WO2015102302A1

WO2015102302A1 - Poly(cyclohexylenedimethylene terephthalate) copolymer having improved impact strength, discoloration resistance and reflexibility and resin molded product formed therefrom

Info

Publication number: WO2015102302A1
Application number: PCT/KR2014/012830
Authority: WO
Inventors: 이수민; 김종량; 김태영; 백지원; 이부연
Original assignee: 에스케이케미칼주식회사
Priority date: 2013-12-30
Filing date: 2014-12-24
Publication date: 2015-07-09
Also published as: KR102252792B1; KR20150079432A; TWI653260B; TW201527357A

Abstract

The present invention relates to a poly(cyclohexylenedimethylene terephthalate) copolymer and a resin molded product formed therefrom. The poly(cyclohexylenedimethylene terephthalate) copolymer according to the present invention has excellent intrinsic physical properties and enables the provision of a resin molded product having improved impact strength, discoloration resistance and reflexibility without special additives. The resin molded product can maintain excellent initial physical properties even in an environment in which heat and light are continuously supplied, and thus can be used appropriately for LED housings, reflectors, and the like.

Description

【Specification】

[Name of invention]

Poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer having improved impact strength, discoloration resistance and reflectivity and resin molded article formed therefrom

[Detailed Description of the Invention]

Technical Field

The present invention relates to a poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer having improved layer strength, discoloration resistance and reflectivity and a resin molded article formed therefrom.

Background Art

Poly (alkylene terephthalate) (Poly (alkylene terephthalate)) has excellent physical properties such as wear resistance, durability, thermal stability, and is widely used as a material for fibers, films, molded articles and the like. Such poly (alkylene terephthalate) is typically poly (ethylene terephthalate) (hereinafter referred to as 'PET'), poly (butylene terephthalate) (P y (butylene terephthalate), referred to as "ΡΒΤ" ), Poly (cyclonuylene dimethylene terephthalate) (Poly (1,4-cyclohexylenedimethylene terephthalate), hereinafter 'PCT') and the like have been commercialized.

The increasing PCT is attracting attention as a new material that can overcome the problems of polyester materials such as PET and PBT, namely, deterioration of moldability due to slow crystallization rate and limitation of use due to low thermal deformation silverness.

These PCTs are composed of terephthalic acid (ΤΡΑ ') or dimethyl terephthalate (, ΜΓ).

Ester of 1,4-cyclohexanedimethanol (hereinafter referred to as 'CHDM') or crystalline polyesters produced by transesterification and polycondensation reactions. Has a fast crystallization rate.

PCT has excellent heat resistance, chemical resistance, hygroscopicity, and flowability compared to general-purpose polyesters PET and PBT, among which heat deflection temperature7> 245 ~ 260 ^° C, continuous (continuous-use) temperature 7} 130 to 150 ^° C. has a characteristic. Accordingly, PCT is liquid crystalline Super engineering, the only non-wholly aromatic polyester commercialized except for polyester, means metal-substituted engineering plastics such as polyamide, polyphenylene sulfide, liquid crystalline polymer Belongs to plastic group.

These PCTs are used in electronic materials where surface mounting technology is advanced at high temperatures, or in light emitting diodes (LEDs) that are constantly exposed to heat and light while the product is in use _. It is applied to the use of a housing or a reflector.

In addition, as the field of application of PCT is gradually expanded, various methods for improving color, crystallization characteristics, and the like of PCT using various additives such as stabilizers and glass fibers have been proposed. However, since these methods are mostly related to compounds including PCT, they are not evaluated as a fundamental method for improving the physical properties of PCT.

[Content of invention]

[Problem to solve]

The present invention is to provide a poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer which enables the provision of a resin molded article having excellent discoloration resistance and reflectivity while having improved impact strength.

In addition, the present invention is to provide a resin molded article formed from the poly (cyclonuclear silane dimethylene terephthalate) copolymer.

[Measures of problem]

According to the invention,

A repeating unit represented by the following formula (1),

There is provided a poly (cyclonuylene dimethyl dimethylene terephthalate) copolymer comprising repeating units derived from a polysiloxane compound represented by the following formula (2):

[Formula 2]

In Chemical Formula 2,

R ¹ to R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms;

D ¹ and D ² are each independently a C1 to ^"20 aliphatic hydro car invoke, or cycloaliphatic having 4 to 10 carbon atoms dihydro car invoking gt;

L ¹ and L ² are each independently a hydroxy group or a hydroxy phenyl group;

n and m is an integer of from 5 to 300 _r each independently.

According to the invention, the repeating units derived from the polysiloxane compound may be included as 0.1 to 30 parts by weight ^_0/0 of the total weight of the copolymer.

