TW202128825A - Polyester resin, polyester resin composition, and molded product thereof - Google Patents

Abstract

The present invention relates to a polyester resin, at least prepared from polymerization of a dicarboxylic acid component and a diol component. The dicarboxylic component contains terephthalic acid and/or a derivative thereof able to form an ester, the diol component contains 1,4-butanediol and a diol having a relatively short side chain. Relative to the total mass of the diol units in the polyester resin, the content of monomeric units originating from the 1,4-butanediol is 70-98 mol%, and the content of monomeric units originating from the diol having a relatively short side chain is 2-30 mon%. The melting point of the polyester resin is 185 DEG C or higher.

Description

Polyester resin, polyester resin composition and its molded products

The present invention relates to a polyester resin, a polyester resin composition and a molded product thereof with low dielectric loss.

With the rapid development of the microelectronics industry, the size of electronic parts tends to be miniaturized, and the wiring density of transistors has risen sharply. Negative effects such as signal interference between lines, resistance and capacitance (RC) delays, and increased heat generation per unit area of the circuit board Occurring, there is a demand for the development of high-efficiency, high-speed, low-energy consumption, and multi-functional electronic products. From a technical point of view, in order to meet the needs of high-speed data transmission brought about by the high frequency of communication, a high-performance substrate that can greatly reduce the loss of transmission signals is essential. Smaller dielectric loss is conducive to greatly reducing the signal loss in high-frequency communication propagation. Therefore, in order to reduce signal transmission loss, materials with low dielectric loss must be used for the substrate.

Recently, various polymer materials have been widely developed and researched as low-dielectric loss materials. Researches are mostly concentrated on polyimines, polyaryletherketones, polybenzoxazoles, liquid crystal polymers, etc. These materials have high mechanical strength because of the large number of aromatic rings in the main chain structure, but they have melting The problem is difficult to process. Therefore, there are requirements for the development of polyester resins with excellent melt processability and low dielectric loss.

In recent years, there has been a lot of research and development on polyester resins, but there are no reports on the use of copolymerization modification methods to reduce the dielectric loss of polyester resins.

Patent Document 1 (Chinese Patent Document CN102585180A) discloses a 2,3-butanediol modified polyester resin with high molecular weight and high glass transition temperature, but it has the problem of low crystallinity, so there is still a dielectric The problem of large loss.

Patent Document 2 (Chinese Patent Document CN101831057A) discloses a 1,3-butanediol modified polybutylene terephthalate/polytrimethylene terephthalate copolymer with good dyeing properties, but this modification Polyester resin has the problem of low crystallinity, so there is still the problem of large dielectric loss.

Patent Document 3 (Japanese Patent Document 2014-218652A) discloses a 2-methyl-1,3-propanediol modified polybutylene terephthalate resin with rapid melting properties, but the modified polyester resin is low Melting point and low crystallinity, so there is still the problem of large dielectric loss.

In view of the above-mentioned problems, the object of the present invention is to provide a polyester resin with low dielectric loss, a composition containing the polyester resin, and a molded product thereof.

After intensive research, the inventors found that by adjusting the monomer unit derived from 1,4-butanediol in the polyester resin and the side chain-containing monomer unit derived from the diol represented by the following formula 1 The content of the polyester resin can maintain the crystallinity of the polyester resin and suppress the molecular movement in the amorphous region, thereby preparing a polyester resin with small dielectric loss, and achieving the purpose of the present invention.

That is, in order to achieve the above-mentioned object, the present invention has the following configuration.

The polyester resin of the present invention is prepared by polymerizing at least a dicarboxylic acid component and a diol component; wherein the dicarboxylic acid component contains terephthalic acid and/or its ester-forming derivative, and the diol component contains 1, 4-butanediol and the diol represented by formula 1; relative to the total amount of monomer units derived from the diol component in the above-mentioned polyester resin, the content of monomer units derived from 1,4-butanediol is 70~ 98 mol%, the content of the monomer unit derived from the diol represented by Formula 1 is 2-30 mol%; the melting point Tm of the above-mentioned polyester resin is 185°C or higher. [Formula 1]

The above formula 1 satisfies any of the following conditions (A) to (D). (A): n is an integer from 1 to 4, R1 and R2 are hydrogen elements, and R3 is an aliphatic hydrocarbon group with 1 to 6 carbon atoms; (B): n is an integer from 0 to 4, R2 is a hydrogen element, and R1 and R3 are independently aliphatic hydrocarbon groups with 1 to 6 carbon atoms; (C): n is an integer from 1 to 4, R1 and R3 are hydrogen elements, R2 is independently a hydrogen element or an aliphatic hydrocarbon group with 1 to 6 carbon atoms, wherein at least one of R2 is a carbon number of 1~ 6 aliphatic hydrocarbon group; (D): n is 0, R1 is a hydrogen element, and R3 is an aliphatic hydrocarbon group with 2 to 8 carbon atoms.

In the present invention, the diol represented by the above formula 1, for example, the diol that satisfies the condition (A) includes 1,3-butanediol, 1,3-pentanediol, 1,3-hexanediol, 1 ,3-Heptanediol, 1,4-pentanediol, 1,5-hexanediol; diols satisfying condition (B) include 2,3-butanediol, 2,3-pentanediol, 2,3-hexanediol, 2,3-heptanediol, 2,3-octanediol, 3,4-hexanediol, 3,4-heptanediol, 3,4-octanediol, 4, 5-octanediol, 2,4-pentanediol, 2,4-hexanediol, 2,4-octanediol, 3,5-heptanediol, 2,5-hexanediol, 2,5- Heptanediol, 2,5-octanediol, 3,6-octanediol, 1,5-hexadiene-3,4-diol, etc.; diols satisfying condition (C) include 2-methyl -1,3-propanediol, 2-ethyl-1,3-propanediol, 2-propyl-1,3-propanediol, 2-isopropyl-1,3-propanediol, 2-methylene-1, 3-Propanediol; Diols satisfying condition (D) include 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2 -Octanediol, 1,2-decanediol, 3,3-dimethyl-1,2-butanediol, 7-octene-1,2-diol, 3-butene-1,2- Glycol and so on.

For the diol structure shown in Formula 1, if n is an integer of 5 or more, or for any of the conditions (A), (B), and (C), where R1, R2, and R3 of an aliphatic hydrocarbon group are used When any one of them has 7 or more carbon atoms, or when R3 is an aliphatic hydrocarbon group with 9 or more carbon atoms for condition (D), the crystallinity of the polyester resin will decrease, which will cause its dielectric loss to change. Big. N in Formula 1 that satisfies the condition (A) or (C) is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. N in Formula 1 that satisfies the condition (B) is preferably an integer of 0 to 3, and more preferably an integer of 0 to 2. In addition, with regard to Formula 1 satisfying any of the conditions (A), (B), and (C), any one of R1, R2, and R3 is preferably an aliphatic hydrocarbon group with 1 to 5 carbon atoms , More preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms. R3 in Formula 1 that satisfies the condition (D) is preferably an aliphatic hydrocarbon group having 2 to 6 carbon atoms, and more preferably an aliphatic hydrocarbon group having 2 to 4 carbon atoms.

