19.15 parts by weight of 1N sodium hydroxide. This solution was designated as Solution C. 2.00 parts by weight of 2,4-dichloro-6-phenyl-1,3,5-triazine [3], 0.213 parts by weight of tetrabutylammonium bromide, and 13.9 parts by weight of methylene chloride were added to a glass reactor equipped with a reactor stirrer and a reactor heater. After the external temperature of the reactor was raised to 30°C and the contents were dissolved, Solution C was added and the mixture was stirred for 3.5 hours. The organic layer was extracted by adding 20 parts by weight of demineralized water and 13.9 parts by weight of methylene chloride to the reaction mixture, and then washed with 10 parts by weight of 0.1 N hydrochloric acid. The organic layer was then washed with 20 parts by weight of demineralized water. This washing with demineralized water was repeated three times. The results are shown in Tables 1B and 2B.

[0331] [Examples 8-1 to 8-4] 0.5 parts by weight of the washed organic layer was sampled, the solvent was distilled off, and the resulting solid was dried at 80°C for 6 hours to obtain a white solid polymer sample for evaluating thermal stability. (This polymer sample is referred to as the crude product.) The amount of residual cyclic oligomer in this polymer sample was measured by gel permeation chromatography (GPC). The weight loss rate after heating at 340°C for 30 minutes was also measured. The results are shown in Table 3. One part by weight of the washed organic layer was sampled, added to 10 parts by weight of methanol, and stirred for one hour. The resulting precipitate was removed and dried at 80°C for six hours to obtain a white solid polymer sample for evaluating thermal stability. (This polymer sample is referred to as the methanol precipitate.) The amount of residual cyclic oligomer in this polymer sample was measured by gel permeation chromatography (GPC). The weight loss rate after heating at 340°C for 30 minutes was also measured. The results are shown in Table 3. One part by weight of the washed organic layer was sampled, added to 5 parts by weight of ethyl acetate, and stirred for 1 hour. The resulting precipitate was collected and dried at 80°C for 6 hours to obtain a white solid polymer sample for evaluating thermal stability. (This polymer sample is referred to as Ethyl Acetate Precipitate 1.) The amount of residual cyclic oligomer in this polymer sample was measured by gel permeation chromatography (GPC). The weight loss rate after heating at 340°C for 30 minutes was also measured. The results are shown in Table 3.

[0332] The remaining washed organic layer was added to 330 parts by weight of ethyl acetate and stirred for 1 hour. The resulting precipitate was collected and dried in vacuum at 80°C for 6 hours to obtain the target product in a yield of 60%. (This polymer sample is referred to as Example 8 or Ethyl Acetate Precipitate 2.) The monomer composition, polymerization conditions, reduced viscosity, molecular weight, and oligomer content are shown in Table 1B. In addition, the glass transition temperature (Tg), relative dielectric constant (ε r The measurement results of the dielectric loss tangent (tan δ) and coefficient of linear expansion (CTE) are shown in Table 2B together with the monomer composition. The amount of residual cyclic oligomer in this polymer sample was measured by gel permeation chromatography (GPC), and the weight loss rate after heating at 340°C for 30 minutes was also measured. The results are shown in Table 3. The filtrate obtained in the procedure for obtaining the ethyl acetate precipitate 2 was concentrated to obtain a white solid. The obtained sample was subjected to mass spectrometry using matrix-assisted laser desorption / ionization mass spectrometry, and it was confirmed that the sample was composed of nine types of cyclic oligomers represented by the following formula (50A).

[0333] [ka]

[0334] [Example 9] The procedure described in Example 8 was repeated, except that instead of BPC, 2.58 parts by weight of 4,4'-methylenebis(2,6-dimethylphenol) [TmBPF] (referred to as "TmBPF" in Tables 1A, 1B, 2A, and 2B) were used, 2.288 parts by weight of 1N sodium hydroxide, 2.27 parts by weight of 2,4-dichloro-6-phenyl-1,3,5-triazine [3], and 0.242 parts by weight of tetrabutylammonium bromide were used, and the target product was obtained in 63% yield. The results are shown in Tables 1B and 2B.

[0335] [Example 10] 2.05 parts by weight of TmBPF was dissolved in 18.30 parts by weight of 1N sodium hydroxide. This solution was designated as Solution D. 2.05 parts by weight of 4,6-dichloro-N-phenyl-N-methyl-1,3,5-triazin-2-amine [7], 0.194 parts by weight of tetrabutylammonium bromide, and 14.7 parts by weight of nitrobenzene were added to a glass reactor equipped with a reactor stirrer and a reactor heater. The external temperature of the reactor was raised to 35°C to dissolve the contents, and then Solution D was added and stirred for 5.5 hours. To the reaction mixture, 20 parts by weight of demineralized water and 15 parts by weight of methylene chloride were added to extract the organic layer, which was then washed with 10 parts by weight of 0.1 N hydrochloric acid. The organic layer was then washed with 20 parts by weight of demineralized water. This washing with demineralized water was repeated three times. The washed organic layer was added to 270 parts by weight of ethyl acetate, and the precipitated white solid was collected and dried in vacuum at 100°C for 6 hours to obtain the target product in a yield of 65%. The results are shown in Tables 1B and 2B.