GREE: TL, the poly (cyclonuclearylenedimethylene terephthalate) copolymer can have a weight average molecular weight of 10,000 to 100,000 and a number average molecular weight of 10,000 to 50,000.

Meanwhile, according to the present invention,

In the presence of a catalyst, mixing and diesterizing a diol compound, a dicarboxylic acid compound, and a polysiloxane compound represented by Formula 2; And a polycondensation reaction of the product obtained by the esterification reaction, provides a method for producing the poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer. According to the present invention, the esterification reaction is based on 100 parts by weight of a diol compound containing 1,4-cyclonucleic acid dimethane, a dicarboxylic acid compound containing terephthalic acid, dimethyl terephthalate or a mixture thereof 90 to 90 1 10 parts by weight, and may be carried out using a composition comprising 0.01 to 10 parts by weight of the polysiloxane compound.

And, if necessary, the composition for the esterification reaction, trimethyl phosphate (trimethyl phosphate), triethyl phosphate (triethyl phosphate), triphenyl phosphate (triphenyl phosphate), triethyl phosphono acetate (triethyl One or more phosphorus stabilizers selected from the group consisting of phosphonoacetate, phosphoric acid, and phosphorous acid may be further included in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the diol compound.

In addition, according to the present invention, the esterification reaction may be performed for 120 to 600 minutes under a temperature of 230 to 290 ^° C and a pressure of 0.01 to 3.0 kg / cm ² .

And, according to the present invention, the catalyst is titanium oxide, titanium chelate compound, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-butyl titanate, tetra-isobutyl titanate, and butyl-isopropyl It may be one or more titanium-based catalyst selected from the group consisting of titanate.

In addition, according to the present invention, the polycondensation reaction may be performed for 60 to 360 minutes under a temperature of 290 to 320 ^° C and a pressure of 0.1 to ZO torr.

On the other hand, according to this invention, the resin molded article formed from the said poly (cyclonuclear silane dimethylene terephthalate) copolymer is provided.

According to the present invention, the resin molded article may exhibit an impact strength (ASTM D256) of 20 J / m or more for a 1/8 "thick specimen at 25 ^° C.

In addition, the resin molded article may exhibit a physical property of Color L ^* -b ^* value is 95% or more compared to the initial value under the phase silver after standing for 48 hours at 140 ^° C.

As such, the resin molded article may exhibit physical properties of reflectance of at least 95% of the initial value at room temperature after leaving for 48 hours at 14 CTC.

Such a resin molded article can be used for the purpose of the housing or reflector for LED. Hereinafter, a poly (cyclonuylene dimethyl dimethylene terephthalate) copolymer according to specific embodiments of the present invention, a method for preparing the same, and a resin molded article formed therefrom will be described in more detail.

Prior to this, the terminology is for the purpose of describing particular embodiments only and is not intended to limit the present invention unless explicitly stated throughout this specification. And the singular forms used herein have the opposite meanings in which the phrases Unless indicated, it also includes plural forms. In addition, the meaning of "include" as used in the specification embodies a specific characteristic, region, integer, step, operation, element and / or component, and other specific characteristics, region, integer, step, operation, element, component and / or component. It does not exclude the presence or addition of groups.

I. PCT Copolymer

According to one embodiment of the present invention,

A repeating unit represented by the following formula (1),

Poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer comprising a repeating unit derived from a polysiloxane compound represented by the following formula (2)

'PCT ^ polymer') is provided:

In Chemical Formula 2,

D ¹ and D ² are each independently an aliphatic hydrocarbyl group having 1 to 20 carbon atoms, or an alicyclic hydrocarbyl group having 4 to 10 carbon atoms;

L ¹ and L ² are each independently a hydroxy group or a hydroxy phenyl group;

n and _m are each independently an integer of 5 to 300.

According to the continuous studies of the present inventors, after the esterification reaction using a diol compound and a dicarboxylic acid compound, the copolymer obtained through the polycondensation reaction by mixing the polysiloxane compound represented by the formula (2), the discoloration resistance and reflectivity It has been found that it is possible to provide a resin molded article having an excellent but especially improved laminar strength.

That is, the PCT copolymer is a copolymer including a basic repeating unit of the PCT as shown in Formula 1 and a repeating unit by a polysiloxane compound as shown in Formula 2. Such PCT copolymers have improved intrinsic properties compared to conventional PCTs, and thus are improved without additional additives, as compared to conventionally known PCT compounds (i.e., compositions comprising additives applied for the purpose of improving PCT and physical properties). It is possible to provide a resin molded article having physical properties (in particular, improved impact strength, discoloration resistance and reflectivity, etc.).

In the PCT copolymer of the above embodiment, the repeating unit of Chemical Formula 1 may include a diol compound (eg, 1,4-cyclohexanedimethane) and a dicarboxylic acid compound (eg, terephthalic acid, dimethyl terephthalate Or a mixture thereof) and the polycondensation reaction.