The diol component used in the present invention contains 1,4-butanediol and the diol represented by Formula 1 above. In addition, as the diol component of the present invention, one or more selected from the diols listed below can also be included. Specifically, the following examples can be listed but not limited to the following examples: ethylene glycol, 1,3-propanediol , 1,5-pentanediol, 1,6-hexanediol, or aliphatic diols such as decanediol; 1,1-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,4 -Cyclohexane dimethanol, 1,4-dicyclohexane dimethanol, or tricyclodecane dimethanol and other alicyclic diols; benzene dimethanol, bis(p-hydroxy)biphenyl, bis(p-hydroxy)di Phenylpropane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl] ash, 1,1-bis[4- (2-Hydroxyethoxy)phenyl]cyclohexane, 4,4-dihydroxyp-terphenyl, or 4,4-dihydroxyp-tetraphenyl and other aromatic diols; the above-mentioned diols can also be acetone It is used in the form of a chemical compound or an alkali metal salt.

In the present invention, the content of the 1,4-butanediol-derived monomer unit is 70 to 98 mol% with respect to the total amount of the monomer unit derived from the diol component in the polyester resin. Further, from the viewpoint of improving the crystallinity of the polyester resin, the lower limit of the content of the 1,4-butanediol-derived monomer unit is preferably 80 mol% or more, and more preferably 85 mol% or more. On the other hand, from the viewpoint of reducing the dielectric loss tangent value, the upper limit is preferably 96 mol% or less.

Furthermore, in the present invention, the content of the monomer unit derived from the diol represented by the above formula 1 is 2 to 30 mol% with respect to the total amount of the monomer unit derived from the diol component in the above polyester resin. Further, from the viewpoint of suppressing the molecular mobility of the amorphous region, the content of the monomer unit derived from the diol represented by Formula 1 is preferably 4 mol% or more. On the other hand, from the viewpoint of maintaining the crystallinity of the polyester resin, its content is preferably 20 mol% or less, and more preferably 15 mol% or less.

The dicarboxylic acid component used in the present invention contains terephthalic acid and/or its ester-forming derivative. Examples of the ester-forming derivatives of terephthalic acid include: alcohol ester derivatives such as dimethyl terephthalate and diethyl terephthalate; terephthalic acid chloride and other ester-forming derivatives . In addition, as the dicarboxylic acid component of the present invention, one or more selected from the dicarboxylic acid components listed below and their ester-forming derivatives may be included. Specifically, the following examples may be mentioned but not limited to the following Examples: isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1, 5-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 4,4'-dicarboxydiphenylmethane, anthracene dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane Aromatic dicarboxylic acids such as dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfoisophthalic acid, monosodium 5-sulfoisophthalate or sodium 3-sulfoisophthalate Acid; 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, or 4,4'-dicyclohexyldicarboxylic acid and other alicyclic dicarboxylic acids ; Oxalic acid, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedione acid, dimer acid and other aliphatic dicarboxylic acids; corresponding to the above-mentioned dicarboxylic acids Alkyl diester and dichloride are also exemplified as monomer raw materials.

The content of monomer units derived from terephthalic acid and/or its ester-forming derivatives relative to the total amount of monomer units derived from the dicarboxylic acid component in the polyester resin obtained in the present invention is preferably 80~100mol%, when the content of the monomer units derived from terephthalic acid and/or its ester-forming derivatives is less than 80mol%, the crystallinity of the polyester resin will decrease and the dielectric loss of the polyester resin will occur The tendency to become bigger. In addition, the content of the monomer unit derived from terephthalic acid and/or its ester-forming derivative is preferably 90 mol% or more, and more preferably 95 mol% or more.

The polyester resin of the present invention is prepared from at least the above-mentioned dicarboxylic acid component and diol component, but in addition to the above-mentioned dicarboxylic acid component and diol component, as a monomer of the polyester resin, it may also contain selected from the following Monobasic acid and monohydric alcohol. Specific examples can be listed but not limited to the following examples: acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptanoic acid, n-octanoic acid, 2,2-dimethylpropionic acid, 3-methylbutanoic acid, 3 ,3-Dimethyl-1-butyric acid, 4-methylvaleric acid, 3,3-dimethylvaleric acid, 4-methylhexanoic acid, 2,4-dimethylvaleric acid, 3,5- Aliphatic monocarboxylic acids such as dimethylhexanoic acid and phenoxyacetic acid, and their derivatives capable of forming esters; benzoic acid, 4-methylbenzoic acid, 4-tert-butylbenzoic acid, 4-n-propoxy Aromatics such as methyl benzoic acid, 4-n-butoxy benzoic acid, 4-n-hexyloxy benzoic acid, 4-octyloxy benzoic acid, 4-phenyl benzoic acid, 4-benzyl benzoic acid, p-chlorobenzoic acid, etc. Monobasic carboxylic acids and their derivatives capable of forming esters; anhydrides of monobasic acids such as acetic anhydride and benzoic anhydride; monohydric alcohols such as butanol, cyclohexanol, and benzyl alcohol. The above monobasic acid or monohydric alcohol may be used alone or in combination of two or more kinds.

Derived from the above 1,4-butanediol and diol components other than the diol represented by formula 1, dicarboxylic acid components other than terephthalic acid and its ester-forming derivatives, monobasic acids, and monohydric alcohols The total content of monomer units in the polyester resin is preferably 15% by weight or less by weight, more preferably 10% by weight or less, and still more preferably 5% by weight or less.

The melting point (Tm) of the polyester resin of the present invention is 185°C or higher. In the present invention, the melting point of the polyester resin can be measured by the following method: using a differential scanning calorimeter in a nitrogen environment, the polyester resin is reduced from the molten state to 30°C at a temperature drop rate of 20°C/min, and then Keep the temperature for 2 minutes, and then increase the temperature at a temperature increase rate of 20°C/min, and measure the endothermic peak temperature that appears during the temperature increase process, which is the melting point of the polyester resin. From the viewpoint of heat resistance and melt processability, the melting point of the polyester resin is preferably 190°C or higher, and more preferably 195°C or higher. In addition, in the case where multiple endothermic peak temperatures occur during the above-mentioned heating process, the highest endothermic peak temperature is taken as the melting point.

In the present invention, the polyester resin in the present invention uses a differential scanning calorimeter in a nitrogen environment to reduce the temperature from the molten state to 30°C at a cooling rate of 20°C/min, and keep it at this temperature for 2 minutes, and then increase the temperature at a rate of 20°C/min. When the temperature is raised, the heat amount ΔHm of the endothermic peak that appears during the temperature rise process is preferably 30 J/g or more. If there are more than two endothermic peaks during the heating process, then the heat ΔHm is the sum of the two or more endothermic peaks. If ΔHm is less than 30 J/g, the crystallinity of the polyester resin decreases, and the dielectric loss tends to increase. Furthermore, ΔHm is preferably 35 J/g or more, and still more preferably 40 J/g or more.

