Molded articles for communication equipment and polycyanurate

Abstract

A molded article for communication equipment incorporating a microwave and / or millimeter-wave antenna, obtained using a thermoplastic resin composition. The thermoplastic resin composition contains a polycyanurate comprising repeating units represented by the following formula (1). TIFF2026062627000077.tif35140(Y 1 Z is a divalent organic group. 1 (This includes hydrogen atoms, substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl groups having 5 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted aralkyl groups, substituted or unsubstituted amino groups, substituted or unsubstituted linear or branched alkoxy groups having 1 to 20 carbon atoms, or substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms.)

Description

[Technical Field]

[0001] The present invention relates to a molded article for communication equipment that incorporates a microwave and / or millimeter-wave antenna, which has excellent radio wave transmission in the microwave and / or millimeter-wave band, excellent heat resistance, and a low coefficient of linear expansion. The present invention also relates to a polycyanurate for this molded article for communication equipment and a thermoplastic resin composition containing this polycyanurate. The present invention also relates to a communication device using this molded article for communication equipment. [Background technology]

[0002] In recent years, high-frequency radio waves such as microwaves and millimeter waves have come into use in the fields of electrical and electronic equipment and automobiles, and consequently, there is a demand for materials that possess both low relative permittivity and low dielectric loss tangent. In particular, in the electrical and electronic fields, in addition to a low relative permittivity and a 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) and refractive index, as well as excellent chemical and heat resistance. However, there are no reported examples of dielectric properties, and no examples of their use in communication equipment using molded bodies for communication devices.

[0004] Patent Document 1 discloses polycyanurates having various bifunctional phenolic structures, demonstrating excellent heat resistance and flame retardancy. However, it makes no mention of dielectric properties.

[0005] Non-patent documents 1-4 disclose polycyanurates having various bifunctional phenolic structures. However, they do not mention anything about dielectric properties.

[0006] Polycarbonate excels in mechanical strength, electrical properties, and transparency, and as an engineering plastic, it is widely used in various fields such as electrical and electronic equipment and the automotive industry.

[0007] Patent Document 2 proposes a millimeter-wave radar cover in which the dielectric loss tangent is reduced and millimeter-wave transmission is improved by using polycarbonate made from bisphenol having a specific substituent. However, the thermoplastic resin composition described therein had insufficient heat resistance for use in information and communication equipment such as laptop computers, tablet terminals, smartphones, or router devices.

[0008] Patent Document 3 discloses polycarbonate compositions and copolymers with excellent heat resistance and fire resistance, manufactured using two specific types of bisphenols as raw materials. However, it makes no mention of dielectric properties. [Prior art documents] [Patent Documents]

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

[0010] [Non-Patent Document 1] Journal of Industrial Science, 1967, Vol. 70, No. 11, 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, Vol. 7, No. 11, 1969, pp. 3089-3100 [Overview of the Initiative] [Problems that the invention aims to solve]

[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 exceeding 3 GHz, classified as the microwave band, have been used. For the next-generation, fifth-generation mobile communication system (5G), the market for the even higher frequency 28 GHz band within the microwave band is considered promising. Furthermore, it is anticipated that millimeter-wave radio waves will be used in future generations of communication.

[0012] Consequently, there is a growing demand for higher performance in molded materials for communication equipment, such as sheets, films, coatings, and multilayer films, which are incorporated into information and communication equipment intended for use in the microwave and / or millimeter-wave bands. Radio waves in such high-frequency bands have greater transmission loss and poorer permeability to materials than radio waves in lower-frequency bands. Therefore, molded materials for communication equipment used in microwave and / or millimeter-wave communications are required to have even better radio wave permeability than before.

[0013] Transmission loss is due to the relative permittivity (ε) of the dielectric material. r It is proportional to the square root of ) and the dielectric loss tangent (tanδ) of the dielectric. Therefore, in order to improve the radio wave transmittance of molded bodies for communication equipment, the relative permittivity ε of the material used in the molded bodies for communication equipment is proportional. r Furthermore, the dielectric loss tangent tanδ must be kept small.

[0014] Information and communication equipment that transmits and receives high-frequency radio waves such as microwaves and / or millimeter waves tends to generate heat. Furthermore, in environments with large temperature fluctuations, cracks can form in solder joints due to differences in the coefficient of linear expansion between the molded resin and the copper foil, reducing the reliability of the connection. For this reason, materials used in such fields should not only have a low relative permittivity and a low dielectric loss tangent, but also appropriate heat resistance and low thermal expansion. Materials that meet these conditions are in high demand. However, conventional materials could not meet all of these requirements.

[0015] The present invention aims to provide a molded body for communication equipment and a communication device that incorporates a microwave and / or millimeter-wave antenna, which has excellent radio wave transmission properties in the microwave and / or millimeter-wave band, excellent heat resistance, and a low coefficient of linear expansion. [Means for solving the problem]

[0016] The inventors have found that the above problems can be solved by providing a molded article for communication equipment incorporating a microwave and / or millimeter-wave antenna, comprising a specific polycyanurate and a thermoplastic resin composition containing the polycyanurate.

[0017] The purpose of this invention is as follows:

[0018] [1] A molded article for a communication device, comprising a microwave and / or millimeter-wave antenna, obtained using a thermoplastic resin composition, wherein the thermoplastic resin composition comprises a polycyanurate containing repeating units represented by the following formula (1).

[0019] [ka]

[0020] (In formula (1), Y 1 represents a divalent organic group. 1 This group is 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] The 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. The molded body for a communication device according to [1].

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

[0023] [4] The thermoplastic resin composition further has a repeating unit represented by the following formula (2). The molded body for a communication device according to any one of [1] to [3].

[0024] [Chemical formula]

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

[0026] [5] The Y 1 and Y 2 are the same. The molded body for a communication device according to [4].

[0027] [6] The Y 1 and Y 2 are different. The molded body for a communication device according to [4].

[0028] [7] The Y 1 and Y 2 are divalent organic groups having an aromatic ring. The molded body for a communication device according to [4].

[0029] [[ID=​​​​​

[0030] [ka]

[0031] (In formula (3), X 1 R represents a single bond, oxygen atom, sulfur atom, or divalent organic group. 1 ~R 4 Each of these independently represents a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms 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. However, R 1 and R 3 , or R 2 and R 4 They may be joined to each other to form a ring.

[0032] [9] Y 1 and Y 2 However, the molded article for communication equipment described in [8] is a divalent organic group represented by the following formula (4).

[0033] [ka]

[0034] (In formula (4), X 1 , R 1 ~R 4 These are the X values ​​in equation (3) above, respectively. 1 , R 1 ~R 4 (This is synonymous with...)

[0035]

[10] Y 1 and Y 2 The molded article for communication equipment described in [9], wherein the group is a divalent organic group represented by the following formula (5).

[0036] [ka]

[0037] (In formula (5), X 1 , R 1 ~R 4 These are equivalent to those in equation (3) above, but R 1 and R 3 , R 2 and R 4 They do not combine with each other to form a ring.

[0038]

[11] X 1 A molded article for communication equipment according to any of [8] to

[10] , wherein the group is a divalent organic group represented by the following formula (6).

[0039] [ka]

[0040] (In formula (6), R 9 , R 10 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms 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 These may be bonded to each other to form a ring which may have substituents. )

[0041]

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

[11] , wherein the divalent organic group represented by formula (4) is a divalent organic group selected from the group of formulas (7a) to (7r) below.

[0042] [ka]

[0043]

[13] The dielectric loss tangent of the polycyanurate is 4.5 × 10 -3 A molded body for communication equipment as described in any of the following [1] to

[12] .

[0044]

[14] The dielectric loss tangent of the polycyanurate is 3.0 × 10 -3 The following is a molded article for communication equipment as described in

[13] .

[0045]

[15] The dielectric loss tangent of the polycyanurate is 1.5 × 10 -3 The following is a molded article for communication equipment as described in

[14] .

[0046]

[16] The average coefficient of linear expansion of the polycyanurate is 7.3 × 10 -5 A molded body for communication equipment as described in any of [1] to

[15] , wherein the temperature is below / ℃.

[0047]

[17] The average coefficient of linear expansion of the polycyanurate is 7.0 × 10 -5 A molded article for communication equipment as described in

[16] , wherein the temperature is below / ℃.

[0048]

[18] The average coefficient of linear expansion of the polycyanurate is 6.4 × 10 -5 A molded article for communication equipment as described in

[17] , wherein the temperature is below / ℃.

[0049]

[19] The average coefficient of linear expansion of the polycyanurate is 5.5 × 10 -5 A molded article for communication equipment as described in

[18] , wherein the temperature is below / ℃.

[0050]

[20] A molded article for communication equipment according to any one of [1] to

[19] , wherein the dielectric constant of the thermoplastic resin is 2.6 or less.

[0051]

[21] The molded article for communication equipment according to

[20] , wherein the relative permittivity of the thermoplastic resin is 2.5 or less.

[0052]

[22] A molded article for communication equipment according to any one of [1] to

[21] , wherein the thermoplastic resin composition comprises one or more additives selected from the group consisting of crosslinking agents, ultraviolet absorbers, antistatic agents, antioxidants, coupling agents, plasticizers, flame retardants, colorants, dispersants, emulsifiers, deelasticizing agents, diluents, defoaming agents, ion trapping agents, thickeners, leveling agents, inorganic particles, and organic particles.

[0053]

[23] A molded article for communication equipment according to any one of [1] to

[22] , obtained by extruding, injection molding, blow molding, vacuum molding, pressure molding, press molding or casting film formation of the thermoplastic resin composition.

[0054]

[24] The communication equipment molded body according to any one of [1] to

[23] , wherein the communication equipment molded body is one selected from the group consisting of a sheet, a film, a printed circuit board, a coating, and a multilayer film that is incorporated into the communication equipment.

[0055]

[25] The molded body for communication equipment according to any one of [1] to

[23] , wherein the molded body for communication equipment is a thin-film transistor in which an insulating film, a encapsulant, and a gate electrode layer are stacked in that order.

[0056]

[26] The communication equipment molded body according to any one of [1] to

[23] , wherein the communication equipment molded body is a housing for communication equipment or a cover for a housing for communication equipment.

[0057]

[27] A molded body for a communication device according to any one of [1] to

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

[0058]

[28] A communication device having a built-in microwave and / or millimeter-wave antenna, obtained using a molded body for communication devices described in any of [1] to

[27] .

[0059]

[29] A metal-clad laminate having a film layer and a metal foil layer laminated together, A metal-clad laminate in which the film layer is a molded body for communication equipment as described in any of [1] to

[27] .