In the repeating unit of Formula 1, n is not particularly limited. However, according to an embodiment of the present invention, n may be 5 or more, preferably 5 to 300, or 5 to 200, or 5 to 150, or 5 to 100, which may be advantageous for securing physical properties of the PCT copolymer.

In addition, the polysiloxane compound represented by Formula 2 is polycondensed together with the reaction product of the esterification reaction of the diol compound and the dicarboxylic acid compound, and the repeating unit derived therefrom may be included in the copolymer.

In the polysiloxane compound of Formula 2, R ¹ to R ⁴ are each independently a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms. For example, R ¹ to R ⁴ are each independently an alkyl group such as methyl, ethyl, propyl or butyl; Or an aryl group such as a phenyl or naphthyl group, and the hydrogen atom included in the alkyl group and the aryl group is unsubstituted or substituted with an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and the like. Can be.

In the polysiloxane compound of Formula 2, D ¹ and D ² are each independently an aliphatic hydrocarbyl group having 1 to 20 carbon atoms, or an alicyclic hydrocarbyl group having 4 to 10 carbon atoms. For example, the D ¹ and D ² are each independently It may be an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms.

In addition, in the polysiloxane compound of Formula 2, L ¹ and L ² are terminal groups having a hydroxy group, and may each independently be a hydroxy group or a hydroxy phenyl group.

In Formula 2, m is 5 or more, preferably 5 to 300, or 5 to 200, or 5 to 150, or 5 to 100, and the expression of the effect of introducing the repeating unit derived from the polysiloxane compound and the PCT aerial It may be advantageous to secure the properties of the coalescence.

As a non-limiting example, the polysiloxane compound represented by Formula 2 may have a weight average molecular weight of 500 to 15,000, preferably 1,000 to 15,000, or 1,000 to 12,000, according to the introduction of repeating units derived from the polysiloxane compound. It may be advantageous to express the effect and to secure the physical properties of the PCT copolymer.

On the other hand, according to one embodiment, the repeating unit derived from the polysiloxane compound is 0.1 to 30 weight ⁰ /., Or 0.1 to 25 weight%, or 1 to 20 weight ⁰ / or 1 to 15 of the total weight of the copolymer it is preferably included in a weight ^_0/0. In other words, while expressing the effect of improving the stratification strength due to the introduction of the repeating unit derived from the polysilicon special compound, it is impossible to discharge from the inside of the reactor to the outside during the manufacturing process when the excessive amount of the repeating unit is included. Thus, the content ratio of the repeating unit is preferably adjusted in the above range.

Such poly (cyclonucleosildimethylene terephthalate) copolymers have a weight average molecular weight of 10,000 to 100,000, or 30,000 to 8,000; Having a number average molecular weight of 10,000 to 50,000, or 15,000 to 35,000 may be advantageous for the expression of suitable mechanical properties.

In addition, the poly (cyclonucleosildimethylene terephthalate) copolymer may have an intrinsic viscosity of 1.1 dl / g or less, or 0.5 to 1.0 dl / g, which may be advantageous for ensuring proper processability.

II. Method of Making PCT Copolymer

Meanwhile, according to another embodiment of the present invention, In the presence of a catalyst, a diol compound, a dicarboxylic acid compound, and the above formula. Mixing and esterifying the polysiloxane compound represented by 2; And

There is provided a method for producing the poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer comprising the step of polycondensation reaction of the product obtained by the esterification reaction.

According to one embodiment, the esterification reaction,

Dialkyl compounds containing 1,4-cyclonucleic acid dimethane and dicarboxylic acid compounds including terephthalic acid, dimethyl terephthalate or a mixture thereof can be mainly used.

In addition, the esterification reaction includes ethylene glycol, diethylene glycol,

Diol compounds such as 1,4-butanediol, 1,3-propane diol and neopentyl glycol; Isophthalic acid, naphthalene 2,6-dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, dimethylisophthalate, dimethyl naphthalene 2,6-dicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylate Dicarboxylic acid compounds such as may be used together. However, in order to ensure the intrinsic physical properties of the PCT copolymer, 80 mol% or more of 1,4- _cyclonucleic acid _{dimethane is} used as the diol compound, and terephthalic acid, dimethyl terephthalate or a _mixture thereof is used as the dicarboxylic acid compound. Preference is given to using at least 80 mol%.

And, in order to ensure the efficiency of the appropriate esterification reaction, the esterification reaction is 90 to 1 10 parts by weight, or 80 to 100 parts by weight, or 75 to 90 parts by weight of the dicarboxylic acid compound relative to 100 parts by weight of the diol compound It is preferably carried out using the composition comprising.