In the present invention, the glass transition temperature of the polyester resin is preferably 41°C to 90°C. The above-mentioned glass transition temperature can be measured by the following method: using a differential scanning calorimeter in a nitrogen environment, the polyester resin is rapidly cooled from the molten state, and then the temperature is raised at a heating rate of 20°C/min. The measurement is performed during the heating process The glass transition temperature that occurs. When the glass transition temperature is less than 41°C, the mobility of the amorphous region of the polyester resin will increase, and the dielectric loss of the polyester resin will tend to increase. Furthermore, the lower limit of the glass transition temperature of the polyester resin of the present invention is preferably 42°C or higher, and more preferably 43°C or higher. On the other hand, when the glass transition temperature is higher than 90°C, the proportion of amorphous regions of the polyester resin becomes larger, resulting in a decrease in its crystallinity, and the dielectric loss of the polyester resin tends to become larger. The upper limit of the glass transition temperature is preferably 70°C or less, more preferably 60°C or less.

The dielectric loss tangent value of the polyester resin obtained in the present invention at a frequency of 5.8 GHz measured by the cavity resonance method is preferably 0.0060 or less, more preferably 0.0055 or less, and still more preferably 0.0051 or less.

The polyester resin of the present invention can be prepared by the following method: a raw material with a molar ratio of diol component to dicarboxylic acid component of 1.05 to 1.50 in a temperature range of 150 to 250 ℃, under normal pressure or reduced pressure conditions The esterification reaction or transesterification reaction is carried out below, and then the condensation reaction is carried out at a temperature of 240 to 270°C and a pressure of 500 Pa or less. The molar ratio of the diol component and the dicarboxylic acid component is controlled within the above-mentioned range, and the diol component represented by Formula 1 can be efficiently polymerized into the polyester resin. Further, the molar ratio of the diol component/dicarboxylic acid component is preferably 1.10 or more, more preferably 1.15 or more, on the other hand, the molar ratio is preferably 1.40 or less, and more preferably 1.30 or less.

In order to obtain a polyester resin with a high degree of polymerization, the above-mentioned condensation reaction time is preferably 100 minutes or more, and more preferably 110 minutes or more. On the other hand, in order to suppress thermal decomposition of the polyester resin, it is preferably 350 minutes or less, and more preferably 300 minutes or less.

In order to effectively carry out the esterification reaction, transesterification reaction and condensation reaction, it is better to add a polymerization catalyst during these reactions. Specific examples of polymerization reaction catalysis include: methyl titanate, tetra-n-propyl titanate, and tetra-n-butyl titanate. , Tetraisopropyl titanate, tetraisobutyl titanate, tetra-tertiary butyl titanate, cyclohexyl titanate, tetraphenyl titanate, tetrabenzyl titanate, tetramethylphenyl titanate, or Organic titanium compounds such as mixtures of these titanates, dibutyl tin oxide, methyl phenyl tin oxide, tetraethyl tin oxide, hexaethyl tin dioxide, cyclohexyl tin dioxide, didodecyl oxide Tin, triethyltin hydroxide, triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, butyltin trichloride, dibutyltin dichloride, three Tin compounds such as butyl tin chloride, dibutyl tin sulfide, butyl oxyhydroxide, alkyl stannic acid (such as methyl stannic acid, ethyl stannic acid, butyl stannic acid, etc.), zirconium compounds such as n-butoxide, Antimony compounds such as antimony trioxide and antimony acetate. From the viewpoints of promoting the polymerization reaction rate and inhibiting thermal degradation and side reactions during the reaction, organic titanium compounds and tin compounds are more preferred, and tetra-n-propyl titanate and tetra-n-butyl titanate are more preferred. And tetraisopropyl titanate, the most preferred is tetra-n-butyl titanate. The above-mentioned polymerization catalysts may be added singly or two or more of them may be added in combination. According to mechanical properties, formability and color requirements, relative to 100 parts by weight of the polyester resin, the addition amount of the polymerization catalyst is preferably 0.005 to 0.5 parts by weight, and more preferably 0.01 to 0.2 parts by weight.

In addition, the present invention also relates to a polyester resin composition containing the above-mentioned polyester resin. In addition, the above-mentioned polyester resin composition may further include a filler. The above-mentioned filler materials can include but are not limited to the following examples: glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber or Fibrous inorganic or organic filler materials such as metal fibers; wollastonite, zeolite, sericite, kaolin, mica, talc, clay, pyrophyllite, bentonite, montmorillonite, asbestos, silicate, alumina, silica, Magnesium oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride , Silicon carbide or silicon dioxide and other non-fibrous inorganic fillers. The filling material may be hollow. In addition, the filling material may be treated with a coupling agent such as an isocyanate compound, an organosilane compound, an organic titanate compound, an organoborane compound, or an epoxy compound. The above-mentioned montmorillonite may also be an organic montmorillonite in which the interlamellar ions are cation-exchanged by an organic ammonium salt. From the viewpoints of improving the mechanical properties of the polyester resin composition and reducing the molding shrinkage rate, the above-mentioned filler is preferably a fibrous inorganic filler, and more preferably glass fiber or carbon fiber. The cross-sectional shape of the fibrous filler is not particularly limited, and it may be circular or flat. In addition, the above-mentioned fillers can be added alone or two or more of them can be added in combination.

The above-mentioned polyester resin composition preferably contains the above-mentioned filler in a mixing amount of 0.1 to 150 parts by weight relative to 100 parts by weight of the polyester resin. The lower limit of the mixing amount of the filler is more preferably 1 part by weight or more, still more preferably 10 parts by weight or more, and still more preferably 30 parts by weight or more. On the other hand, the upper limit of the mixing amount of the filler is more preferably 100 parts by weight or less, and still more preferably 80 parts by weight or less.

The polyester resin composition of the present invention may also contain additives such as stabilizers, nucleating agents, antioxidants, mold release agents, flame retardants, and color master batches.

The above-mentioned stabilizer can be exemplified as phosphoric acid, trimethyl phosphate, triethyl phosphate, triethyl phosphinyl acetate, 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy )-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, tetrakis(2,4-di-tert-butyl-5-methylphenyl)[1 ,1-Biphenyl] -4,4'-diyl bisphosphonate and the like.

One or more of inorganic crystal nucleating agents and organic crystal nucleating agents can be used as the above-mentioned nucleating agent. The above-mentioned inorganic crystal nucleating agent may be exemplified by silica, alumina, zirconia, titania, wollastonite, kaolin, talc, mica, or silicon carbide.