[0060]

[30] A polycyanurate containing a repeating unit represented by formula (1), wherein the total content of the cyclic oligomer represented by formula (51) and the cyclic oligomer represented by 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 Y2 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 or aromatic ring.

[0064]

[31] A polycyanurate consisting of repeating units 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). 2This group is selected from the group consisting of substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups, and substituted or unsubstituted aryloxy groups 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 of these 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 of these 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 following are polycyanurates as described in any one of items

[30] to

[32] :

[0073]

[34] The mean coefficient of linear expansion of the polycyanurate is 7.5 × 10 -5 Polycyanurate as described in any of

[30] to

[33] , which is below / ℃.

[0074] A thermoplastic resin composition comprising a polycyanurate as described in any of

[35]

[30] to

[34] , wherein the thermoplastic resin composition comprises repeating units represented by formula (1) or formula (8). A thermoplastic resin composition in which the content of is 10% by weight or more.

[0075] A molded article for communication equipment incorporating a microwave and / or millimeter-wave antenna, obtained using a polycyanurate described in any of

[30] to

[34] or a thermoplastic resin composition described in

[35] . [Effects of the Invention]

[0076] The molded articles for communication equipment provided by the present invention have excellent microwave and / or millimeter-wave band radio wave transmission, as well as excellent heat resistance and a low coefficient of linear expansion. For this reason, the molded articles for communication equipment provided by the present invention can be widely used as sheets, films, coatings, printed circuit boards, multilayer films, thin-film transistors in which an insulating film, a encapsulant, and a gate electrode layer are laminated in that order, as well as as housings for communication equipment and covers for housings for communication equipment, which incorporate microwave and / or millimeter-wave antennas, such as notebook computers, tablet terminals, smartphones, or router devices. [Modes for carrying out the invention]

[0077] The present invention will be described in detail below with reference to embodiments and examples. The present invention is not limited to the embodiments and examples shown below. In this specification, unless otherwise specified, "~" means that the numbers before and after it are included as the lower and upper limits. When describing two or more subjects together, the term "independently" means that those two or more subjects may be the same or different.

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

[0079] The following describes in detail the polycyanurate of the present invention and the components constituting the thermoplastic resin composition of the present invention containing the polycyanurate of the present invention.

[0080] <Polycyanurate> The polycyanurate of the present invention is characterized by containing repeating units represented by the following formula (1). The polycyanurate of the present invention may consist of repeating units represented by the following formula (1), or it may be a copolymerized polycyanurate containing the repeating units represented by the following formula (1) and other repeating units. By using a thermoplastic resin composition containing polycyanurate with repeating units represented by the following formula (1), the radio wave transmission in the microwave and / or millimeter wave band, heat resistance, and low thermal expansion properties of the molded article for communication equipment of the present invention can be improved.

[0081] [ka]

[0082] (In formula (1), Y 1 represents a divalent organic group. 1This group is 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 equation (1), Z 1 This group is 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 substituents 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 substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms in the above include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; Methyl ethyl group, methyl propyl group, methyl butyl group, methyl pentyl group, methyl hexyl group, methyl heptyl group, methyl octyl group, methyl nonyl group, methyl decyl group, methyl undecyl group, methyl dodecyl group, methyl tridecyl group, methyl tetradecyl group, methyl pentadecyl group, methyl hexadecyl group, methyl heptadecyl group, methyl octadecyl group, methyl nonadecyl 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; These are some examples.

[0086] Of these, methyl and ethyl groups are preferred because they more readily exhibit various properties such as heat resistance and dielectric properties derived from the compound when used as a polycyanurate.

[0087] Z 1 Specific examples of substituted or unsubstituted carbon 5-20 cycloalkyl groups in this context include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, bicyclo[2,2,1]heptyl group, cyclooctyl group, and adamantyl group.

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

[0089] Of these, phenyl groups, methylphenyl groups such as 2-methylphenyl groups, methoxyphenyl groups such as 2-methoxyphenyl groups, and naphthyl groups are preferred because they more readily exhibit various properties such as heat resistance and dielectric properties derived from the compound when used as a polycyanurate.

[0090] Z 1 Specific examples of substituted or unsubstituted aralkyl groups in this context include the benzyl group and the phenylethyl group.

[0091] Z1 A specific example of an amino group in this context is the amino group represented by the following formula (15).

[0092] [ka]

[0093] In the above equation (15), R 38 and R 39 Each of these independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. These organic groups may have any substituents. 38 and R 39 These may be bonded to each other to form a ring. The asterisks (*) in formula (15) and the substituent groups (16), (17), etc., described later, indicate the bond to the triazine ring in formula (1).

[0094] R 38 and R 39 Examples of organic groups having 1 to 20 carbon atoms include alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups. A specific example of such an organic group is the aforementioned Z 1 These are similar to the specific examples of alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups in [reference].

[0095] R 38 and R 39 Specific examples of amino groups that bond to each other to form a ring include those represented by the following group of substituents (16).

[0096] [ka]

[0097] Of these, Z is more likely to exhibit the various properties derived from this compound, such as heat resistance and dielectric properties, when used as a polycyanurate. 1 The amino group in this case is R 38 and R 39 is a methyl group, R 38 and R 39 is an ethyl group, R38 where R is a methyl group 39 is a combination of a phenyl group, R 38 where R is an ethyl group 39 is a combination of a phenyl group, R 38 and R 39 is preferably an amino group of formula (15) in which are bonded to each other to form a 6-membered ring piperidinyl group.

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

[0099]

Chemical formula

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

[0101] Z 1 ​Specific examples of substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms in the above include, for example, phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 3-methylphenoxy group, 4-ethylphenoxy group, 2-ethylphenoxy group, 2,6-dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,3-dimethylphenoxy group, 3,4-dimethylphenoxy group, 2,5-dimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 4-butylphenoxy group, 2-tert-butylphenoxy group, 4-tert-butylphenoxy group, 3-tert-butylphenoxy group, 4-sec-butylphenoxy group, 4-isopropylphenoxy group, 2-isopropylphenoxy group, 4-amylphenoxy group, 4-tert-amylphenoxy group, 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 Examples include the 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, naphthoxy group, etc.

[0102] Of these, the phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group, and naphthoxy group are preferred because they more readily exhibit the heat resistance, dielectric properties, and other characteristics derived from the compound when used as a polycyanurate.

[0103] When used as a polycyanurate, this compound exhibits various properties such as heat resistance and dielectric properties more readily, and from the viewpoint of thermal stability, Z 1 It is preferably selected from the group consisting of substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups, and substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, and more preferably selected from the group consisting of substituted or unsubstituted aryl groups having 6 to 20 carbon atoms and substituted amino groups.

[0104] In the above equation (1), Y 1 Y is a divalent organic group, selected from aliphatic and aromatic groups. When used as a polycyanurate, Y is chosen because of the heat resistance derived from this compound. 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 equation (2)> The thermoplastic resin composition of the present invention may contain repeating units of carbonatenate bonds represented by the following formula (2). In this case, the repeating units represented by the following formula (2) may be included in the polycyanurate of the present invention together with the repeating units represented by the above formula (1), or they may be included in a resin other than the polycyanurate of the present invention, for example, 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 it may contain the polycyanurate and polycarbonate of the present invention.

[0106] Even when the thermoplastic resin composition of the present invention contains repeating units represented by the following formula (2), it can exhibit the excellent heat resistance and dielectric properties of the polycyanurate of the present invention. In other words, by incorporating the polycyanurate of the present invention into existing bisphenol-based polycarbonates, excellent heat resistance and dielectric properties can be imparted.

[0107] [ka]

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

[0109] In this case, the divalent organic group Y in (1) above 1 and Y in equation (2) 2 Whether they are the same or different, they exhibit excellent heat resistance and dielectric properties. 1 and Y 2 By freely selecting these elements, the heat resistance and dielectric properties of the thermoplastic resin composition of the present invention can be adjusted, as well as its processability and application, including fluidity and surface hardness.

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

[0111] <Y 1 , Y 2 Detailed explanation > Y 1 Any divalent organic group will do, Y 2 Y can be any divalent organic group having an aliphatic or aromatic ring, and is not particularly limited. 1 and Y 2 The preferred structure is a divalent organic group having an alicyclic or aromatic ring.

[0112] Specific examples of organic groups having a divalent aliphatic ring include those represented by formulas (12a) to (12g) below, and divalent aliphatic groups in which the aromatic ring structure is substituted, as shown in formulas (13) and (14) below.

[0113] [ka]

[0114] (In formula (13), R 17 ~R 19 Each of these is an alkylene group having 1 to 4 carbon atoms, which may be directly bonded or substituted. 20 ~R 25 Each of these is independently a hydrogen atom, an optionally substituted C1-C10 alkyl group, an optionally substituted C4-C10 aryl group, an optionally substituted C1-C10 acyl group, an optionally substituted C1-C10 alkoxy group, an optionally substituted C4-C10 aryloxy group, an optionally substituted C1-C10 acyloxy group, an optionally substituted amino group, an optionally substituted C2-C10 alkenyl group, an optionally substituted C2-C10 alkynyl group, a substituted sulfur atom, a substituted silicon atom, a halogen atom, a nitro group, or a cyano group. 20 ~R 25 At least two adjacent groups may be bonded to each other to form a ring. In formula (14), R 26 ~R 29 R 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 of these independently represents a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group. m and n are each independently integers from 0 to 5.

[0115] Y 1 , Y 2 Specific examples of organic groups having a divalent aromatic ring include those listed below as examples Y-1 to Y-20 of divalent organic groups containing an aromatic ring. However, Y1 , Y 2 The organic groups are 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]

Chem.

[0127]

Chem.

[0128]

Chem.

[0129]

Chem.

[0130]

Chem.

[0131]

Chem.

[0132]

Chem.

[0133]

Chem.

[0134]

Chem.

[0135]

Chem.

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

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

[0138] [ka]

[0139] (In formula (3), X 1 R represents a single bond, oxygen atom, sulfur atom, or divalent organic group. 1 ~R 4 Each of these independently represents a hydrogen atom, a halogen atom, a halogen-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, or a substituted or unsubstituted aryl group. 1 and R 3 , or R 2 and R 4 They may be joined to each other to form a ring.

[0140] X in equation (3) above 1 X represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group. 1 If it is a sulfur atom, it will represent one of the following: a sulfide group, a sulfoxide group, or a sulfone group.