In this case, the polysiloxane compound may be mixed with 0.01 to 10 parts by weight, or 0.1 to 10 parts by weight, or 1 to 5 parts by weight based on 100 parts by weight of the diol compound used in the esterification reaction. That is, the polysiloxane, while fully expressing the effect of improving the stratification strength according to the introduction of repeating units derived from the polysiloxane compound, may include a problem that it may be impossible to discharge from the inside of the reactor to the outside during the manufacturing process when the excess amount of the repeating units is included. It is preferable that the addition amount of a compound is adjusted in the above-mentioned range.

And, the esterification reaction of the catalyst (preferably titanium-based catalyst) Can be performed in the presence. By way of non-limiting example, the titanium-based catalyst is titanium oxide, titanium chelate compound, tetra-n-propyl titanate, tetra-isopropyl titanate, tetra-n-butyl titanate, tetra-isobutyl titanate, and butyl- At least one compound selected from the group consisting of isopropyl titanate.

At this time, the titanium-based catalyst is preferably adjusted so that the content of the titanium element contained in the catalyst relative to the weight of the final PCT copolymer is 20 ppm or less. That is, while inducing an appropriate polycondensation reaction, the amount of the catalyst in consideration of the yellowing of the resin (increased color-b) due to side reactions or the decrease in molecular weight of the resin due to side reactions may be caused when the excess amount of the catalyst is added. Is preferably adjusted in the above-described range.

In addition, a phosphorus stabilizer may be further used in the esterification reaction to ensure thermal stability. Such phosphorus stabilizers include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonoacetate, phosphoric acid, and phosphorous acid. It may be one or more compounds selected from the group consisting of.

In addition, the phosphorus stabilizer may be included in an amount of 0.001 to 5 parts by weight, or 0.01 to 5 parts by weight, 0.01 to 1 part by weight, based on 100 parts by weight of the compound, in order to sufficiently express the effect of the addition of the stabilizer. have. Alternatively, the phosphorus stabilizer is preferably adjusted so that the content of phosphorus element included in the stable relative to the weight of the final PCT copolymer is 30 ppm or less. This is because when the content of the phosphorus-based stabilizer exceeds 30 ppm, the color of the copolymer may be deteriorated and the catalytic activity of the polycondensation reaction may be degraded, thereby affecting the reaction time and the degree of polymerization.

This esterification reaction can be carried out under conventional conditions, and preferably for 120 to 600 minutes under silver conditions of 230 to 290 ° C and pressure conditions of 0.01 to 3.0 kg / cm ² .

On the other hand, after the esterification reaction step, the step of polycondensation reaction for the product obtained by the esterification reaction can be performed. In one implementation example According to this, the polycondensation reaction can be carried out continuously with the esterification reaction. Here, the polycondensation reaction may be carried out under conventional conditions, preferably 60 to 360 minutes under a temperature of 290 to 320 ^° C and a pressure of 0.1 to 2.0 torr.

In addition, in the method of manufacturing a PCT copolymer according to the embodiment, a conventional resin processing process such as extruding the product of the condensation reaction to prepare pellets, and crystallizing the pellets to solid phase polymerization, may be necessary. May be included.

III. Resin molding

On the other hand, according to another embodiment of the present invention, there is provided a resin molded article formed from the above-mentioned poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer.

As the resin molded article is formed using the PCT copolymer, as compared with resin molded articles formed using conventionally known PCT compounds (i.e., compositions comprising PCT and additives applied for the purpose of improving physical properties), It can exhibit improved physical properties (particularly improved impact strength, discoloration resistance and reflectivity) without the additive of. .

Specifically, the resin molded article has a layer strength of 20 J / m or more, preferably 20 to 100 J / m, or 20 to 85 J / m, for a 1/8 "thick specimen at 25 ° C. (ASTM D256) Can be represented.

In addition, the resin molded article may exhibit excellent heat resistance and discoloration resistance after being left at 140 ^° C. for 48 hours at a Color L ^* -b ^* value of 95% or more compared to the initial value at room temperature.

In addition, the resin molded article has a reflectance of 450 nm or more after being left at 140 ° C. for 48 hours at 95% or more of the initial value at room temperature, and can maintain excellent reflectivity even in a poor environment.

Accordingly, such resin molded articles can be suitably used for applications such as housings for LEDs, reflectors for LEDs, and housings for various light emitting devices, which are continuously exposed to heat and light, and electronics for which surface mount technology is applied at high temperatures. It can also be applied to the field of materials. 【Effects of the Invention】

The poly (cyclonuclear silane dimethylene terephthalate) copolymer according to the present invention exhibits excellent intrinsic physical properties, thereby enabling the provision of a resin molded article having improved impact strength, discoloration resistance and reflectivity without additional additives. Such a resin molded article can maintain excellent initial properties even in an environment in which continuous heat and light are applied, and can be suitably used for applications such as a housing or reflector for an LED.