In addition, the above-mentioned organic crystal nucleating agent may, for example, be an aliphatic carboxylic acid amide, a carboxylic acid metal salt, or a sorbitol-based derivative. Among the above-mentioned aliphatic carboxylic acid amides, for example, lauric acid amide, palmitic acid amide, oleic acid amide, stearic acid amide, erucic acid amide, ricinoleic acid amide, ricinoleic acid amide, etc. , Or aliphatic monocarboxylic acid amides such as hydroxystearate, N-oleyl palmitate, N-oleyl oleate, N-oleyl stearate, N-stearyl oleic acid amide, N-stearyl stearic acid amide, N-stearyl erucic acid amide, N-hydroxymethyl stearic acid amide, or N-hydroxymethyl sucrose N-substituted aliphatic monocarboxylic acid amides such as amides, methylene bisstearate amide, ethylene bislaurate amide, ethylene biscaprate amide, ethylene bisoleic acid Ethylene bis-stearic acid amide, ethylene bis-erucamide, ethylene bis-stearic acid amide, ethylene bis-isostearic acid amide, ethylene bis-hydroxystearic acid Acid amide, butylene bisstearate amide, hexamethylene bis oleic acid amide, hexamethylene bis behenate amide, hexamethylene bis behenate amide, hexamethylene bis Aliphatic dicarboxylic acid amides such as hydroxystearic acid amide, metaxylylene bisstearic acid amide, or metaxylylene bis-12-hydroxystearic acid amide, N,N' -Dioleyl sebacate amide, N,N'-dioleyl adipate amide, N,N-distearyl adipate amide, N,N'-distearyl decanoate N-substituted aliphatic carboxylic acid diamides such as diacid amides, N,N'-distearyl isophthalic acid amides, or N,N'-distearyl terephthalic acid amides , N-butyl-N'-stearyl urea, N-propyl-N'-stearyl urea, N-stearyl-N'-stearyl urea, N-phenyl-N'-hard Fatty urea, xylylene bisstearyl urea, tolyl bisstearyl urea, hexamethylene bisstearyl urea, diphenylmethane bisstearyl urea, or diphenylmethane bisstearyl urea, etc. The N-substituted ureas.

Examples of the above-mentioned carboxylic acid metal salts include sodium benzoate, potassium benzoate, lithium benzoate, calcium benzoate, magnesium benzoate, barium benzoate, lithium terephthalate, sodium terephthalate, and terephthalic acid. Potassium, calcium oxalate, sodium laurate, potassium laurate, sodium myristate, potassium myristate, calcium myristate, sodium octadecyl, calcium octadecyl, sodium stearate, hard Potassium stearate, lithium stearate, calcium stearate, magnesium stearate, barium stearate, sodium montanate, calcium montanate, sodium toluate, sodium salicylate, potassium salicylate, zinc salicylate , Aluminum dibenzoate, potassium dibenzoate, lithium dibenzoate, sodium naphthalate, sodium cyclohexanoate.

Examples of the above-mentioned sorbitol derivatives include bis(p-methylbenzylidene)sorbitol, bis(p-methylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, bis(p-chloro (Benzylidene)sorbitol, bis(p-bromobenzylidene)sorbitol, or sorbitol derivatives obtained by chemical modification of the above-mentioned sorbitol derivatives, etc.

Considering the effect of promoting the crystallization of the polyester resin, the nucleating agent is preferably silica, wollastonite, kaolin, talc, mica or aliphatic amide carboxylate. In addition, in the polyester resin composition of the present invention, the content of the nucleating agent is preferably 0.05 to 5 parts by weight relative to 100 parts by weight of the polyester resin. Within this range, the crystallization promotion effect can be maintained, and a polyester resin composition having excellent toughness can be obtained. Furthermore, the lower limit of the content of the nucleating agent is more preferably 0.1 part by weight or more. In addition, the upper limit is more preferably 3 parts by weight or less, and still more preferably 2 parts by weight or less.

The above-mentioned antioxidant is preferably at least one of a phenol-based antioxidant or a sulfur-based antioxidant. In order to obtain better heat resistance and thermal stability, it is preferable to use a phenolic antioxidant and a sulfur antioxidant in combination.

Among the above-mentioned phenolic antioxidants, for example, 2,4-dimethyl-6-tertiary butyl phenol, 2,6-di-tertiary butyl phenol, 2,6-di-tertiary butyl p-methyl Phenol, 2,6-di-tert-butyl-4-ethylphenol, 4,4'-butylene bis(6-tert-butyl-3-methylphenol), 2,2'-methylene bis (4-methyl-6-tertiary butylphenol), 2,2'-methylene-bis(4-ethyl-6-tertiary butylphenol), octadecyl-3-(3' , 5'-di-tert-butyl-4'-hydroxybenzene) propionate, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxybenzene)] propionate], 1,1 , 3-Tris(2-methyl-4-hydroxy-5-di-tert-butylphenyl)butane, tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, Triethylene glycol-bis[3-(3-tertiary butyl-4-hydroxy-5-methylbenzene) propionate], 1,6-hexanediol bis[3-(3,5-two third Butyl-4-hydroxyphenyl)propionate), 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3 ,5-Tris, 2,2-thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxybenzene) propionate], N,N'-hexamethylene bis( 3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 3,5-di-tert-butyl-4-hydroxybenzyl diethyl phosphonate, 1,3,5-trimethyl- 2,4,6-Tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2 , 4-bis[(octylthio)methyl] o-cresol, or isooctyl-3-(3,5-di-tert-butyl-4-hydroxybenzene) propionate, etc.

The sulfur-based antioxidants include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, and di(tridecyl)thiodipropionate. Dipropionate, pentaerythryl (3-lauryl thiopropionate), or 2-mercaptobenzimidazole, etc.

The above-mentioned antioxidants can be used alone, and at the same time, since the combination of two or more antioxidants will produce additive or synergistic effects, they can also be used in combination.

In the polyester resin composition of the present invention, the content of the antioxidant is preferably 0.01 to 3 parts by weight relative to 100 parts by weight of the polyester resin. Within this range, the anti-oxidation effect can be maintained while suppressing the generation of gas during melt processing. Furthermore, the lower limit of the antioxidant content is more preferably 0.05 parts by weight or more, and still more preferably 0.1 parts by weight or more. In addition, the upper limit is more preferably 2 parts by weight or less, and still more preferably 1 part by weight or less.

The above-mentioned mold release agent is not particularly limited, and any mold release agent used for general thermoplastic resins can be used. Specifically, fatty acids, fatty acid metal salts, hydroxy fatty acids, fatty acid esters, aliphatic partially saponified esters, paraffins, low molecular weight polyolefins, fatty acid amides, alkylene bis fatty acid amides, aliphatic ketones, Fatty acid lower alcohol esters, fatty acid polyol esters, fatty acid polyglycol esters, or modified polysiloxanes, etc.

The above-mentioned fatty acids are preferably fatty acids with 6 to 40 carbon atoms, specifically oleic acid, lauric acid, stearic acid, hydroxystearic acid, behenic acid, arachidonic acid, and linoleic acid , Linolenic acid, ricinoleic acid, palmitic acid, stearic acid, montanic acid, or their mixtures.