[0336] [Example 11] 1.106 parts by weight of 2,4-dichloro-6-phenyl-1,3,5-triazine [3] was added to 14 parts by weight of methylene chloride to form a solution. This solution was designated as Solution E. 1.502 parts by weight of 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol (referred to as "BP-TMC" in Tables 1A, 1B, 2A, and 2B) and 10.23 parts by weight of a 1N aqueous solution of sodium hydroxide were placed in a glass reactor equipped with a reactor stirrer and a reactor heater. After the external temperature of the reactor was raised to 30°C and the contents were dissolved, 0.079 parts by weight of tetrabutylammonium bromide was added, followed by the addition of Solution E, and the mixture was stirred for 2.5 hours. 20 parts by weight of methylene chloride and 20 parts by weight of demineralized water were added to the reaction solution, and the organic layer was extracted and then washed with 10 parts by weight of 0.1 N hydrochloric acid. Thereafter, the organic layer was washed with 20 parts by weight of demineralized water. This washing with demineralized water was repeated three times. The washed organic layer was added to 100 parts by weight of ethyl acetate, and the precipitated white solid was collected and dried in vacuum at 100°C for 6 hours to obtain the target product in a yield of 62%. The results are shown in Tables 1B and 2B.

[0337] [Comparative Example 1] As the resin of Comparative Example 1, polycarbonate resin (Iupilon S3000 manufactured by Mitsubishi Engineering Plastics Corporation) was used, and the glass transition temperature (Tg), relative dielectric constant (ε r ), dielectric loss tangent (tan δ), and coefficient of linear expansion (CTE) were measured in the same manner as above. The results are shown in Table 2A.

[0338] Comparative Example 2 A polymer was obtained in the same manner as in Example 1, except that the raw material mixture was prepared as follows. A raw material mixture was prepared by adding 100 parts by weight of BPC, 100 parts by weight of DPC, and 0.32 parts by weight of a 0.4 wt % aqueous solution of cesium carbonate as a catalyst to a glass reactor equipped with a reactor stirrer, a reactor heater, and a reactor pressure regulator. The results are shown in Table 2B.

[0339] [Table 1A]

[0340] [Table 1B]

[0341] [Table 2A]

[0342] [Table 2B]

[0343] [Table 3]

[0344] [Consideration] From the above results, the following can be seen: The polycyanurate of the present invention having a repeating unit represented by formula (1) (Examples 1 and 2) and the polycyanurate-polycarbonate copolymer resin of the present invention having a repeating unit (A) represented by formula (8) and a repeating unit (B) represented by formula (11) (Examples 3, 4, 5, and 6) are superior in relative permittivity, dielectric loss tangent, heat resistance, and low linear expansion compared to Comparative Example 1. Furthermore, the polycyanurate of the present invention having a repeating unit represented by formula (1) (Example 8) and the polycyanurate-polycarbonate copolymer resin of the present invention having a repeating unit (A) represented by formula (8) and a repeating unit (B) represented by formula (11) (Example 7) are superior in relative permittivity, dielectric loss tangent, heat resistance, and low linear expansion compared to Comparative Example 2. Furthermore, it is preferable that the polycyanurate of the present invention contains as little cyclic oligomer by-product as possible in terms of thermal stability.

[0345] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2021-59998, filed on March 31, 2021, the entire contents of which are incorporated by reference.

Claims

1. A molded article for a communication device having a built-in microwave and / or millimeter wave antenna, obtained using a thermoplastic resin composition, The thermoplastic resin composition contains, as a thermoplastic resin, a polycyanurate containing a repeating unit represented by the following formula (1): The molded article for a communication device, wherein the thermoplastic resin composition further has a repeating unit represented by the following formula (2): 【Chemistry 1】 (In formula (1), Y １ represents a divalent organic group. １ is a group selected from the group consisting of a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted linear or branched alkoxy group having 1 to 20 carbon atoms, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms. 【Chemistry 2】 (In formula (2), Y 2 is a divalent organic group having an alicyclic ring or an aromatic ring.)

2. Said Z １ is a group selected from the group consisting of a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted amino group, and a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

3. Y １ 3. The molded article for a communication device according to claim 1, wherein is a divalent organic group having an aliphatic ring or an aromatic ring.