[Specific contents to carry out invention]

Hereinafter, preferred embodiments will be presented to aid in understanding the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

Example 1

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about-38 g of polydimethylsiloxane

(In the formula 2, R ¹ to R ⁴ are each methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxy group, Mw 2,253), and about 0.15 g of titanium oxide based catalyst (Sachtleben's Hombifast PC

15%) was added to the reactor, the temperature was raised to 280 ^° C for 3 hours at normal pressure and the esterification reaction was carried out.

Subsequently, the polycondensation reaction was carried out on the product obtained by the above esterification reaction under 30C C and 0.5 to 1 torr for 150 minutes to obtain a poly (cyclonuylene dimethyl dimethyl terephthalate) co-polymer (Mw 51,000 , Mn 25,000 and intrinsic viscosity 0.73 dl / g) were obtained. Example 2

About 46 kg of 1,4-cyclohexanedimethanol (trans 70%), about 36 kg terephthalic acid, about 8.7 g triethyl phosphate, about 911 g polydimethylsiloxane (the above formula

2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxy group, Mw 2,253, and about 4.1 g of titanium oxide catalyst (Sachtleben Hombifast PC, 15% catalytic increase effective Ti ratio) was added to the reaction vessel, and the esterification reaction was carried out while the temperature was raised to 280 ^° C for 3 hours at normal pressure. Subsequently, the polycondensation reaction was carried out for 150 minutes under the conditions of 300 ° C. and 0.5 to 1 torr with respect to the product obtained by the esterification reaction to obtain a poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer (Mw 53,225, Mn 23,945 and intrinsic viscosity 0.68 dl / g) were obtained. Example 3

Approximately 732 kg of 1,4-cyclohexanedimethano! (trans 70%), about 600 kg terephthalic acid, about 108 g triethyl phosphate, about 15.2 kg polydimethylsiloxane

(In Formula 2, R ^{1 To} R ⁴ Are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxy group, Mw 2,253), and about 35.8 g of titanium oxide Catalysts (Sachtleben's Hombifast PC, Effective Ti Ratio in Catalysts

15%) was added to the reaction vessel, and the esterification reaction was performed while raising the temperature to 280 ° C for 3 hours at normal pressure.

Subsequently, the product obtained by the esterification reaction was subjected to a condensation reaction for 150 minutes under the conditions of 30 C C and 0.5 to 1 torr, thereby obtaining a poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer (Mw 47,168). , Mn 21, 886 and intrinsic viscosity 0.64 dl / g) were obtained. . Example 4

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 19 g of polydimethylsiloxane

(In formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxy group, Mw 2,253), and about 0.15 g of titanium oxide based A catalyst (Sachtleben's Hombifast PC, 15% effective Ti ratio in the catalyst) was added to the reactor, and the esterification reaction was performed by raising the temperature to 280 ^° C for 3 hours at normal pressure.

Subsequently, the polycondensation reaction was carried out on the product obtained by the esterification reaction under a condition of 300 ° C. and 0.5 to 1 torr for 150 minutes to obtain a poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer (Mw 51, 295, Mn 24,549 and intrinsic viscosity 0.71 dl / g) were obtained. Example 5

About 1.7 kg of 1,4-cydohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 57 g of polydimethylsiloxane (In Formula 2, R ¹ to R ⁴ are each methyl, Compounds where D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxy group, Mw 2,253), and about 0.15 g of titanium oxide catalyst (Hmbifast PC from Sachtleben, 15% effective Ti ratio in the catalyst) It was added to the reaction vessel, the reaction was proceeded to an esterification reaction at normal pressure to 280 ^° C. for 3 hours.

. Subsequently, the polycondensation reaction was carried out on the product obtained by the esterification reaction under a condition of 300 ^° C. and 0.5 to 1 torr for 150 minutes to obtain a poly (cyclonuylene dimethyl dimethyl terephthalate) copolymer (Mw 49,985, Mn 23,750 and intrinsic viscosity 0.65 dl / g) were obtained. Example 6

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 57 g of polydimethylsiloxane

(In formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxy group, Mw 1,418), and about 0.15 g of titanium oxide catalyst (Sachtleben's Hombifast PC, effective Ti ratio in the catalyst

15%) was added to the reactor, the reaction temperature was raised to 280 ^° C for 3 hours at atmospheric pressure and the esterification reaction was carried out.