The fatty acid metal salt is preferably an alkali metal salt or alkaline earth metal salt of a fatty acid having 6 to 40 carbon atoms, specifically, calcium stearate, sodium montanate, or calcium montanate.

The above-mentioned hydroxy fatty acid may be exemplified by 1,2-hydroxy fatty acid and the like.

The above fatty acid esters may be exemplified as stearate, oleate, linoleate, linoleate, adipate, behenate, arachidonic acid, montanate, iso Stearic acid ester, or ester of polymeric acid, etc.

The aliphatic partially saponified ester may be, for example, montanic acid partially saponified ester.

The above-mentioned paraffin is preferably a paraffin having 18 or more carbon atoms, and can be exemplified by liquid paraffin, natural paraffin, microcrystalline wax, or petrolatum.

The low-molecular-weight polyolefins are preferably polyolefins with a weight average molecular weight of 5000 or less. Specifically, polyethylene waxes, maleic acid-modified polyethylene waxes, oxidized polyethylene waxes, chlorinated polyethylene waxes, Or polypropylene wax and so on.

The above-mentioned fatty acid amides are preferably fatty acid amides having 6 or more carbon atoms, and specific examples include oleic acid amides, erucic acid amides, or behenic acid amides.

The above-mentioned alkylene bis-fatty acid amides are preferably alkylene bis-fatty acid amides having 6 or more carbon atoms, and specific examples include methylene bis-stearyl amide, ethylene bis-stearyl amide, Or N,N-bis(2-hydroxyethyl)stearylamine, etc.

The above-mentioned aliphatic ketones may be exemplified by higher aliphatic ketones and the like.

The above-mentioned fatty acid lower alcohol esters are preferably fatty acid lower alcohol esters with 6 or more carbon atoms, specifically, ethyl stearate, butyl stearate, ethyl behenate, or rice wax, etc. .

The fatty acid polyol esters may be exemplified by glycerol monostearate, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol adipate stearate, dipentaerythritol adipate stearate, Or sorbitan monostearate and so on.

The fatty acid polyglycol ester may be exemplified by polyethylene glycol fatty acid ester or polypropylene glycol fatty acid ester.

The above-mentioned modified polysiloxanes can be exemplified by methyl styrene-based modified polysiloxanes, polyether modified polysiloxanes, higher fatty acid alkoxy modified polysiloxanes, and higher fatty acid-containing polysiloxanes. Silicone, higher fatty acid ester modified polysiloxane, methacrylic acid modified polysiloxane, or fluorine modified polysiloxane, etc.

The above flame retardants can be exemplified as bromine-based flame retardants, including decabromodiphenyl ether, octabromodiphenyl ether, tetrabromodiphenyl ether, tetrabromophthalic anhydride, hexabromocyclododecane , Bis(2,4,6-tribromophenoxy)ethane, ethylenebistetrabromophthalimide, hexabromobenzene, 1,1-sulfonyl[3,5-dibromo -4-(2,3-dibromopropoxy)]benzene, polydibromophenylene oxide, tetrabromobisphenol-S, tris(2,3-dibromopropyl) isocyanurate, Tribromophenol, tribromophenyl allyl ether, tribromoneopentyl alcohol, brominated polystyrene, brominated polyethylene, tetrabromobisphenol-A, tetrabromobisphenol-A derivatives, brominated ring Oxygen resins such as tetrabromobisphenol-A-epoxide oligomers or polymers and brominated phenol novolac epoxides, tetrabromobisphenol-A-carbonate oligomers or polymers, tetrabromobisphenol -A-bis(2-hydroxydiethyl ether), tetrabromobisphenol-A-bis(2,3-dibromopropyl ether), tetrabromobisphenol-A-bis(allyl ether), four Bromocyclooctane, ethylenebispentabromodiphenyl, tris(tribromoneopentyl) phosphate, poly(pentabromobenzyl polyacrylate), octabromotrimethylphenylindane, dibromide Neopentyl glycol, pentabromobenzyl polyacrylate, dibromotolyl glycidyl ether, or N,N'-ethylene-bis-tetrabromoterephthalimide, etc. In the present invention, the aforementioned flame retardant may also be exemplified as a chlorine-based flame retardant, including chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane, or tetrachlorophthalic anhydride, and the like.

The polyester resin of the present invention or the composition containing the polyester resin of the present invention can be molded by any molding method such as injection molding, extrusion molding, blow molding, vacuum molding, melt spinning, or film molding. A molded product with the desired shape.

The molded article of the present invention can be used as a mechanical structural component, an electrical component, an electronic component, an automobile component, etc. due to its good mechanical properties and heat resistance. Since the molded article of the present invention has excellent dielectric properties at high frequencies, it can be used particularly as a high-frequency communication transmission member.

Specific examples of mechanical structural components, electrical components, electronic components, and automotive components include: circuit breakers, electromagnetic switches, focus boxes, flyback transformers, fuser components such as copies and printers, general household electrical products, OA equipment, etc. Components, variable capacitors, various terminal boards, converters, printed circuit boards, housing protection components, terminal blocks, coil bobbins, connectors, relays, magnetic drive brackets, transformers, switch components, socket components, motor components, jacks , Plugs, concentrators, various housings, resistors, metal terminals and wire combination electrical and electronic components, computer-related components, sound components such as sound components, lighting components, telecommunication equipment-related components, telephone equipment-related components, and air-conditioning components , VTR, TV and other household appliances components, photocopy mechanism components, fax components, optical instrument components, automotive ignition components, automotive connectors, and various automotive electrical components.

High-frequency communication transmission components can include various resin components such as 5G communication industry, wireless communication industry, satellite communication, base station, navigation, medical treatment, transportation, warehouse, etc., in mobile communication terminals, communication base stations, millimeter wave sensors, Electrical and electronic components used in in-vehicle communication equipment, such as printed circuit boards, antenna base materials, connectors, frames, antenna housings, sensor housings, power amplifiers, power supply components, and high-frequency filters.

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited thereto.

The various properties of the polyester resins obtained in the examples and comparative examples were measured according to the following methods.

(1) Measurement of the content of the monomer unit derived from the diol component The polyester resin used in each example or comparative example was dissolved in deuterated HFIP (hexafluoroisopropanol) at a concentration of 30 mg/ml, Under the condition of 256 scans, JEOL ECX 400P was used for ¹ H-NMR nuclear magnetic test. _{The peaks corresponding to hydrogen on the methylene group (-CH 2} -O-) adjacent to oxygen in various structures in the ¹ H-NMR spectrum, and the main component of the polyester main chain repeating unit derived from p-benzene After assigning the peaks corresponding to hydrogen on the monomer unit of the dicarboxylic acid and/or its ester-forming derivative, the peak areas are obtained by integrating the peaks. The polyester resin is calculated based on the peak area corresponding to hydrogen on the monomer unit of the polyester main chain derived from terephthalic acid and/or its ester-forming derivative, and combined with the number of hydrogen atoms contained in each structure The content of various structural units in.