[0141] R in equation (3) above 1 ~R 4In the case of an unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, specific examples 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, an n-icosyl group; a methylethyl group, a methylpropyl group, a methylbutyl group, a methylpentyl group, a methylhexyl group, a methylheptyl group, a methyloctyl group, a methylnonyl group, a methyldecyl group, a methylundecyl group, a methyldodecyl group, a methyltridecyl group, a methyltetradecyl group, a methylpentadecyl group, a methylhexadecyl group, a methylheptadecyl group, a methyloctadecyl group, a methylnonadecyl group; a dimethylethyl group, a dimethylpropyl group, a dimethylbutyl group, a dimethylpentyl group, a dimethylhexyl group, a dimethylheptyl group, a dimethyloctyl group, a dimethylnonyl group, a dimethyldecyl group, a dimethylundecyl group, a dimethyldodecyl group, a dimethyltridecyl group, a dimethyltetradecyl group, a dimethylpentadecyl group, a dimethylhexadecyl group, a dimethylheptadecyl group, a dimethyloctadecyl group; a trimethylbutyl group, a trimethylpentyl group, a trimethylhexyl group, a trimethylheptyl group, a trimethyloctyl group, a trimethylnonyl group, a trimethyldecyl group, a trimethylundecyl group, a trimethyldodecyl group, a trimethyltridecyl group, a trimethyltetradecyl group, a trimethylpentadecyl group, a trimethylhexadecyl group, a trimethylheptadecyl group; an ethylpentyl group, an ethylhexyl group, an ethylheptyl group, an ethyloctyl group, an ethylnonyl group, an ethyldecyl group, an ethylundecyl group, an ethyldodecyl group, an ethyltridecyl group, an ethyltetradecyl group, an ethylpentadecyl group, an ethylhexadecyl group, an ethylheptadecyl group, an 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; These are some examples.

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

[0143] When used as a polycyanurate, this compound exhibits various properties such as heat resistance, low coefficient of thermal expansion, and low dielectric properties more readily, R 1 ~R 4 The group is preferably a methyl group, a phenyl group, or a naphthyl group, with methyl and phenyl groups being particularly preferred.

[0144] Specific examples of the structure represented by formula (3) include the aforementioned divalent organic group Y-3 to Y-20, which contain an aromatic ring.

[0145] From the viewpoint of solubility, processability, etc., the structure represented by formula (3) above is less desirable than the structure shown by formula (4) below.

[0146] [ka]

[0147] (In formula (4), X 1 , R 1 ~R 4 These are the X values ​​in equation (3) above, respectively. 1 , R 1 ~R 4 (This is synonymous with...)

[0148] Specific examples of the structure represented by formula (4) are the aforementioned divalent organic group examples Y-3, Y-5, Y-7, Y-9, Y-11, Y-13, Y-15, Y-16, Y-18, Y-19, and Y-20, which contain aromatic rings. Among these, the structure shown in formula (5) below is preferred because it allows polycyanurate to exhibit various properties such as low dielectric properties more easily.

[0149] [ka]

[0150] (In formula (5), X 1 , R 1 ~R 4 These are equivalent to those in equation (3) above, but R 1 and R 3 , R 2 and R 4 They do not combine with each other to form a ring.

[0151] Furthermore, among these, polycyanurate is superior in terms of impact resistance and heat resistance, X 1 A structure represented by the following formula (6) is preferred.

[0152] [ka]

[0153] (In formula (6), R 9 , R 10 Each of these independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms 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 They may be bonded to each other to form a ring which may have substituents.

[0154] X 1 If R is a divalent organic group represented by the above formula (6), 9 , R 10 This 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 the case where is an unsubstituted alkyl group having 1 to 20 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group; Methyl ethyl group, methyl propyl group, methyl butyl group, methyl pentyl group, methyl hexyl group, methyl heptyl group, methyl octyl group, methyl nonyl group, methyl decyl group, methyl undecyl group, methyl dodecyl group, methyl tridecyl group, methyl tetradecyl group, methyl pentadecyl group, methyl hexadecyl group, methyl heptadecyl group, methyl octadecyl group, methyl nonadecyl 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; These are some examples.

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

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

[0158] Of these, the structure represented by formulas (7a) to (7r) below is more preferable in that the heat resistance, dielectric properties, and other characteristics derived from this compound are more easily exhibited when it is in the form of a polycyanurate. In particular, the introduction of methyl groups, phenyl groups, cycloalkyl groups, etc., into the monomer, such as (7c), (7d), (7e), (7f), (7g), (7h), (7i), (7j), (7k), (7l), (7m), (7n), (7o), (7p), (7q), (7r), etc., suppresses the movement of the molecular chain and is therefore more preferable. Among these, (7d), (7k), (7l), (7p), and (7r) are particularly preferred because the monomers are readily available.

[0159] [ka]

[0160] These aliphatic and aromatic groups can be used individually or in any combination and ratio of two or more.

[0161] <Polycyanurate containing repeating units represented by formula (8)> The polycyanurate of the present invention includes a repeating unit represented by formula (1). The polycyanurate of the present invention may also include 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 This group is selected from the group consisting of substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups, and substituted or unsubstituted aryloxy groups 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 of these 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 of these 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 This is selected from the group consisting of substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups, and substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms. Z 2 Specific examples of substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms in Z 1 It is equivalent to that in Z. 2 Specific examples of substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups, and substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms in Z 1 It is synonymous with that in [the context of the text].

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

[0170] Of these, when used as a polycyanurate, it exhibits various properties such as heat resistance and dielectric properties derived from this compound more readily, R 11 ~R 14 The group is preferably a methyl group, a phenyl group, or a naphthyl group, with the methyl group being particularly preferred.

[0171] X 2 X represents a single bond, an oxygen atom, a sulfur atom, or a divalent organic group represented by formula (10). 2 If it is a sulfur atom, it will represent one of the following: a sulfide group, a sulfoxide group, or a sulfone group. X 2 In the case of a divalent organic group represented by formula (10), R in formula (10)15 , R 16 A hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, or a substituted or unsubstituted aryl group is R in formula (6) above. 9 , R 10 It is synonymous with [the above].

[0172] <Polycyanurate and polycarbonate resin composition> Even when the polycyanurate contains repeating units of polycarbonate 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 incorporating the polycyanurate of the present invention into existing bisphenol-based polycarbonates, excellent heat resistance and dielectric properties can be imparted.

[0173] [ka]

[0174] (In formula (11), Y 4 Y in equation (8) above 3 (This is synonymous with...)

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

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

[0177] The ratio of repeating units (A) to repeating units (B) in the polycyanurate-polycarbonate copolymer resin or 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 most preferably 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 viewpoint of impact resistance, heat resistance, and processability, it is usually 0.1 dL / g or more, preferably 0.2 dL / g or more, preferably 0.4 dL / g or more, 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 viewpoint 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, particularly preferably 180°C or higher, 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 its molecular chain and a large dipole, which allows for a high glass transition temperature. Furthermore, the polycyanurate of the present invention offers many options for substituents, and by appropriately adjusting the size of the substituents, the internal rotational potential in the molecular chain can be adjusted to achieve a desired range of glass transition temperatures. By setting the glass transition temperature within a favorable range using this method, good heat resistance and processability can be obtained during the fabrication of molded articles. The glass transition temperature is measured by the method described in the examples.

[0181] <Relative permittivity (εr), dielectric loss tangent (tanδ)> The relative permittivity (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 × 10¹⁶, measured at a temperature of 23°C and a frequency of 10 GHz. -3 Preferably, it is 4.0 × 10 -3 It is more preferable that the following conditions apply: 3.0 × 10 -3 It is even more preferable that the following conditions apply: 2.5 × 10 -3 The following is particularly preferable: 1.5 × 10 -3 The following is particularly preferable:

[0182] By keeping the relative permittivity and dielectric loss tangent below the above upper limits, good transmission of microwave and / or millimeter-wave radio waves is achieved. The relative permittivity and dielectric loss tangent are measured by the method described in the examples.

[0183] Generally, chemical structural techniques for reducing the dielectric constant of polymers involve suppressing the ease of polarization of the molecule, while reducing the dielectric loss tangent involves suppressing the rotation of the molecular dipole. The polycyanurate of the present invention has a triazine ring with a large dipole in its molecular chain, but since the dipole moment of the triazine ring is 0, it can contribute to achieving a low dielectric constant and a low dielectric loss tangent. Furthermore, the dielectric loss tangent depends on the molecular motion when electrolysis is applied to the dielectric, and in order to achieve an even lower dielectric loss tangent, substituent Z in equation (1) 1 Yes, organic group Y 1 The selection of a preferred substituent Z is also important. 1 As explained in the section on <polycyanurate>, the most preferred substituent is Z 1Examples of the most preferred groups are the methyl group and ethyl group for linear alkyl groups, and the cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, bicyclo[2.2.1]heptyl group, cyclooctyl group, and adamantyl group for cycloalkyl groups. For aryl groups, the most preferred groups are the phenyl group, methylphenyl group such as 2-methylphenyl group, methoxyphenyl group such as 2-methoxyphenyl group, and naphthyl group. For amino groups, the R of the amino group represented by the following formula (15) is preferred. 38 and R 39 is a methyl group, R 38 and R 39 is an ethyl group, R 38 R is a methyl group 39 is a combination of phenyl groups, R 38 is an ethyl group R 39 is a combination of phenyl groups, R 38 and R 39 The most preferred amino group is the piperidinyl group represented by formula (15) below, which is among the group of substituents (16) below in which the substituents are mutually bonded to form a 6-membered ring.

[0184] [ka]

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

[0186] In formula (15) above and the group of substituents (16) shown below, the asterisk (*) indicates the bond to the triazine ring in formula (1).

[0187] [ka]

[0188] substituent Z 1If it is an aryloxy group, then the most preferred groups are phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-methoxyphenoxy, and naphthoxy. Also, preferred organic group Y 1 This is also explained in the section on <polycyanurate>, but the more preferred organic group Y 1 Examples of substituents Z are more preferably those represented by the following formulas (7a) to (7r), and in particular, by introducing methyl groups, phenyl groups, cycloalkyl groups, etc., into the monomer, such as (7c), (7d), (7e), (7f), (7g), (7h), (7i), (7j), (7k), (7l), (7m), (7n), (7o), (7p), (7q), (7r), etc., the motion 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 readily available. 1 or organic group Y 1 By adjusting this setting, the motion of polymer chains when an alternating electric field is applied to the dielectric can be suppressed, resulting in lower dielectric constant and dielectric loss tangent.

[0189] [ka]

[0190] <Mean coefficient of linear thermal expansion (CTE)> In this invention, as a reliability evaluation of the resin used in molded articles for communication equipment, the CTE was measured by the method described in (4) of the Examples section <Measurement and Evaluation Method of Physical Properties> below. The CTE of the polycyanurate of this invention is preferably 7.5 × 10 as the average coefficient of linear expansion in this measurement method. -5 / ℃ or less, more preferably 7.3 × 10 -5 / ℃ or lower, more preferably 7.0 × 10 -5 / ℃ or lower, particularly preferably 6.4 × 10 -5 / ℃ or lower, particularly preferably 5.5 × 10 -5 It exhibits a low CTE of less than / ℃.