Then, 300 ° C. and about the product obtained by the esterification reaction

The polycondensation reaction was performed for 150 minutes on the conditions of 0.5-1 torr, and the poly (cyclonuylene dimethyl dimethylene terephthalate) copolymer (Mw 51,769, Mn 23,084, intrinsic viscosity 0.71 dl / g) was obtained. Example 7

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 57 g of polydimethylsiloxane (In Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxy group, Mw 2,253), and about 0.15 g of titanium oxide based The catalyst (Sachtleben's Hombifast PC, 15% effective Ti ratio in the catalyst) was added to the reactor, and the esterification reaction was performed while raising the temperature to 280 ^° C for 3 hours at normal pressure.

Subsequently, the polycondensation reaction was carried out on the product obtained by the esterification reaction under a condition of 300 ^° C. and 0.5 to 1 torr for 150 minutes to obtain a poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer (Mw 51, 622, Mn 22,106 and intrinsic viscosity 0.69 dl / g) were obtained. Example 8

(In Formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxy group, Mw 4,172), and about 0.15 g of titanium oxide based Catalyst (Sachtleben's Hombifast PC, Effective Ti Ratio in Catalyst

15%) was added to the reactor, and the esterification reaction was performed while raising the temperature to 28 CTC at normal pressure for 3 hours.

Subsequently, the product obtained by the esterification reaction was subjected to a polycondensation reaction for 150 minutes under conditions of 300 ° C. and 0.5 to 1 torr to obtain a poly (cyclonuylene dimethyl dimethyl terephthalate) copolymer (Mw 52,551, Mn 22,726 and intrinsic viscosity 0.70 dl / g) were obtained. Example 9

(In formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, L ¹ and L ² are each a hydroxy group, Mw 9,178), and about 0.15 g of titanium oxide bran ) A catalyst (Sachtleben's Hombifast PC, 15% effective Ti ratio in the catalyst) was added to the reactor and sublimed to 280 ^° C for 3 hours at atmospheric pressure. The esterification reaction proceeded.

Subsequently, the polycondensation reaction was carried out on the product obtained by the esterification reaction under a condition of 300 ° C. and 0.5 to 1 torr for 150 minutes to obtain a poly (cyclonuylene dimethyl dimethyl terephthalate) copolymer (Mw 49,016, Mn 21,627 and intrinsic viscosity 0.67 dl / g) were obtained. Comparative Example 1

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, and about 0.15 g of titanium oxide based catalyst (Hombifast PC from Sachtleben, effective Ti ratio in the catalyst 15 %) Was added to the reactor, and the esterification reaction was performed while raising the temperature to 280 ^° C for 3 hours at normal pressure.

Subsequently, the product obtained by the esterification reaction was subjected to a polycondensation reaction under a condition of 300 ° C. and 0.5 to 1 torr for 150 minutes to obtain a poly (cyclonuylene dimethyl dimethylene terephthalate—) (Mw 50,349, Mn 23,800 and intrinsic viscosity 0.65 dl / g) were obtained. Comparative Example 2

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, about 38 g of polytetramethyleneglycol, and about 0.15 g of titanium oxide based catalyst (Sachtleben! "Hombifast PC, catalytic increase effective Ti ratio 15%) was added to the reactor, and the esterification reaction was carried out at elevated temperature up to 280 ^° C for 3 hours at normal pressure.

Subsequently, the polycondensation reaction was carried out on the product obtained by the esterification reaction under a condition of 300 ° C. and 0.5 to 1 torr for 150 minutes to give a poly (cyclohexylenedimethylene terephthalate) (Mw 52,000, Mn 24,500 , Intrinsic viscosity 0.69 dl / g) was obtained. Comparative Example 3

About 46 kg of 4-cyclohexanedimethanol (trans 70%), about 36 kg of terephthalic acid, about 6.5 g of triethyl phosphate, and about 4.1 g of titanium oxide catalyst (Sachtleben's Hombifast PC, 15% effective Τί in catalyst) were charged into the reactor, and the temperature was raised to 280 ^° C for 3 hours at atmospheric pressure. The reaction proceeded. Subsequently, the product obtained by the esterification reaction was subjected to a condensation reaction for 150 minutes under conditions of 300 ° C. and 0.5 to 1 torr to obtain poly (cyclonuylene dimethyl dimethylene terephthalate) (Mw 48,637, Mn 22,406). , Intrinsic viscosity 0.67 dl / g) was obtained. Comparative Example 4

About 732 kg of 1,4-cyclohexanedimethanol (trans 70%), about 600 kg of terephthalic acid, about 108 g. Triethyl phosphate, and about 35.8 g of titanium oxide catalyst (Sachtleben's Hombifast PC, 15% effective Ti ratio in the catalyst) were added to the reactor, and the esterification reaction was performed by raising the temperature to 280 ^° C for 3 hours at normal pressure.