(2) Melting point (Tm) Using TA DSC-discover250 analytical instrument, accurately weigh about 5mg of the polyester resin sample prepared in the embodiment or comparative example, and measure it according to the following test conditions: under a nitrogen environment, the obtained polyester resin is heated at a rate of 20°C/min Raise the temperature from 30°C to 250°C to reach a fully molten state, keep it at this temperature for 2 minutes, then decrease the temperature to 30°C at a cooling rate of 20°C/min, and keep it at this temperature for 2 minutes. Next, the temperature is raised to 250°C at a heating rate of 20°C/min. The temperature of the endothermic peak observed during this heating process was taken as the melting point of the polyester resin.

(3) Heat of endothermic peak (ΔHm) Using the TA DSC-discover250 analytical instrument, accurately weigh about 5 mg of the polyester resin sample prepared in the embodiment or the comparative example, and perform the test according to the following conditions. In a nitrogen environment, the obtained polyester resin is heated from 30°C to 250°C at a heating rate of 20°C/min to reach a fully molten state, and kept at this temperature for 2 minutes, and then reduced to a temperature of 20°C/min. 30°C and keep it at this temperature for 2 minutes. Next, the temperature is increased to 250°C at a temperature increase rate of 20°C/min, and the heat amount ΔHm of the endothermic peak that appears during this temperature rise process is measured.

(4) Glass transition temperature (Tg) Using the TA DSC-discover250 analytical instrument, accurately weigh about 5 mg of the polyester resin sample prepared in the embodiment or the comparative example, and perform the test according to the following conditions. In a nitrogen environment, the obtained polyester resin is heated from 20°C to 250°C at a heating rate of 20°C/min to reach a fully molten state, and maintained at this temperature for 2 minutes, and then rapidly cooled from the molten state. The temperature is increased at a temperature increase rate of 20°C/min, and the glass transition temperature that occurs during the temperature increase process is measured.

(5) Dielectric loss tangent value (tanδ) Test sample: 1mm*30mm*0.5 obtained by injection molding the polyester resin obtained in the example or comparative example with the injection molding machine (TR30EHA) manufactured by Sodick Co., Ltd at a molding temperature of 250°C and a mold temperature of 80°C mm slender rectangular sample. Dielectric loss tangent value test: The cavity resonator CP521 manufactured by Agilent Technologies Co., Ltd./Kanto Electronics Co., Ltd. was used, and the dielectric loss tangent value measured under the condition of a frequency of 5.8 GHz.

The raw materials used in the examples and comparative examples are as follows: Diacid composition: Dimethyl terephthalate (DMT): TCI (Shanghai) Chemical Industry Development Co., Ltd. Terephthalic acid (TPA): Mitsui Chemicals Co., Ltd. Dimethyl 2,6-naphthalenedicarboxylate (DMN): Tishai (Shanghai) Chemical Industry Development Co., Ltd. Glycol composition: 1,4-Butanediol (1,4-BDO): Mitsubishi Chemical Corporation The glycol component that satisfies the condition (A) shown in Formula 1: 1,3-Butanediol (1,3-BDO): n=1, R3 is methyl; Tichiai (Shanghai) Chemical Industry Development Co., Ltd. 1,3-octanediol (1,3-ODO): n=1, R3 is n-pentyl; Tichiai (Shanghai) Chemical Industry Development Co., Ltd. The glycol component that satisfies the condition (B) shown in Formula 1: 2,5-Hexanediol (2,5-HDO): n=2, R1 is methyl, R3 is methyl; Tishai (Shanghai) Chemical Industry Development Co., Ltd. 2,5-Heptanediol (2,5-HPDO): n=2, R1 is methyl, R3 is ethyl; Tishai (Shanghai) Chemical Industry Development Co., Ltd. 2,3-Butanediol (2,3-BDO): n=0, R1 is a methyl group, R3 is a methyl group; Tichiai (Shanghai) Chemical Industry Development Co., Ltd. The diol component that satisfies the condition (C) shown in Formula 1: 2-Methyl-1,3-propanediol (2-M-1,3-PDO): n=1, R2 is methyl; Tichiai (Shanghai) Chemical Industry Development Co., Ltd. 2,3-Dimethyl-1,4-butanediol (2,3-2M-1,4-BDO): n=2, R2 is methyl; Tishai (Shanghai) Chemical Industry Development Co., Ltd. The diol component that satisfies the condition (D) shown in Formula 1: 1,2-Butanediol (1,2-BDO): R3 is ethyl; Tichia (Shanghai) Chemical Industry Development Co., Ltd. Other glycol components: Ethylene Glycol (EG): TCI (Shanghai) Chemical Industry Development Co., Ltd. 1,3-Propanediol (1,3-PDO): TCI (Shanghai) Chemical Industry Development Co., Ltd. 1,10-Decanediol (DDO): TCI (Shanghai) Chemical Industry Development Co., Ltd. 1,2-tetradecanediol (1,2-TDDO): TCI (Shanghai) Chemical Industry Development Co., Ltd.

catalyst: Tetrabutyl titanate (TBT): TCI (Shanghai) Chemical Industry Development Co., Ltd. Tin Butoxide (Ⅱ) Acid (MBO): Tichai (Shanghai) Chemical Industry Development Co., Ltd. Other additives: Antioxidant IR1010: BASF AG Phosphoric acid: Tishai (Shanghai) Chemical Industry Development Co., Ltd.

[Preparation Example 1]: Preparation of TBT catalyst solution 100g of 1,4-butanediol and 11.2g of n-tetrabutyl titanate were added to a 250ml three-necked flask with a condenser, and heated at 150°C for 3 hours in a nitrogen environment. [Preparation Example 2]: Preparation of BDO solution of phosphoric acid 100g of 1,4-butanediol and 11.2g of phosphoric acid were added to a 250ml three-necked flask equipped with a condenser and fully blended.

[Example 1] 0.640mol of dimethyl terephthalate (DMT, 124.3g), 0.691mol of 1,4-butanediol (1,4-BDO, 62.3g), 0.077mol of 1,3-butanediol ( 1,3-BDO, 7.0g), 0.733ml of the TBT catalyst solution of Preparation Example 1 was added to a 250ml three-necked flask reactor equipped with a rectification tower. Blow in nitrogen and start stirring, and the temperature is raised to 150°C. After the transesterification reaction starts under normal pressure, the temperature is slowly raised, and the transesterification reaction is carried out when the final temperature reaches 220°C. Add the TBT catalyst solution of Preparation Example 1 to the obtained prepolymer (addition of TBT: 0.050wt% relative to the quality of the final polyester resin), IR1010 (addition: 0.050wt% relative to the quality of the final polyester resin) . Then, the polycondensation reaction was carried out under the conditions of a temperature of 250°C and a pressure of 300 Pa or less. When the torque of the stirrer reaches the desired value, the polycondensation reaction is stopped, and the polyester resin is spit out.