[0191] Generally, the chemical structural factors governing the thermal expansion behavior of polymers are such that polymers with linear and rigid structures exhibit a lower coefficient of linear expansion than polymers with non-linear, flexible, and conformable chains. The molecular chain structure of the polycyanurate in this invention is linear and rigid, and therefore exhibits a low coefficient of linear expansion. Furthermore, to achieve an even lower coefficient of linear expansion, substituent Z in equation (1) 1 Yes, organic group Y 1 The selection of a preferred substituent Z is also important. 1 As explained in the section on <polycyanurate>, the most preferred substituent is Z 1 Examples of the most preferred groups are the methyl group and ethyl group for linear alkyl groups, and the cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, bicyclo[2,2,1]heptyl group, cyclooctyl group, and adamantyl group for cycloalkyl groups. For aryl groups, the most preferred groups are the phenyl group, methylphenyl group such as 2-methylphenyl group, methoxyphenyl group such as 2-methoxyphenyl group, and naphthyl group. For amino groups, the R of the amino group represented by the following formula (15) is preferred. 38 and R 39 is a methyl group, R 38 and R 39 is an ethyl group, R 38 R is a methyl group 39 is a combination of phenyl groups, R 38 is an ethyl group R 39 is a combination of phenyl groups, R 38 and R 39 The most preferred amino group is the piperidinyl group represented by formula (15) below, which is among the group of substituents (16) below in which the substituents are mutually bonded to form a 6-membered ring.

[0192] [ka]

[0193] In the above equation (15), R 38 and R 39 Each of these independently represents a hydrogen atom or an organic group having 1 to 20 carbon atoms. These organic groups may have any substituents. 38 and R39 These may be bonded to each other to form a ring. In formula (15) above and the group of substituents (16) shown below, the asterisk (*) indicates the bond to the triazine ring in formula (1).

[0194] [ka]

[0195] substituent Z 1 If it is an aryloxy group, then the most preferred groups are phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-methoxyphenoxy, and naphthoxy. Also, preferred organic group Y 1 This is also explained in the section on <polycyanurate>, but the more preferred organic group Y 1 Examples of substituents Z are more preferably those represented by the following formulas (7a) to (7r), and in particular, by introducing methyl groups, phenyl groups, cycloalkyl groups, etc., into the monomer, such as (7c), (7d), (7e), (7f), (7g), (7h), (7i), (7j), (7k), (7l), (7m), (7n), (7o), (7p), (7q), (7r), etc., the motion 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 readily available. 1 or organic group Y 1 By adjusting this, the movement of polymer chains can be suppressed, resulting in a lower coefficient of linear expansion. In environments with large temperature fluctuations, 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, achieving a desirable effect improves reliability.

[0196] [ka]

[0197] <Method for producing polycyanurate> The polycyanurate of the present invention can be produced by conventional polymerization methods. These polymerization methods are not particularly limited. Examples of polymerization methods include interfacial polymerization and molten transesterification.

[0198] (interfacial polymerization method) [Polymerization reaction] In the interfacial polymerization method, polycyanurates are obtained by interfacial polymerization of a dihydroxy compound (a starting material) and a 2,6-dihalogeno-1,3,5-triazine compound represented by formula (41) below, in the presence of a polymerization catalyst, usually maintaining a pH of 9 or higher in the presence of an organic solvent and an alkaline aqueous solution that are inert to the reaction. Molecular weight modifiers (end-terminating agents) may be added to the reaction system as needed. Antioxidants may also be added to prevent oxidation of the starting material dihydroxy compound.

[0199] [ka]

[0200] (In formula (41), Hal 1 Hal 2 Z represents a halogen atom. 1 This is Z in equation (1) above. 1 (This is synonymous with...)

[0201] As the starting material, 2,6-dihalogeno-1,3,5-triazine compounds are preferred because they are easily derivatized from cyanuryl chloride. The 2,6-dihalogeno-1,3,5-triazine compound may be used alone, or two or more may be used in any combination and ratio.

[0202] As the starting material dihydroxy compound, at least one 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] Examples of dihydroxy compounds used as raw materials for the production of the polycyanurate of the present invention include dihydroxy compounds represented by the following formula (X). HO-Y 1 -OH (X) In formula (1), Y 1 Y in equation (1) above is 1 This is synonymous with Y in formula (2) above. 2 It is more preferably represented by formula (3), even more preferably by formula (4), and particularly preferably by formula (5). 1 More specifically, these include those represented by the above formulas (7a) to (7r).

[0204] Specific examples of such dihydroxy compounds include, for example, 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; and 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 hue, impact resistance, and heat resistance of the resulting polycyanurate, and the 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 individually, or two or more may be used in any combination and ratio.

[0207] The organic solvent that is inert to the reaction is not particularly limited, but examples 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; and so on. One organic solvent may be used, or two or more may be used in any combination and ratio.

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

[0209] There are no restrictions on the concentration of alkaline compounds in an alkaline aqueous solution, but typically, to control the pH of the alkaline aqueous solution to 10-12, the concentration of alkaline compounds is used at 5-10% by weight.

[0210] Since residual alkaline compounds in polycyanurate worsen the thermal stability of the polycyanurate, it is preferable that the polymerization of the polycyanurate of the present invention includes a step to remove the used alkaline compounds. Specific examples of the alkaline compound removal step include a neutralization step with acid and washing with distilled water or deionized water. Among these, including a neutralization step with acid tends to efficiently remove alkaline compounds and is therefore preferable. These alkaline compound removal steps may be performed individually or in combination of two or more. It is desirable that the alkaline compounds and the acid used for neutralization after washing be removed as much as possible by washing with distilled water or deionized water. Dilute hydrochloric acid is preferred as the acid used in the neutralization step, but organic acids such as acetic acid, citric acid, succinic acid, and malic acid, as well as phosphoric acid, phosphoric acid with sodium hydrogen, phosphoric acid with potassium hydrogen, ammonium chloride, monosodium citrate, and other acids containing heteroatoms other than oxygen may also be used.

[0211] The polymerization catalyst is not particularly limited, but examples 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; salts of guanidine; and the like. One polymerization catalyst may be used, or two or more may be used in any combination and ratio.

[0212] Molecular weight modifiers are not particularly limited, but examples include aromatic phenols having a monovalent phenolic hydroxyl group; aliphatic alcohols such as methanol and butanol; mercaptans; phthalimides, etc., but aromatic phenols are preferred among them. Specifically, 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, pn-nonylphenol Examples 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 with an average of 12 to 35 carbon atoms in the ortho, meta, or para position, 9-(4-hydroxyphenyl)-9-(4-methoxyphenyl)fluorene, 9-(4-hydroxy-3-methylphenyl)-9-(4-methoxy-3-methylphenyl)fluorene, 4-(1-adamantyl)phenol, etc. Among these, phenol, pt-butylphenol, p-phenylphenol, and p-cumylphenol are preferably used. The molecular weight adjusting agent may be used alone, or two or more may be used in any combination and ratio.

[0213] The amount of molecular weight adjusting agent used is not particularly limited, but for example, it is 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 dihydroxy compound raw material.

[0214] While not particularly limited, examples of antioxidants include hindered phenol-based antioxidants. Specific examples 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]phosphoate, 3,3',3”,5,5',5”-hexa-tert-butyl-a,a',a”-(mesitylene-2,4,6- Examples include triyl)tri-p-cresol, 4,6-bis(octylthiomethyl)-o-cresol, ethylenebis(oxyethylene)bis[3-(5-tert-butyl-4-hydroxy-m-tolyl)propionate], hexamethylenebis[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-triazine-2-ylamino)phenol, and 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate.

[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. Examples of commercially available phenolic antioxidants include BASF's "Irganox 1010" and "Irganox 1076," and ADEKA's "ADEKA Stab AO-50" and "ADEKA Stab AO-60."

[0216] The antioxidant may be used alone, or two or more may be used in any combination and ratio.

[0217] The amount of antioxidant used is not particularly limited, but is preferably 0.001 parts by weight or more, more preferably 0.01 parts by weight or more, and even more preferably 0.1 parts by weight or more, per 100 parts by weight of the raw material dihydroxy compound. By using an amount of antioxidant above the lower limit, the antioxidant effect will be sufficient. The amount of antioxidant used is preferably 1 part by weight or less, more preferably 0.5 parts by weight or less, per 100 parts by weight of the raw material dihydroxy compound. By using an amount of antioxidant below the upper limit, gas generation during injection molding can be suppressed.

[0218] The order in which the reaction substrate (reaction raw materials), reaction solvent (organic solvent), catalyst, additives, etc. are mixed during the reaction is arbitrary as long as the desired polycyanurate is obtained, and any appropriate order can be set as desired.

[0219] As a method for synthesizing a copolymer resin of repeating units of polycyanurate (A) and repeating units of polycarbonate resin (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 performing interfacial polymerization in the presence of a polymerization catalyst.

[0220] In the above case as well, the same specifications and amounts as in the polycyanurate synthesis described above can be applied to 2,6-dihalogeno-1,3,5-triazine, dihydroxy compounds, reaction-inert organic solvents, alkali compounds contained in alkaline aqueous solutions, polymerization catalysts, molecular weight modifiers, and antioxidants.

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

[0222] The order in which the reaction substrate (reaction raw materials), reaction solvent (organic solvent), catalyst, additives, etc. are mixed during the reaction is arbitrary as long as the desired polycyanurate is obtained, and any appropriate order can be set. Molecular weight modifiers can be mixed at any time from the initial stages of the reaction until 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 (e.g., 10 minutes) to several hours (e.g., 6 hours).

[0224] [Alkaline compound removal process] Since residual alkaline compounds in polycyanurate worsen the thermal stability of the polycyanurate, it is preferable that the polymerization of the polycyanurate of the present invention includes a step to remove the used alkaline compounds. Specific examples of the alkaline compound removal step include a neutralization step with acid and washing with distilled water or deionized water. Among these, including a neutralization step with acid tends to be preferable as it efficiently removes alkaline compounds. These alkaline compound removal steps may be performed individually or in combination of two or more. It is desirable that the alkaline compounds and the acid used for neutralization after washing be removed as much as possible by washing with distilled water or deionized water. Dilute hydrochloric acid is preferred as the acid used in the neutralization step, but organic acids such as acetic acid, citric acid, succinic acid, and malic acid, as well as phosphoric acid, phosphoric acid with sodium hydrogen, phosphoric acid with potassium hydrogen, ammonium chloride, monosodium citrate, and other acids containing heteroatoms other than oxygen may also be used.