Subsequently, 300 ^° C. and about the product obtained with the esterification reaction

The polycondensation reaction was performed for 150 minutes on the conditions of 0.5-1 torr, and the poly (cyclonuylene dimethyl dimethylene terephthalate) (Mw 46,708, Mn 22,225, the intrinsic viscosity 0.66 dl / g) was obtained. Comparative Example 5

About 1.7 kg of 1,4-cyclohexanedimethanol (trans 70%), about 1.5 kg terephthalic acid, about 38 g of octamethylcyclotetrasiloxane, about 0.4 g of triethyl phosphate, and about 0.15 g of titanium oxide based catalyst (Hombifast PC from Sachtleben, catalyst in the ratio of the effective ^Ti, 15%) in half unggi and sikimyeo raised at normal pressure up to 3 hours 280 ^° C was carried out the esterification banung.

Subsequently, the product obtained by the esterification reaction was subjected to a polycondensation reaction for 150 minutes under conditions of 30C C and 0.5 to 1 torr, to obtain poly (cyclonuylene dimethyl dimethylene terephthalate) (Mw 48,000, Mn 23,000, Intrinsic viscosity 0.68 dl / g) was obtained. Comparative Example 6

Effective Ti ratio of 1, 4-cyclohexanedimethanol (trans 70 %), about 1.5 kg of terephthalic acid, about 0.4 g of triethyl phosphate, ^and, about 0.15 g of the titanium oxide-based catalyst (Sachtleben Corporation Hombifast PC, the catalyst of from about 1.7 kg 15%) was added to the reactor, and the esterification reaction was performed while raising the temperature to 280 ° C for 3 hours at normal pressure. Subsequently, the product obtained by the esterification reaction was subjected to a condensation reaction for 150 minutes under conditions of 300 ^° C. and 0.5 to 1 torr.

And about 57 g of polydimethylsiloxane (in formula 2, R ¹ to R ⁴ are each a methyl group, D ¹ and D ² are each a propylene group, and L ¹ and L ² are each a hydroxy group, Mw 2,253) Was added, and it stirred for 10 minutes, and obtained poly (cyclonuclear silane dimethylene terephthalate) resin composition (Mw28,158, Mn 13,743, intrinsic viscosity 0.47 dl / g). Test Example 1

Each PCT resin obtained in Examples and Comparative Examples was dissolved in o-chlorophenol at a concentration of 1.2 g / dl, and the intrinsic viscosity was measured using a Ubbelodhe viscous tube. At this time, the temperature of the viscosity tube is maintained at 35 ° C., the time taken for the solvent (s to vent) to pass through the interval between the inner sections ab of the viscosity tube (efflux time) and the time required for the solution to pass. When time is t ₀ , specific viscosity is defined as in Equation 1 below, and the intrinsic viscosity is calculated using Equation 2 below.

[Equation 1]

In Equation 2, A was 0.247 as Huggins constant, and c was 1.2 g / dl as the concentration value. Test Example 2 For each specimen prepared using the PCT resin obtained through the examples and comparative examples, the initial Color L -b ^* value at room temperature was measured according to the CIE LAB index. Then, the color L ^' -b ^' value over time after leaving the same specimen at 140 ^° C was measured, and the results are shown in Table 1 and Table 2.

CIE LAB indicator was used for color measurement. CIE LAB system is yellow to the human senses the colors - blue, green - ^"as defined by the color space coordinates, L ^'in the CIE based on the opposite saekseol such as red brightness value (from 0 to 100; 0 is black, 100 is white ), a ^' value is green-red ([+] is red based on 0, [-] is green), and b ^' value is yellow-blue ([+] is yellow based on 0, [-] is Blue).

Table 1 1

Test Example 3

Initial reflectance in the blue (450 nm) wavelength band was measured for the specimens prepared using the respective PCT resins obtained in Examples and Comparative Examples. In addition, the reflection on the blue (450 nm) wavelength over time after leaving the same specimen at 140 ^° C was measured, and the results are shown in Table 3 and Table 4.

Table 3

Test Example 4

Notched Izod was measured according to ASTM D256 under 25 ^° C. on a 1/8 "thick specimen prepared using each PCT resin obtained through Examples and Comparative Examples, and the results are shown in Table 5 below. Indicated. Table 5

Referring to Tables 1 to 5, the specimen using the PCT co-polymer according to the embodiments showed a high impact strength of 20 J / m or more, and has a layer strength of about 2 times improved compared to the specimen according to the comparative examples Confirmed. Furthermore, according to the embodiments

The specimen using PCT copolymer showed 95% or more of Cc) br L ^* -b ^* value and reflectance after aging, and it was confirmed that it can maintain high reflectance while maintaining excellent discoloration resistance compared to the comparative examples. It became.

In particular, the comparative example using the siloxane compound which does not contain a hydroxyl group at the terminal.

In the case of 5, it was confirmed that the effect of the addition of the siloxane compound was hardly observed because it did not cause reaction with the dicarboxylic acid compound.