[Example 2] Example 1 was repeated, except that 1,4-BDO was 0.653 mol and 1,3-BDO was 0.115 mol. The results are shown in Table 1.

[Example 3] Repeat Example 1, except that 1,4-BDO is 0.653 mol, and 1,3-BDO is replaced with 0.115 mol 1,3-ODO. The results are shown in Table 1.

[Example 4] Example 1 was repeated, except that 1,4-BDO was 0.768 mol, and 1,3-BDO was replaced with 0.192 mol of 2,5-HDO. The results are shown in Table 1.

[Example 5] Example 1 was repeated, except that 1,4-BDO was 0.768 mol, and 1,3-BDO was replaced with 0.192 mol of 2,5-HPDO. The results are shown in Table 1.

[Example 6] Example 1 was repeated, except that 1,3-BDO was replaced with 0.077 mol of 2-M-1,3-PDO. The results are shown in Table 1.

[Example 7] Repeat Example 1, except that 1,4-BDO is 0.653 mol, and 1,3-BDO is replaced with 0.115 mol of 2-M-1,3-PDO. The results are shown in Table 1.

[Example 8] Example 1 was repeated, except that 1,3-BDO was replaced with 0.077 mol of 2,3-2M-1,4-DO. The results are shown in Table 1.

[Example 9] Example 1 was repeated, except that 1,3-BDO was replaced with 0.077 mol of 1,2-BDO. The results are shown in Table 1.

[Example 10] Example 1 was repeated, except that 1,4-BDO was 0.653 mol, and 1,3-BDO was replaced with 0.115 mol of 1,2-BDO. The results are shown in Table 1.

[Example 11] Example 1 was repeated, except that 1,4-BDO was 0.614 mol, and 1,3-BDO was replaced with 0.154 mol of 1,2-BDO. The results are shown in Table 1.

[Example 12] Example 1 was repeated, except that 1,4-BDO was 0.499 mol, and 1,3-BDO was replaced with 0.269 mol of 1,2-BDO. The results are shown in Table 1.

[Example 13] Example 1 was repeated, except that DMT was 0.608 mol, DMN was 0.032 mol, 1,4-BDO was 0.653 mol, and 1,3-BDO was replaced with 0.115 mol of 1,2-BDO. The results are shown in Table 1.

[Example 14] Example 1 was repeated, except that DMT was 0.544 mol, DMN was 0.096 mol, 1,4-BDO was 0.653 mol, and 1,3-BDO was replaced with 0.115 mol of 1,2-BDO. The results are shown in Table 1.

[Example 15] Add 0.640mol of terephthalic acid (TPA, 106.2g), 0.749mol of 1,4-butanediol (1,4-BDO, 67.5g), MBO (addition amount: 0.042 relative to the final polyester resin quality) wt%) and IR1010 (addition: 0.019wt% relative to the final polyester resin quality) were added to a 250ml four-neck flask reactor equipped with a rectification tower. Blow in nitrogen and start stirring. After the temperature is raised to 100°C, the TBT catalyst solution of Preparation Example 1 (addition amount: 0.045wt% relative to the final polyester resin quality) is added. Raise the temperature, after 60 minutes of reaction, when the temperature is raised to 195℃, return to normal pressure with nitrogen and slowly add 0.083 mol of 1,2-butanediol (1,2-BDO, 7.5g) under a nitrogen flow of 50ml/min , And added within 60 minutes. The esterification reaction was carried out under the condition that the final temperature reached 233°C after the reaction for 200 minutes, and the reaction was terminated when the reaction liquid became transparent. The TBT catalyst solution of Preparation Example 1 (TBT addition amount: 0.050 wt% relative to the quality of the final polyester resin) was added to the obtained prepolymer, and the phosphoric acid solution of Preparation Example 2 (phosphoric acid addition amount: relative to the final polyester resin Quality 0.017wt%), IR1010 (addition: 0.021wt% relative to the final polyester resin quality). Then, the polycondensation reaction was carried out under the conditions of a temperature of 245°C and a pressure of 500 Pa or less. When the torque of the stirrer reaches the desired value, the polycondensation reaction is stopped, and the polyester resin is spit out.

[Comparative Example 1] Example 1 was repeated, except that 1,4-BDO was 0.768 mol, and 1,3-BDO was not added. The results are shown in Table 2.

[Comparative Example 2] Example 1 was repeated, except that 1,4-BDO was 0.422 mol, and 1,3-BDO was replaced with 0.347 mol of 1,2-BDO. The results are shown in Table 2.

[Comparative Example 3] Example 1 was repeated, except that 1,3-BDO was replaced with 0.077 mol of EG. The results are shown in Table 2.

[Comparative Example 4] Example 1 was repeated, except that 1,3-BDO was replaced with 0.077 mol of 1,3-PDO. The results are shown in Table 2.

[Comparative Example 5] Example 1 was repeated, except that 1,3-BDO was replaced with 0.077 mol of DDO. The results are shown in Table 2.

[Comparative Example 6] Example 1 was repeated, except that 1,4-BDO was 0.653 mol, and 1,3-BDO was replaced with 0.115 mol of 1,2-TDDO. The results are shown in Table 2.

[Comparative Example 7] Example 1 was repeated, except that 1,4-BDO was 0.320 mol, and 1,3-BDO was replaced with 0.320 mol of 2,3-BDO. The results are shown in Table 2.

[Comparative Example 8] Example 1 was repeated, except that 1,4-BDO was 0.192 mol, 1,3-BDO was 0.061 mol, and 0.515 mol of 1,3-PDO was added. The results are shown in Table 2.