4. The Y １ and Y ２ The molded article for a communication device according to claim 1 , wherein the first and second conductive layers are the same.

5. The Y １ and Y ２ The molded article for a communication device according to claim 1 , wherein the first and second conductive layers are different from each other in the following respects:

6. The Y １ and Y ２ The molded article for a communication device according to claim 1 , wherein is a divalent organic group having an aromatic ring.

7. The Y １ and Y ２ The molded article for a communication device according to claim 6 , wherein is a divalent organic group represented by the following formula (3): 【Transformation 3】 (In formula (3), X １ represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. １ ~R ４ each independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, or a substituted or unsubstituted aryl group. １ and R ３ , or R ２ and R ４ may be bonded to each other to form a ring.

8. The Y １ and Y ２ The molded article for a communication device according to claim 7 , wherein is a divalent organic group represented by the following formula (4): 【Chemistry 4】 (In formula (4), X １ , R １ ~R ４ are X in the formula (3), respectively. １ , R １ ~R ４ is synonymous with

9. The Y １ and Y ２ The molded article for a communication device according to claim 8 , wherein is a divalent organic group represented by the following formula (5): 【Transformation 5】 (In formula (5), X １ , R １ ~R ４ are the same as those in the formula (3), but R １ and R ３ , R ２ and R ４ do not bond to each other to form a ring.)

10. X １ The molded article for a communication device according to claim 7 , wherein is a divalent organic group represented by the following formula (6): 【Transformation 6】 (In formula (6), R ９ , R １０ R each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with a halogen atom, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group. ９ and R １０ may be bonded to each other to form a ring which may have a substituent. ）

11. The molded article for a communication device according to any one of claims 8 to 10, wherein the divalent organic group represented by formula (4) is a divalent organic group selected from the group consisting of the following formulas (7a) to (7r): 【Transformation 7】

12. The dielectric loss tangent of the polycyanurate is 4.5 × 10 －３ The molded article for a communication device according to claim 1 , wherein:

13. The dielectric loss tangent of the polycyanurate is 3.0 × 10 －３ The molded article for a communication device according to claim 12, wherein:

14. The dielectric loss tangent of the polycyanurate is 1.5 × 10 －３ The molded article for a communication device according to claim 13, wherein:

15. The average linear expansion coefficient of the polycyanurate is 7.3 × 10 －５ The molded article for a communication device according to claim 1 , wherein the temperature is 100° C. / ° C. or lower.

16. The average linear expansion coefficient of the polycyanurate is 7.0 × 10 －５ The molded article for a communication device according to claim 15, wherein the temperature is 1000°C or lower.

17. The average linear expansion coefficient of the polycyanurate is 6.4 × 10 －５ The molded article for a communication device according to claim 16, wherein the temperature is 1000°C or lower.

18. The average linear expansion coefficient of the polycyanurate is 5.5 × 10 －５ The molded article for a communication device according to claim 17, wherein the temperature is 1000°C or lower.

19. The molded article for a communication device according to claim 1 , wherein the thermoplastic resin has a relative dielectric constant of 2.6 or less.

20. 20. The molded article for a communication device according to claim 19, wherein the thermoplastic resin has a relative dielectric constant of 2.5 or less.

21. 21. The molded article for a communication device according to claim 1, wherein the thermoplastic resin composition contains one or more additives selected from the group consisting of a crosslinking agent, an ultraviolet absorber, an antistatic agent, an antioxidant, a coupling agent, a plasticizer, a flame retardant, a colorant, a dispersant, an emulsifier, an elasticity reducing agent, a diluent, an antifoaming agent, an ion trapping agent, a thickener, a leveling agent, inorganic particles, and organic particles.

22. 22. The molded article for a communication device according to claim 1, which is molded by extrusion molding, injection molding, blow molding, vacuum molding, pressure molding, press molding, or film casting of the thermoplastic resin composition.

23. 23. The molded article for a communication device according to claim 1, wherein the molded article for a communication device is any one selected from the group consisting of a sheet, a film, a printed wiring board, a coating, and a multilayer film that are built into the communication device.

24. The molded article for a communication device according to claim 1 , wherein the molded article for a communication device is a thin film transistor in which an insulating film, a sealing material, and a gate electrode layer are laminated in this order.

25. The molded article for a communications device according to claim 1 , which is a housing for a communications device or a cover for a housing for a communications device.

26. The molded article for a communication device according to claim 1 , wherein the communication device is a notebook computer, a tablet terminal, a smartphone, or a router device.

27. A communication device having a built-in microwave and / or millimeter wave antenna, obtained using the molded article for a communication device according to any one of claims 1 to 26.

28. A metal-clad laminate in which a film layer and a metal foil layer are laminated, A metal-clad laminate, wherein the film layer is the molded article for a communication device according to any one of claims 1 to 26.

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