In addition, in the case of Comparative Example 6 in which the polysiloxane compound was physically mixed after the polycondensation reaction, pyrolysis occurred during the mixing process, resulting in a problem that the molecular weight was lowered and the color was bad. In addition, when the polysiloxane is added in the compounding process, it was confirmed that the improvement of physical properties is not large due to the problem of dispersion.

Claims

[Patent Claims]

[Claim 1]

A repeating unit represented by the following formula (1),

Poly (cyclonuclear silane dimethylene terephthalate) copolymer comprising a repeating unit derived from a polysiloxane compound represented by the following formula (2):

[Formula 1]

[Formula 2]

In Chemical Formula 2,

D ¹ and D ² are each independently an aliphatic hydrocarbyl group having 1 to 20 carbon atoms or an alicyclic hydrocarbyl group having 4 to 10 carbon atoms;

L ¹ and L ² are each independently a hydroxy group or a hydroxy phenyl group;

n and m are each independently an integer of 5 to 300.

[Claim 2]

The method of claim 1,

The repeating unit derived from the said polysiloxane compound is a poly (cyclonucleodimethyldimethylene terephthalate) copolymer comprised from 0.1-30 weight ⁰ /. Of the total weight of a copolymer.

[Claim 3]

The method of claim 1, A poly (cyclonucleodimethyldimethylene terephthalate) copolymer having a weight average molecular weight of 10,000 to 100,000 and a number average molecular weight of 10,000 to 50,000.

[Claim 4]

The method of claim 1,

Poly (cyclonucleosildimethylene terephthalate) copolymers having an intrinsic viscosity of 1.1 dl / g or less.

[Claim 5]

In the presence of a catalyst, mixing and reacting a diol compound, a dicarboxylic acid compound, and a polysiloxane compound represented by Formula 2 below; And

A process for preparing the poly (cyclonuylene dimethyl dimethylene terephthalate) copolymer according to claim 1 comprising the step of polycondensing the product obtained by the esterification reaction:

In Chemical Formula 2,

L ¹ and L ² are each independently a hydroxy group or a hydroxy phenyl group;

m is an integer of 5 to 300.

[Claim 6]

The method of claim 5,

The esterification reaction is a diol compound containing 1,4-cyclonucleic acid dimethanol Poly (cyclo), which is carried out using a composition comprising 90 to 110 parts by weight of a dicarboxylic acid compound comprising terephthalic acid, dimethyl terephthalate or a mixture thereof, and 0.01 to 10 parts by weight of the polysiloxane compound, based on 100 parts by weight. Process for the preparation of nuxylenedimethylene terephthalate) copolymer.

5

[Claim 7]

The method of claim 6,

Compositions for the esterification reaction include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, triethyl phosphonoacetate, phosphoric acid, and ^ό ]. A process for producing a poly (cyclonuclear dimethyl dimethylene terephthalate) copolymer, wherein at least one phosphorus stabilizer selected from the group consisting of phosphoric acid is further contained in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the diol compound. .

15

[Claim 8]

The method of claim 5 wherein ^'

The esterification reaction is carried out for 120 to 600 minutes under a temperature of 230 to 290 ^° C and a pressure condition of 0.01 to 3.0 kg / cm ² , a method for producing a poly (cyclonuclear dimethyl dimethylene 20. terephthalate) copolymer.

[Claim 9]

The method of claim 5,

The catalyst is a group consisting of titanium oxide, titanium chelate compound, tetra-n-propyl 25 titanate, tetra-isopropyl titanate tetra-n-butyl titanate, tetra-isobutyl titanate, and butyl-isopropyl titanate A process for producing a poly (cyclonuclear silane dimethylene terephthalate) copolymer, which is at least one compound selected from.

30 [claim 10] The method of claim 5

The polycondensation reaction is carried out for 60 to 360 minutes under a temperature of 290 to 320 ^° C and a pressure condition of 0.1 to 2.0 torr, a method for producing a poly (cyclonuylene dimethyl dimethyl terephthalate) copolymer.

[Claim 1 _1], to polyester as claimed in claim 1 (cyclo nucleus xylene dimethylene terephthalate) resin molded article formed from the copolymer. [Claim 12]

The method of claim 1 1 wherein ^"

Under 25 ^° C 1/8 "Impact on the specimen thickness strength (ASTM D256) is 20 J / m or more resin molded article. [Claim ^13]

The method of claim Π,

Resin molded article whose Color L ^* -b ^* value is 95% or more of the initial value at room temperature after 48 hours ^at 140 ^° C. 【Claim 14】.

The method of claim 1,

Resin molded article having a reflectance of at least 95% of the initial value at room temperature after leaving for 48 hours ^at 140 ^° C. [Claim 15]

The method of claim 1,

Resin molded article used for LED housing or reflector.