[0225] The residual alkali content in the polycyanurate of the present invention is preferably less than 50 ppm. A residual alkali metal content of 50 ppm or more tends to worsen the moldability of the polycyanurate and is therefore undesirable. The residual alkali content in the polycyanurate can be quantified 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, and more preferably less than 100 ppm. A residual catalyst amount of 200 ppm or more tends to degrade the dielectric properties and is therefore undesirable. The amount of residual catalyst in the polycyanurate can be quantified using gas chromatography.

[0226] [Obtaining polycyanurate] Methods for obtaining a solid polycyanurate from a reaction mixture containing the polycyanurate of the present invention after a polymerization reaction step and an alkali compound removal step include distilling off the organic solvent to obtain it as a solid, spraying the polycyanurate solution and drying it instantaneously to obtain it as granules or fine particles, adding it to hot water and distilling off the solvent to obtain it as a solid, and dropping the polycyanurate solution after alkali compound removal into an organic solvent in which polycyanurate is poorly soluble to obtain it as 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 formula (52) is produced in an amount of about 5% to 20% by weight relative to the amount of polycyanurate produced. The reason for the difference in the amount of cyclic oligomer produced is the substituent Z of the polycyanurate. 1 or organic group Y 1 This is because the ease of cyclization and the amount produced vary depending on the substitution position and size of the molecule.

[0227] [ka]

[0228] (In formulas (51) and (52), Z 1 ,Y 1 This is equivalent to the one in equation (1) above, and Y in equation (52) 2 This is equivalent to the expression in equation (2) above.

[0229] If a large amount of cyclic oligomers remain in the polycyanurate of the present invention, the thermal stability of the polycyanurate deteriorates and surface defects described later 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 the polycyanurate solution to an organic solvent in which the polycyanurate is poorly soluble and which dissolves the cyclic oligomers, and obtain the polycyanurate from which the cyclic oligomers have been removed as a solid. 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 for cyclic oligomers and low solubility for polycyanurate are more preferred, and ethyl acetate is the most preferred.

[0230] When choosing a method to obtain polycyanurate as a solid by adding a polycyanurate solution to an organic solvent in which polycyanurate is poorly soluble, 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, if a large amount of cyclic oligomer is purified by the polymerization reaction, a large amount of solvent must be used to remove the cyclic oligomer from the polycyanurate, which is undesirable.

[0231] The amount of residual cyclic oligomers in the polycyanurate of the present invention is preferably less than 5% by weight, more preferably less than 3% by weight, and most preferably less than 1% by weight, as the total content of the cyclic oligomer represented by formula (51) and the cyclic oligomer represented by formula (52). When polycyanurate is used as a molded article for communication equipment such as sheets, films, coatings, and multilayer films incorporated into information and communication equipment intended for use in the microwave and / or millimeter wave bands, the presence of low molecular weight components such as monomers and oligomers can lead to various problems, such as surface defects caused by bleeding out to the surface over time, resulting in transmission loss, or transfer to rolls, resulting in process defects. Furthermore, a high amount of residual cyclic oligomers is undesirable because it worsens the thermal stability of the polycyanurate as shown in Table 3 below. The amount of residual cyclic oligomers in polycyanurate can be determined by gel permeation chromatography (GPC), proton nuclear magnetic resonance ( 1 It can be quantified by 1H NMR. Furthermore, considering the need to remove cyclic oligomers from the polycyanurate, the amount of residual cyclic oligomers in the polycyanurate of the present invention is preferably 100 ppb by weight or more, and more preferably 1 ppm by weight or more, as the total content of the cyclic oligomer represented by formula (51) and the cyclic oligomer represented by formula (52).

[0232] (Fresh transesterification method) The molten transesterification method is a method for producing polycyanurates by carrying out a transesterification reaction via polycondensation of a starting material containing, for example, a bifunctional triazine compound represented by formula (42) below, a starting dihydroxy compound, and a catalyst. The starting dihydroxy compound is an aromatic dihydroxy compound similar to that used in the interfacial polymerization method, as well as a divalent aliphatic diol represented by formulas (12a) to (12g) below, or a divalent aliphatic diol in which the aromatic ring structure is substituted, such as those shown in formulas (13) and (14) below.

[0233] [ka]

[0234] (In formula (13), R 17 ~R 19 Each of these is an alkylene group having 1 to 4 carbon atoms, which may be directly bonded or substituted. 20 ~R 25 Each of these is independently a hydrogen atom, an optionally substituted C1-C10 alkyl group, an optionally substituted C4-C10 aryl group, an optionally substituted C1-C10 acyl group, an optionally substituted C1-C10 alkoxy group, an optionally substituted C4-C10 aryloxy group, an optionally substituted C1-C10 acyloxy group, an optionally substituted amino group, an optionally substituted C2-C10 alkenyl group, an optionally substituted C2-C10 alkynyl group, a substituted sulfur atom, a substituted silicon atom, a halogen atom, a nitro group, or a cyano group. 20 ~R 25 At least two adjacent groups may be bonded to each other to form a ring. In formula (14), R 26 ~R 29 R 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 of these independently represents a hydrogen atom, a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C6-C20 cycloalkyl group, or a substituted or unsubstituted C6-C20 aryl group. m and n are each independently integers from 0 to 5.

[0235] [ka]

[0236] (In formula (42), L 1 , L 2 Each of these is an aryloxy group independently, and Z 1 This is Z in equation (1) above. 1(This is synonymous with...)

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

[0238] When producing polycyanurates by molten transesterification, a transesterification catalyst is usually used. The transesterification catalyst is not particularly limited, and conventionally known catalysts can be used. For example, alkali metal compounds and / or alkaline earth metal compounds are preferred. As an auxiliary, basic compounds such as basic boron compounds, basic phosphorus compounds, basic ammonium compounds, and amine compounds may be used in combination. One type of transesterification catalyst may be used, or two or more types may be used in any combination and ratio.

[0239] In the molten transesterification method, the reaction temperature is not particularly limited, but is usually between 100 and 320°C. The reaction pressure is not particularly limited, but is usually under reduced pressure conditions of 2 mmHg or less. Specifically, the molten polycondensation reaction can be carried out under the above conditions while removing by-products.

[0240] The polycyanurate of the present invention is significantly affected by thermal history and oxidation in the presence of an alkaline catalyst, which may lead to deterioration of its color. Therefore, it is preferable to keep the reaction temperature below 320°C. Furthermore, 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 approximately 0.05 mmHg.

[0241] The reaction can be carried out in either a batch or continuous manner. In the batch method, the order in which the reaction substrate, reaction solvent, catalyst, additives, etc. are mixed is arbitrary as long as the desired polycyanurate is obtained, and any appropriate order can be set.

[0242] In the molten transesterification process, 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 catalyst deactivator may be used, or two or more may be used in any combination and ratio.

[0243] The amount of 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, and usually 50 equivalents or less, preferably 10 equivalents or less, and more preferably 8 equivalents or less, relative to the transesterification catalyst. The amount of catalyst deactivator used is usually 1 ppm or more, and 100 ppm or less, and preferably 50 ppm or less, relative to the polycyanurate.

[0244] As a method for synthesizing a copolymer resin of repeating units (A) of polycyanurate and repeating units (B) of polycarbonate, 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 a bifunctional triazine compound and a raw material dihydroxy compound represented by formula (42).

[0245] Examples of carbonate esters include compounds represented by the following formula (44). Examples of carbonate esters include aryl carbonates, dialkyl carbonates, biscarbonate forms of dihydroxy compounds, monocarbonate forms of dihydroxy compounds, and carbonate forms of dihydroxy compounds such as cyclic carbonates.

[0246] [ka]

[0247] (In the above formula (44), R 38 and R 39 Each of these 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 However, when it is an alkyl group or arylalkyl group, it is sometimes called a dialkyl carbonate, and when it is an aryl group, it is sometimes called a diaryl carbonate. In particular, from the viewpoint of reactivity with dihydroxy compounds, R 38 and R 39 Both are preferably aryl groups, and more preferably diaryl carbonates represented by the following formula (45).

[0249] [ka]

[0250] (In the above formula (45), R 40 and R 41 Each of these is independently a halogen atom, a nitro group, a cyano group, a C1-C20 alkyl group, a C1-C20 alkoxycarbonyl group, a C4-C20 cycloalkyl group, or a C6-C20 aryl group, and p and q each independently represent an integer from 0 to 5.

[0251] 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"), diaryl carbonates (which may have substituents) such as 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 ditril carbonate. Among these carbonate esters, diphenyl carbonate is preferred. These carbonate esters can be used individually or in combination of two or more.

[0252] The ratio of the difunctional triazine compound, dihydroxy compound, and carbonate ester is arbitrary as long as the desired polycyanurate-carbonate copolymer resin is obtained. It is preferable that the total amount of the difunctional triazine compound and carbonate ester be slightly in excess of the dihydroxy compound when polymerizing with it. The amount of the carbonate ester is preferably 1.01 times (molar ratio) or more, and more preferably 1.02 times or more, relative to the dihydroxy compound. By setting the molar ratio to the lower limit above, the resulting polycyanurate-carbonate copolymer resin will have good thermal stability. The total amount of the difunctional triazine compound and carbonate ester is preferably 1.30 times (molar ratio) or less, and more preferably 1.20 times (molar ratio) or less, relative to the dihydroxy compound. By keeping the molar ratio below the above upper limit, reactivity is improved, resulting in good productivity of polycyanurate-carbonate copolymer resin having the desired molecular weight. Furthermore, the amount of residual difunctional triazine compound and carbonate ester in the resin is reduced, which suppresses discoloration of the resin during molding and when it is formed into a molded article.

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

[0254] [ka]

[0255] (In formulas (51) and (52), Z 1 ,Y 1 This is equivalent to the one in equation (1) above, and Y in equation (52) 2 This is equivalent to the expression in equation (2) above.

[0256] <Thermoplastic resin composition> The thermoplastic resin composition of the present invention may contain other components in addition to the polycyanurate (including polycyanurate-polycarbonate copolymer resin) and the aforementioned polycarbonate, 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, and so on. The other components may be present individually, or two or more may be present in any combination and ratio.

[0257] Examples of resins other than polycyanurate and polycarbonate in 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 polyallyl ether ketone (PAEK).

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

[0259] Examples of resin additives include crosslinking agents, heat stabilizers, antioxidants, coupling agents, mold release agents, UV absorbers, colorants (dyes and pigments), flame retardants, anti-dripping agents, antistatic agents, preservatives, lubricants, anti-blocking agents, flow improvers, plasticizers, dispersants, emulsifiers, de-elasticizing agents, diluents, defoaming 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 of these resin additives, or two or more may be contained in any combination and ratio.