[Comparative Example 9] Example 1 was repeated, except that 1,4-BDO was 0.960 mol, and 1,3-BDO was replaced with 0.320 mol of 2-M-1,3-PDO. The results are shown in Table 2.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Prepolymer preparation Diacid component DMT mol 0.640 0.640 0.640 0.640 0.640 0.640 0.640 0.640 0.640 0.640 0.640 0.640 0.608 0.544 - TPA mol - - - - - - - - - - - - - - 0.640 DMN mol - - - - - - - - - - - - 0.032 0.096 - Glycol composition 1,4-BDO mol 0.691 0.653 0.653 0.768 0.768 0.691 0.653 0.691 0.691 0.653 0.614 0.499 0.653 0.653 0.749 Diol component shown in formula 1 name 1,3-BDO 1,3-BDO 1,3-ODO 2,5-HDO 2,5- HPDO 2-M-1,3- PDO 2-M-1,3- PDO 2,3-2M- 1,4-BDO 1,2-BDO 1,2-BDO 1,2-BDO 1,2-BDO 1,2-BDO 1,2-BDO 1,2-BDO mol 0.077 0.115 0.115 0.192 0.192 0.077 0.115 0.077 0.077 0.115 0.154 0.269 0.115 0.115 0.083 Feed molar ratio of glycol component/diacid component - 1.2 1.2 1.2 1.5 1.5 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.3 TBT wt% 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.045 MBO wt% - - - - - - - - - - - - - - 0.042 IR1010 wt% - - - - - - - - - - - - - - 0.019 Polycondensation reaction TBT wt% 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 IR1010 wt% 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.021 Phosphoric acid wt% - - - - - - - - - - - - - - 0.017 Polycondensation reaction temperature °C 250 250 250 250 250 250 250 250 250 250 250 250 250 250 245 Polycondensation reaction pressure Pa 255 154 165 151 170 265 271 270 248 300 290 285 220 235 245 Resin physical properties Content of monomer units derived from 1,4-BDO mol% 92 87 89 91 89 90 85 90 95 91 86 71 91 91 92 The monomer unit content derived from the diol component shown in formula 1 mol% 8 13 11 9 11 10 15 10 5 9 14 29 9 9 8 Tm °C 213 206 207 211 206 210 199 210 215 209 200 186 201 197 210 ΔHm J/g 48 45 42 47 44 48 40 44 49 47 38 28 39 27 44 Tg °C 43 45 45 41 43 44 45 44 41 47 51 58 48 60 44 tanδ - 0.0052 0.0054 0.0059 0.0056 0.0057 0.0049 0.0055 0.0053 0.0052 0.0050 0.0053 0.0059 0.0053 0.0056 0.0052

[Table 2] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 Prepolymer preparation Diacid DMT mol 0.640 0.640 0.640 0.640 0.640 0.640 0.640 0.640 0.640 Glycol composition 1,4-BDO mol 0.768 0.422 0.691 0.691 0.691 0.653 0.320 0.192 0.960 Other glycol components name - - EG 1,3-PDO DDO 1,2-TDDO - 1,3PDO - mol - - 0.077 0.077 0.077 0.115 - 0.515 - Diol component shown in formula 1 name - 1,2-BDO - - - - 2,3-BDO 1,3-BDO 2-M-1,3-PDO mol - 0.347 - - - - 0.320 0.061 0.320 Feed molar ratio of glycol component/diacid component - 1.2 1.2 1.2 1.2 1.2 1.2 2.4 1.2 2.0 TBT wt% 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 Polycondensation reaction TBT wt% 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 IR1010 wt% 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 0.050 Polycondensation reaction temperature °C 250 250 250 250 250 250 250 250 250 Polycondensation reaction pressure Pa 235 270 271 271 269 176 176 176 265 Resin physical properties Content of monomer units derived from 1,4-BDO mol% 100 65 94 93 91 93 55 30 73 Monomer unit content derived from other glycol components mol% 0 0 6 7 9 7 0 62 0 The monomer unit content derived from the diol component shown in formula 1 mol% 0 35 0 0 0 0 45 8 27 Tm °C 224 179 217 217 211 205 - 175 179 ΔHm J/g 52 14 42 47 43 32 - 8 28 Tg °C 40 61 43 41 38 43 65 30 30 tanδ - 0.0068 0.0082 0.0068 0.0072 0.0071 0.0073 0.0121 0.0130 0.0066

In Table 1 and Table 2, Examples 1 to 12 and Comparative Example 1 illustrate the dielectric loss tangent value of a polyester resin containing a specific amount of monomer units derived from a diol with a side chain shown in Formula 1. smaller. Example 1 and Comparative Example 6 illustrate that the polyester resin with a longer side chain diol unit has a larger dielectric loss tangent value. Examples 9 to 12, Example 15 and Comparative Example 2 demonstrated that for polyester resins, when the content of the monomer unit derived from the diol represented by Formula 1 is too large, the dielectric loss tangent value cannot be reduced. Comparative Examples 3 to 5 illustrate that polyester resins containing linear diol units other than 1,4-butanediol units have relatively large dielectric loss tangent values. Examples 6 and 7 and Comparative Example 9 show that the dielectric loss tangent value becomes significantly larger when the melting point is lower.

Claims (7)

A polyester resin prepared by polymerizing at least a dicarboxylic acid component and a diol component; wherein the dicarboxylic acid component contains terephthalic acid and/or its ester-forming derivatives, and the diol component Contains 1,4-butanediol and the diol represented by the following formula 1; a monomer derived from 1,4-butanediol relative to the total amount of monomer units derived from the diol component in the polyester resin The content of the unit is 70 to 98 mol%, and the content of the monomer unit derived from the diol represented by the following formula 1 is 2 to 30 mol%; the melting point Tm of the above-mentioned polyester resin is 185°C or higher, [Formula 1]

The above formula 1 satisfies any one of the following conditions (A) to (D), (A): n is an integer from 1 to 4, R1 and R2 are hydrogen elements, and R3 is an aliphatic hydrocarbon group with 1 to 6 carbon atoms; (B): n is an integer from 0 to 4, R2 is a hydrogen element, R1 and R3 are independently aliphatic hydrocarbon groups with 1 to 6 carbon atoms; (C): n is an integer from 1 to 4, R1 and R3 are Hydrogen element, R2 is independently hydrogen element or an aliphatic hydrocarbon group with 1 to 6 carbon atoms, wherein at least one of R2 is an aliphatic hydrocarbon group with 1 to 6 carbon atoms; (D): n is 0, R1 is Hydrogen element, R3 is an aliphatic hydrocarbon group with 2-8 carbon atoms. The polyester resin according to claim 1, wherein the monomer units derived from terephthalic acid and/or ester-forming derivatives relative to the total amount of monomer units derived from the dicarboxylic acid component in the polyester resin The body unit content is 80-100 mol%. The polyester resin of claim 1, wherein the above polyester resin is reduced from the molten state to 30°C at a temperature drop rate of 20°C/min using a differential scanning calorimeter in a nitrogen environment, and then at a temperature rise rate of 20°C/min The amount of heat ΔHm of the endothermic peak that appears during the temperature increase measured is 30 J/g or more. Such as the polyester resin of claim 1, wherein the above-mentioned polyester resin has a dielectric loss tangent value of less than 0.0060 as measured by the cavity resonance method at a frequency of 5.8 GHz. A preparation method of the polyester resin according to any one of claims 1 to 4, characterized in that it comprises the following steps: the raw material with the molar ratio of the diol component/dicarboxylic acid component of 1.05 to 1.50 in 150 to 250 In the temperature range of ℃, the esterification reaction or the transesterification reaction is carried out under normal pressure or reduced pressure, and then the condensation reaction is carried out at a temperature of 240~270℃ and a pressure below 500Pa. A polyester resin composition comprising a filler material in a mixing amount of 0.1 to 150 parts by weight relative to 100 parts by weight of the polyester resin in any one of claims 1 to 4. A molded product made from the polyester resin of any one of claims 1 to 4 or the polyester resin composition of claim 6.