[0261] Of these, the thermoplastic resin composition of the present invention preferably contains one or more additives selected from the group consisting of crosslinking agents, ultraviolet absorbers, antistatic agents, antioxidants, coupling agents, plasticizers, flame retardants, colorants, dispersants, emulsifiers, deelasticizing agents, diluents, defoaming agents, ion trapping agents, thickeners, leveling agents, inorganic particles, and organic particles.

[0262] Including these other resins and resin additives, the content of the polycyanurate of the present invention in the thermoplastic resin composition of the present invention 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 70-100% by weight.

[0263] <Method for producing thermoplastic resin compositions> There are no limitations on the method for producing the thermoplastic resin composition of the present invention, and a wide range of known methods for producing thermoplastic resin compositions can be employed. Specifically, examples include melt-kneading methods using a mixture of gas, such as a Banbury mixer, rolls, short-shaft kneading extruder, twin-shaft kneading extruder, and kneader.

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

[0265] There are no particular restrictions on the shape of the molded body, and it can be appropriately selected according to the application and purpose of the molded body. Examples include plate-shaped, rod-shaped, sheet-shaped, film-shaped, cylindrical, annular, circular, elliptical, polygonal, irregularly shaped, hollow, frame-shaped, box-shaped, and panel-shaped products. The molded body may be a molded body having irregularities on its surface, or a molded body with a three-dimensional curved surface and a three-dimensional shape. When used as a sheet, film, or plate, it may be used as a multilayer laminate formed by laminating it with other resin sheets.

[0266] The method for forming the molded article is not particularly limited, and conventionally known molding methods can be employed. Examples include injection molding, injection compression molding, extrusion molding, shape extrusion, transfer molding, hollow molding, gas-assisted hollow 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, lamination, vacuum forming, pressure forming, press molding, and casting. Of these, extrusion molding, injection molding, blow molding, vacuum forming, pressure forming, press molding, or casting is preferred, and injection molding or extrusion molding is 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. Setting the molding temperature above the lower limit improves fluidity and moldability. The molding temperature when molding the thermoplastic resin composition of the present invention is preferably 350°C or lower, and particularly preferably 320°C or lower. Setting the molding temperature below the upper limit improves the color tone of the thermoplastic resin composition.

[0268] The film may be a uniaxially or biaxially oriented film that has been stretched in one or two directions. Methods for manufacturing the stretched film include preparing an unstretched film as a precursor by methods such as the T-die-casting method, pressing method, or calendering method, followed by stretch molding by methods such as roll stretching or tenter stretching, or by methods such as inflation method or tubular method in which melt extrusion and stretch molding are performed integrally.

[0269] The molding temperature in press molding and extrusion casting using T-dies is adjusted as appropriate depending on the flow characteristics and film-forming properties of the thermoplastic resin composition used, but is generally between 280°C and 370°C. For melt mixing, commonly used single-screw extruders, twin-screw extruders, kneaders, and mixers can be used, and there are no particular restrictions.

[0270] When performing injection molding or extrusion molding, pigments, dyes, mold release agents, heat stabilizers, etc., can be appropriately added to the thermoplastic resin composition of the present invention, as long as they do not impair the objectives 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 arbitrarily employed. Examples include ultra-high-speed injection molding, injection compression molding, two-color molding, hollow molding methods such as gas-assisted molding, molding methods using insulated molds, molding methods using rapidly heated molds, 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 using an injection molding machine, the mold temperature is preferably 150°C or lower, more preferably 120°C or lower, and most preferably 100°C or lower. By keeping the mold temperature below the above upper limit, the cooling time during molding can be shortened, shortening the manufacturing cycle of the molded product and improving productivity. When using an injection molding machine, the mold temperature is preferably 30°C or higher, and particularly preferably 50°C or higher. Keeping the mold temperature above the above lower limit is preferable because it allows for the acquisition of a uniform molded product.

[0273] <Extruded product> The thermoplastic resin composition of the present invention can be suitably used as an extruded article by extrusion molding. There are no particular limitations on how an extruded article can be produced from the thermoplastic resin composition of the present invention, but an extruder is usually used. The extruder is generally equipped with a T-die, a round die, etc., and can produce extruded articles of various shapes. Examples of extruded articles include sheets, films, plates, tubes, pipes, etc. Among these, sheets or films are preferred.

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

[0275] Among these, the thermoplastic resin composition of the present invention is particularly effective as a molding material for communication equipment housings incorporating microwave and / or millimeter-wave antennas, covers for communication equipment housings, insulating films, encapsulants, printed circuit boards, and the like, due to its excellent properties of microwave and / or millimeter-wave band radio wave transmission, heat resistance, and low linear expansion.

[0276] <Molded body thickness> In the case of a molded article using the thermoplastic resin composition of the present invention, particularly a molded article for communication equipment incorporating a microwave and / or millimeter-wave antenna as described later, the thickness 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 portion that occupies 50% or more of the area of ​​the entire molded article, for example, the thickness of the main plate surface. If the thickness of the molded body is below the above upper limit, transmission loss can be reduced. If the thickness of the molded body is above the above lower limit, sufficient mechanical strength and other properties can be maintained to preserve the structure of the molded body.

[0277] There are no restrictions on the shape, pattern, color, dimensions, etc., of a molded body for communication equipment that incorporates such a microwave and / or millimeter-wave antenna, and these can be appropriately selected according to the application of the molded body for communication equipment that incorporates the microwave and / or millimeter-wave antenna.

[0278] In this invention, microwaves are radio waves with a frequency of 3.0 to 30 GHz, and millimeter waves are radio waves with a frequency of 30 to 300 GHz. Therefore, microwaves and / or millimeter waves are radio waves with a frequency of 3.0 to 300 GHz. In other words, a communication device that incorporates a microwave and / or millimeter wave antenna is a communication device that incorporates an 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 terminals, smartphones, or router devices that transmit and receive radio waves with a frequency of 3.0 to 300 GHz.

[0279] The frequency transmitted and received by the microwave and / or millimeter-wave antenna of the molded body for communication equipment incorporating the microwave and / or millimeter-wave antenna of the present invention is not particularly limited as long as it is between 3.0 and 300 GHz, but is more suitable for radio waves in the 3.2 to 250 GHz frequency band, and even more suitable for radio waves in the 3.4 to 200 GHz frequency band.

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

[0281] Microwave and / or millimeter-wave radio waves tend to have poor transmission properties. From this perspective, molded bodies for communication equipment that incorporate antennas for transmitting and receiving microwave and / or millimeter-wave radio waves are required to have high radio wave transmission properties. Communication equipment that transmits and receives microwave and / or millimeter-wave radio waves tends to generate heat; therefore, molded bodies for communication equipment that incorporate antennas that transmit and receive microwave and / or millimeter-wave radio waves require high heat resistance and a low coefficient of linear expansion.

[0282] The polycyanurate contained in the thermoplastic resin composition of the present invention, used in molded articles for communication equipment incorporating an antenna for transmitting and receiving microwave and / or millimeter-wave radio waves, possesses a low relative permittivity, low dielectric loss tangent, high heat resistance, and low coefficient of linear expansion. Therefore, the thermoplastic resin composition of the present invention, containing the polycyanurate, possesses a low relative permittivity, low dielectric loss tangent, high heat resistance, and low coefficient of linear expansion, making it suitable for use in molded articles for communication equipment transmitting and receiving microwave and / or millimeter-wave radio waves.

[0283] Specific examples of molded articles for communication equipment incorporating microwave and / or millimeter-wave antennas include sheets, films, coatings, and multilayer films, as well as housings for communication equipment, which are incorporated into notebook computers, tablet terminals, smartphones, or router devices, and thin-film transistors and printed circuit boards in which a cover, insulating film, encapsulant, and gate electrode layer of the housing of the communication equipment are laminated in this order. The molded articles for communication equipment of the present invention, which are made of the thermoplastic resin composition of the present invention, are particularly suitable for these applications.

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

[0285] <Circuit board materials> A resin sheet made from the thermoplastic resin composition of the present invention can be used as a circuit board material by laminating it with a conductor. As conductors, metal foils made of conductive metals such as copper and aluminum, or alloys containing these metals, or metal layers formed by plating or sputtering can be used. When used as a circuit board material for electrical and electronic equipment, the thickness of the resin sheet is preferably 10 μm to 200 μm. Furthermore, the thickness of the conductor is preferably 0.2 μm to 70 μm.

[0286] A circuit board material using the thermoplastic resin composition of the present invention is characterized by having a sufficiently low dielectric loss tangent. The dielectric loss tangent of the circuit board material is preferably less than 0.01 at 12 GHz, and more preferably less than 0.008. A lower dielectric loss tangent is preferable because it allows for higher electrical signal transmission efficiency and faster speeds when used as a circuit board. The lower limit of the dielectric loss tangent is not particularly limited and may be 0 or greater.

[0287] <Manufacturing method for circuit board materials> The circuit board material in this invention can be manufactured, for example, by the following method. After laminating a conductor onto 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 stacked. The lamination of the resin sheet and the conductor may be done by directly overlapping the conductive metal foil onto the resin sheet, or by bonding the resin sheet and the conductive metal foil using an adhesive. Alternatively, the conductive metal layer may be formed by plating or sputtering, or a combination of these methods may be used.

[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, wherein the film layer is the metal-clad laminate which is the molded body for communication equipment of the present invention described above.

[0289] The details of the metal-clad laminate of the present invention are the same as those of the circuit board material described above, with the film layer being a resin sheet made of the thermoplastic resin composition of the present invention, and the metal foil being the conductor described above. In this invention, the film layer is a molded body for communication equipment of the present invention, and the metal foil layer is laminated with it. [Examples]

[0290] The present invention will be described in more detail below based on examples. However, the present invention is not limited to the following examples.

[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 methods described below.

[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.). The reduced viscosity (ηSP / c) was calculated by dividing the measured viscosity 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 a Shimadzu SCL-10AVP under the following conditions. Column: TSKgelα-3000 (particle size 7μm, inner diameter 7.8mm, length 30cm) + TSKgelα-4000 (particle size 10μm, inner diameter 7.8mm, length 30cm) Mobile phase: Tetrahydrofuran (containing 0.03% by volume of 2,6-di-t-butyl-4-methylphenol as a stabilizer) Detection wavelength: 254nm Flow rate: 1.0mL / min Column oven temperature: 40℃

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

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

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

[0297] (6) Dielectric properties: Relative permittivity (ε r ) · Dielectric loss tangent (tanδ) Resin that had been vacuum-dried at 80°C for 5 hours was formed into a film using a hot press molding machine to produce films with a thickness of 200 to 600 μm. The molding conditions of the hot press molding machine were adjusted as appropriate within the range of temperature 150 to 250°C and pressure 10 to 15 MPa. Strips of film measuring 70 mm in length, 1.97 mm to 1.38 mm in width, and 431 to 624 μm in thickness were cut from this film. After humidification at room temperature of 23°C and humidity of 50% for 48 hours, the relative permittivity (ε) was measured at a frequency of 10 GHz using a cavity resonator (CP-531, manufactured by Kanto Applied Electronics Development Co., Ltd.) and a series network analyzer (E8361A PNA, manufactured by Keysight Technologies). r The dielectric loss tangent (tanδ) was measured.

[0298] (7) Mean coefficient of linear expansion (CTE) (3) Dielectric properties: Relative permittivity (ε r Films formed in the same manner as in the previous example were punched out using a 4mm wide, 40mm long super straight cutter, and measured using a TMA / SS6100 manufactured by SII Nanotechnology. The distance between the chucks of the film samples was 10mm, and the CTE between -20°C and 80°C was measured when the temperature was increased from -30°C to 100°C at a heating rate of 10°C / min with 120mL / min of nitrogen.

[0299] (8) Proton nuclear magnetic resonance ( 1 (H NMR) The following apparatus and solvent were used. Equipment: JEOL ECZ400S nuclear magnetic resonance spectrometer, 400MHz Solvent: 0.03 vol% tetramethylsilane-containing deuterated chloroform

[0300] (9) Matrix-assisted laser desorption / ionization mass spectrometry Using the following apparatus, mass spectrometry was performed on the low molecular weight components removed in the ethyl acetate precipitate recovery treatment of Example 8. As a result, it was confirmed that these 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 number range: 50-10,000 (m / z) Sample preparation: 0.2 μL of a mixture of tetrahydrofuran solution of the sample and 10 mg / mL tetrahydrofuran solution of the matrix material was spread onto 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), and under a nitrogen atmosphere, a 3 mol / L phenylmagnesium bromide solution in tetrahydrofuran [2] (397.66 mL) was added dropwise at 0°C. After the addition, the mixture was stirred under a nitrogen atmosphere at 30°C for 12 hours. Then, 100 mL of saturated aqueous ammonium chloride solution was slowly added to the reaction mixture at 0°C to quench it. 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 filtered off, and the filtrate was concentrated to obtain the crude product. The crude product was added to a mixed solution 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] (157g, 694.50 mmol, yield 64.0%, HPLC purity 98.8%) as a light brown solid. Proton nuclear magnetic resonance (hereinafter, 1It is sometimes abbreviated as "H NMR". The spectrum matched that of 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 300 mL of pure water to form a solution, and phenol[4] (134.26 g, 1.43 mol) was added at 0°C and dissolved. This solution was added dropwise at 0°C 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) under a nitrogen atmosphere. The mixture was stirred at 0°C for 1 hour, and then stirred at 30°C for 8 hours. The reaction mixture was filtered, and the filtered cake was washed with heptane (200 mL). Next, the filtered cake was concentrated to dryness to obtain crude crystals (185 g) of 2,4-diphenoxy-6-phenyl-1,3,5-triazine as an off-white solid, which was purified by silica gel column chromatography (eluting by gradually changing the heptane / ethyl acetate ratio from 1 / 0 to 10 / 1). The pure fraction was 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 1H NMR spectrum matched that of the desired product. 1H 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-triazine-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 mixed solution of N-methylaniline [6] (118.53 g, 1.11 mol) in THF (1 L) was added dropwise at 0°C. This mixed solution was stirred at 25°C for 3 hours. Next, the reaction mixture was added to ice water (2 L) to precipitate crystals. The precipitated crystals were filtered off, and ethyl acetate (300 mL) was added to the filtrate to extract the product into the organic layer. This procedure was repeated twice. Anhydrous sodium sulfate was added to the obtained organic layer and dried. After filtering off the sodium sulfate, 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 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 the resulting crystals were dried under reduced pressure to obtain 4,6-dichloro-N-phenyl-N-methyl-1,3,5-triazine-2-amine[7] (132.39 g, yield 48.3%) as a white solid. 1 The 1H NMR spectrum matched that of 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-triazine-2-amine[8]]

[0312] [ka]

[0313] Sodium hydroxide (34.49 g, 862.40 mmol) was added to 30 mL of pure water to form a solution, and phenol [4] (79.32 g, 842.80 mmol) was added at 0°C and dissolved. This solution was added dropwise at 0°C to a mixed solution of 4,6-dichloro-N-phenyl-N-methyl-1,3,5-triazine-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) under a nitrogen atmosphere. The mixture was stirred at 0°C for 1 hour, and then stirred at 25°C for 12 hours. The precipitated crystals were filtered, and the filtered 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 ratio of 90 / 10). The pure fraction was concentrated to dryness and added to n-heptane (400 mL). After stirring at 20°C for 12 hours, the crystals were filtered, and the resulting crystals were dried under reduced pressure to obtain 4,6-diphenoxy-N-methyl-N-phenyl-1,3,5-triazine-2-amine[8] (94.25 g, yield 67.2%, HPLC purity 99.9%) as a white solid. 1 The 1H NMR spectrum matched that of 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 of 2,2-bis(4-hydroxyphenyl)propane

[11] ] [ka]

[0315] In a glass reactor equipped with a reactor stirrer, reactor heating device, and 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 used, and 2.14 × 10¹⁶ cesium carbonate was added. -3 The raw material mixture was prepared by adding parts by weight (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 restored to atmospheric pressure with nitrogen. This process was repeated three times to purge the inside of the reactor with nitrogen. After nitrogen purging, the external temperature of the reactor was raised to 150°C, stirred (100 rpm), and the temperature was raised to 240°C at atmospheric pressure over 60 minutes to dissolve the mixture (dissolution step). As the first step of the polymerization reaction, the mixture was maintained at 240°C for 30 minutes. Then, while distilling off the phenol produced as a by-product by the oligomerization reaction occurring inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) in absolute pressure over 40 minutes.

[0316] Next, the reactor pressure was maintained at 13.3 kPa, and the reaction was carried out for 60 minutes while further distilling off the phenol. As the second stage of polymerization, the external temperature of the reactor was raised to 270°C in 20 minutes, and at the same time, the reactor pressure was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) in absolute pressure over 30 minutes to remove the distilled phenol from the system. Furthermore, the absolute pressure inside the reactor was reduced to below 200 Pa, and the polycondensation reaction was continued. In the case of oligomers, the stirring power does 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 of polymerization to the end of the second stage of polymerization.

[0317] Next, after restoring pressure in the reactor with nitrogen, 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 pale orange solid. 1 The number-average molecular weight was calculated to be 770 based on the integral ratio of the 1H 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 heater, and a reactor pressure regulator.

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

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

[0321] Next, after restoring pressure in the reactor with nitrogen, the molten polymer was removed from the reactor and cooled at room temperature to obtain the polymer. The monomer composition, polymerization conditions, reduced viscosity, molecular weight, and oligomer content were measured and the results are shown in Table 1A. Also, glass transition temperature (Tg), relative permittivity (ε) r The measurement results for dielectric loss tangent (tanδ) and coefficient of linear expansion (CTE) are shown in Table 2A along with the monomer composition.

[0322] [Example 2] 90.03 parts by weight of 4,6-dichloro-N-phenyl-N-methyl-1,3,5-triazine-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 is referred to as 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 1 N sodium hydroxide. This solution is referred to as Solution B. Solution B and 11.30 parts by weight of tetrabutylammonium bromide were added to 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. 904 parts by weight of methylene chloride and 600 parts by weight of demineralized water were added to the reaction solution to extract the organic layer, which was then washed with 100 parts by weight of 0.1 N hydrochloric acid solution. Subsequently, the organic layer was 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 vacuum-dried at 100°C for 6 hours to obtain the target product in 77% yield. The results are shown in Tables 1A and 2A.

[0323] To confirm that the filtrate produced 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 method described in Example 1 was followed, except that the amount of 2,4-diphenoxy-6-phenyl-1,3,5-triazine[5] used was 74.8 parts by weight, 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 described in Table 1A. The results are shown in Tables 1A and 2A.

[0326] [Example 4] The procedure was carried out in the same manner as in Example 1, except that 81.2 parts by weight of 4,6-diphenoxy-N-methyl-N-phenyl-1,3,5-triazine-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 0.043 parts by weight, and the polymerization conditions were as described in Table 1A. The results are shown in Tables 1A and 2A.

[0327] [Example 5] In a glass reactor equipped with a reactor stirrer and a reactor heater, 2.995 parts by weight of polycarbonate oligomer of BPA

[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. After dissolving the contents by raising the external reactor temperature to 30°C, 8.454 parts by weight of 1 N sodium hydroxide was added and the mixture was stirred for 1.5 hours. Ten parts by weight of demineralized water and seven.5 parts by weight of methylene chloride were added to the reaction mixture to extract the organic layer, which was then washed with ten parts by weight of 0.1 N hydrochloric acid solution. Subsequently, the organic layer was washed with ten 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 vacuum-dried 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 reprecipitate. The precipitated white solid was collected and vacuum-dried at 90°C for 3 hours to obtain the target product in 51% yield. The results are shown in Tables 1A and 2A.

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

[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 were added. After dissolving the contents by raising the external temperature of the reactor to 30°C, 4.347 parts by weight of 1 N sodium hydroxide was added and the mixture was stirred for 1 hour. 20 parts by weight of demineralized water and 25 parts by weight of methylene chloride were added to the reaction mixture to extract the organic layer, which was then washed with 20 parts by weight of 0.1 N hydrochloric acid solution. Subsequently, 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 200 parts by weight of ethyl acetate and stirred for 1 hour. The precipitated white solid was collected and vacuum-dried at 90°C for 2 hours to obtain the target product in 53% yield. The results are shown in Tables 1A and 2A.

[0329] [Example 7] In a glass reactor equipped with a reactor stirrer, reactor heating device, and 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 used, and the amount of cesium carbonate added was 4.24 × 10⁻⁶. -3 A raw material mixture was prepared by adding parts by weight. Next, the pressure inside the glass reactor was reduced to approximately 50 Pa (0.38 Torr), and then the pressure was restored to atmospheric pressure with nitrogen. This process was repeated three times to purge the inside of the reactor with nitrogen. After nitrogen purging, the external temperature of the reactor was raised to 150°C, and stirring was performed as needed. The temperature was then raised to 240°C at atmospheric pressure over 60 minutes to dissolve the mixture (dissolution step). As the first step of the polymerization reaction, the mixture was maintained at 240°C for 30 minutes. Then, while distilling off the phenol produced as a by-product by the oligomerization reaction occurring inside the reactor, the pressure inside the reactor was reduced from 101.3 kPa (760 Torr) to 13.3 kPa (100 Torr) in absolute pressure over 40 minutes. Next, the reactor pressure was maintained at 13.3 kPa, and the reaction was carried out for 60 minutes while further distilling off the phenol. As the second stage of polymerization, the external temperature of the reactor was raised to 280°C in 20 minutes, and at the same time, the reactor pressure was reduced from 13.3 kPa (100 Torr) to 399 Pa (3 Torr) in absolute pressure over 30 minutes to remove the distilled phenol from the system. Furthermore, the absolute pressure inside the reactor was reduced to below 200 Pa, and the polycondensation reaction was continued. The polycondensation reaction was terminated when the reactor stirrer reached a predetermined stirring power. The total polymerization time in this example is the time from the start of the first stage of polymerization to the end of the second stage of polymerization. In this example, it was 3 hours and 30 minutes. Next, the reactor was repressurized with nitrogen, and the molten polymer was removed from the reactor and cooled at room temperature to obtain the polymer. The results are shown in Tables 1B and 2B.

[0330] [Example 8] 2.26 parts by weight of BPC were dissolved in 19.15 parts by weight of 1 N sodium hydroxide. This solution is designated as solution C. 2,000 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 dissolving the contents by raising the external reactor temperature to 30°C, solution C was added and the mixture was stirred for 3.5 hours. 20 parts by weight of demineralized water and 13.9 parts by weight of methylene chloride were added to the reaction mixture to extract the organic layer, which was then washed with 10 parts by weight of 0.1 N hydrochloric acid solution. The organic layer was then washed again 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] A 0.5 wt portion of the washed organic layer described above was sampled, the solvent was removed by distillation, and the resulting solid was dried at 80°C for 6 hours to obtain a polymer sample for thermal stability evaluation as a white solid. (This polymer sample is referred to as the crude product.) The amount of residual cyclic oligomers 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 described above was sampled, added to 10 parts by weight of methanol, and stirred for 1 hour. The resulting precipitate was removed and dried at 80°C for 6 hours to obtain a polymer sample for thermal stability evaluation as a white solid. (This polymer sample is referred to as the methanol precipitate.) The amount of residual cyclic oligomers 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 described above was sampled, added to five parts by weight of ethyl acetate, and stirred for one hour. The resulting precipitate was removed and dried at 80°C for six hours to obtain a polymer sample for thermal stability evaluation as a white solid. (This polymer sample is referred to as ethyl acetate precipitate 1.) The amount of residual cyclic oligomers 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 removed and vacuum-dried at 80°C for 6 hours to obtain the target product in 60% yield. (This polymer sample will be referred to as Example 8 or Ethyl Acetate Precipitate 2.) The monomer composition, polymerization conditions, reduced viscosity, molecular weight, and oligomer content measurements are shown in Table 1B. Also, glass transition temperature (Tg), relative permittivity (ε) r The measurement results for dielectric loss tangent (tanδ) and coefficient of linear expansion (CTE), along with the monomer composition, are shown in Table 2B. Furthermore, the amount of residual cyclic oligomers 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. The filtrate obtained in the procedure for acquiring ethyl acetate precipitate 2 was concentrated to obtain a white solid. Mass spectrometry of the obtained sample using matrix-assisted laser desorption / ionization mass spectrometry confirmed that it consisted of nine types of cyclic oligomers represented by the following formula (50A).

[0333] [ka]

[0334] [Example 9] The procedure described in Example 8 was carried out, except that 2.58 parts by weight of 4,4'-methylenebis(2,6-dimethylphenol) [TmBPF] (referred to as "TmBPF" in Tables 1A, 1B, 2A, and 2B) was used instead of BPC, 2.288 parts by weight of 1 N 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 a yield of 63%. 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 1 N sodium hydroxide. This solution is designated as solution D. In a glass reactor equipped with a reactor stirrer and a reactor heater, 2.05 parts by weight of 4,6-dichloro-N-phenyl-N-methyl-1,3,5-triazine-2-amine[7], 0.194 parts by weight of tetrabutylammonium bromide, and 14.7 parts by weight of nitrobenzene were added. After dissolving the contents by raising the external reactor temperature to 35°C, solution D was added and the mixture was stirred for 5.5 hours. 20 parts by weight of demineralized water and 15 parts by weight of methylene chloride were added to the reaction mixture to extract the organic layer, which was then washed with 10 parts by weight of 0.1 N hydrochloric acid solution. Subsequently, 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 270 parts by weight of ethyl acetate, and the precipitated white solid was collected and vacuum-dried at 100°C for 6 hours to obtain the target product in 65% yield. 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 and dissolved. This solution is called solution E. In a glass reactor equipped with a reactor stirrer and a reactor heater, 1.502 parts by weight of 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol (indicated as "BP-TMC" in Tables 1A, 1B, 2A, and 2B) and 10.23 parts by weight of 1N sodium hydroxide aqueous solution were added. After dissolving the contents by raising the external reaction temperature to 30°C, 0.079 parts by weight of tetrabutylammonium bromide was added, followed by 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. Then, it was washed with 10 parts by weight of 0.1 N hydrochloric acid water. Subsequently, 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 vacuum-dried at 100°C for 6 hours to obtain the target product in 62% yield. The results are shown in Tables 1B and 2B.

[0337] [Comparative Example 1] For Comparative Example 1, a polycarbonate resin (Yupilon S3000 manufactured by Mitsubishi Engineering Plastics Corporation) was used as the resin, and the glass transition temperature (Tg) and relative permittivity (ε) were determined. r The dielectric loss tangent (tanδ) and coefficient of thermal expansion (CTE) were measured in the same manner as described above. The results are shown in Table 2A.

[0338] [Comparative Example 2] The polymer was obtained by following the method described 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% by weight aqueous solution of cesium carbonate as a catalyst to a glass reactor equipped with a reactor stirrer, a reactor heating device, 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 concluded. The polycyanurate of the present invention having a repeating unit represented by formula (1) (Examples 1, 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, 6) exhibit superior 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, for thermal stability reasons, the polycyanurate of the present invention preferably contains as few cyclic oligomers as possible as by-products.

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

Claims

1. A molded article for communication equipment, which incorporates a microwave and / or millimeter-wave antenna, obtained using a thermoplastic resin composition, A molded article for communication equipment comprising a thermoplastic resin composition containing a polycyanurate having repeating units represented by the following formula (1) as the thermoplastic resin. 【Chemistry 1】 (In formula (1), Y １ Z represents a divalent organic group. １ This group is 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.

2. Said Z １ The molded article for communication equipment according to claim 1, wherein the group is selected from the group consisting of substituted or unsubstituted linear or branched alkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted amino groups, and substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms.

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

4. The dielectric loss tangent of the aforementioned polycyanurate is 4.5 × 10 －３ A molded body for communication equipment according to any one of claims 1 to 3, as follows:

5. The dielectric loss tangent of the aforementioned polycyanurate is 3.0 × 10⁻⁶ －３ The following is the molded body for communication equipment according to claim 4.

6. The dielectric loss tangent of the aforementioned polycyanurate is 1.5 × 10⁻⁶ －３ The following is the molded body for communication equipment according to claim 5.

7. The average linear expansion coefficient of the polycyanurate is 7.3 × 10⁻⁶. －５ A molded article for communication equipment according to any one of claims 1 to 6, wherein the temperature is below / ℃.

8. The average linear expansion coefficient of the polycyanurate is 7.0 × 10 －５ / °C or less, and the molded body for a communication device according to claim 7.

9. The average coefficient of linear expansion of the polycyanurate is 6.4 × 10⁻⁶. －５ A molded article for communication equipment according to claim 8, wherein the temperature is below / ℃.

10. The average coefficient of linear expansion of the polycyanurate is 5.5 × 10⁻⁶. －５ A molded article for communication equipment according to claim 9, wherein the temperature is below / ℃.

11. A molded article for communication equipment according to any one of claims 1 to 10, wherein the relative permittivity of the thermoplastic resin is 2.6 or less.

12. The molded article for communication equipment according to claim 11, wherein the relative dielectric constant of the thermoplastic resin is 2.5 or less.

13. A molded article for communication equipment according to any one of claims 1 to 12, 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, a low-elasticity agent, a diluent, an antifoaming agent, an ion trapping agent, a thickener, a leveling agent, inorganic particles, and organic particles.

14. A molded article for communication equipment according to any one of claims 1 to 13, which is formed by extrusion molding, injection molding, blow molding, vacuum molding, pressure molding, press molding, or casting film formation of the thermoplastic resin composition.

15. The communication equipment molded body according to any one of claims 1 to 14, wherein the communication equipment molded body is one selected from the group consisting of a sheet, a film, a printed circuit board, a coating, and a multilayer film incorporated into the communication equipment.

16. The molded body for communication equipment according to any one of claims 1 to 14, wherein the molded body for communication equipment is a thin-film transistor in which an insulating film, a encapsulant, and a gate electrode layer are stacked in that order.

17. The communication equipment molded body according to any one of claims 1 to 14, wherein the communication equipment molded body is a housing for communication equipment or a cover for a housing for communication equipment.

18. A molded body for a communication device according to any one of claims 1 to 17, wherein the communication device is a notebook computer, a tablet device, a smartphone, or a router device.

19. A communication device having a microwave and / or millimeter-wave antenna, obtained using a molded body for communication devices according to any one of claims 1 to 18.

20. A metal-clad laminate in which a film layer and a metal foil layer are laminated, A metal-clad laminate in which the film layer is a molded body for communication equipment according to any one of claims 1 to 18.

21. The molded article for communication equipment according to claim 1, wherein the total content of the cyclic oligomer represented by the following formula (51) and the cyclic oligomer represented by the following formula (52) in the polycyanurate is less than 5% by weight. 【Chemistry 2】 (In formulas (51) and (52), Y １ Z represents a divalent organic group. １ This 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), Y ２ (It is a divalent organic group having an alicyclic or aromatic ring.)

22. The molded article for communication equipment according to claim 21, wherein the glass transition temperature of the polycyanurate is 150°C or higher.

23. The dielectric loss tangent of the aforementioned polycyanurate is 4.5 × 10 －３ The following is the molded body for communication equipment according to claim 21 or 22.

24. The average coefficient of linear expansion of the polycyanurate is 7.5 × 10⁻⁶. －５ A molded article for communication equipment according to any one of claims 21 to 23, wherein the temperature is below / ℃.

25. A molded article for communication equipment according to any one of claims 21 to 24, wherein the content of the repeating unit represented by formula (1) in the thermoplastic resin composition is 10% by weight or more in the thermoplastic resin composition.

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