KR102396242B1 - Polyester resion for preparing cation dyeable PET and Cation dye-PET composite resin containing the same - Google Patents

Abstract

The present invention relates to a polyester resin and a CD (cation dye)-PET composite resin using the same. It relates to the manufactured CD-PET composite resin and CD-PET fibers, yarns, circular knitted fabrics, etc., which have excellent dyeing rate of cationic dyes manufactured using the same.

Description

Polyester resin for preparing CD-PET and CD-PET composite resin containing the same

The present invention provides a CD-PET composite resin manufactured using a polyester resin and a recycled PET (polyethyleneterephthalate) resin, and a polyester resin for CD-PET manufacturing that enables cationic dyeing when manufacturing fibers and/or yarns using the same, and It relates to fibers and/or yarns dyed with cationic dyes, circular knitted fabrics, and the like.

In general, as a method for producing a cationic dyeable fiber, a known modifier capable of ion bonding with a cationic dye (cation dye) is used in the production of polyester fibers with terephthalic acid (TPA) and ethylene glycol (EG). and EG to directly esterify.

In order to impart cationic dyeing properties to modified polyester products, for example, recycled polyester, flame-retardant polyester, high shrinkage polyester, and polyester having a high concentration of TiO ₂ content, a modifier is added to each polymerization process for transesterification. It must be prepared by reaction.

In order to produce general recycled polyester, first, ethylene glycol (EG) is added to the flake manufactured in the bottle, melted at 180 ° C. ~ 240 ° C., and then a glycolysis reaction is sent under nitrogen pressure to After manufacturing bishydroxyethyl terephthalate), recycled polyester is manufactured through a polycondensation reaction. Here, DMS input to enable cationic dyeing has to be added during the polyification reaction because nitrogen pressurization is performed during the ES reaction. have to do Due to such a process, since the amount of DEG (Diethylene glycol) generated is higher than that of the existing cationic dyeable polyester products, there is a problem in that spinning operability and dyeability after final dyeing are different.

In addition, in the case of general polyester, since there is no site for ionic interaction with the ionic dye, only the dye is dispersed and dyed. Dispersed dyes cannot provide bright and dark colors, and also have relatively poor fastness to sublimation treatment.

Cationic dyeable polyesters (CD-PET) are generally prepared by copolymerization using the sodium salt of 5-sulfoisophthalic acid (Na-SIPA) as a cationic co-monomer, and are prepared by copolymerization of cationic dyes for fibers and filaments. enable use.

Na-SIPA (sodium 5-sulfo-isophthalic acid) used in the production of CD-PET has acidic properties, which increases the formation of diethylene glycol (DEG) in the polyethylene terephthalate esterification step, thereby lowering the melting point and increasing the acidity. Due to its properties, it is difficult to prepare a fiber by promoting TiO ₂ agglomeration. In order to solve this problem, there is an attempt to solve the problem by giving bis (hydroxyl ethyl) isophthalate-5-sulfonate, that is, DMS in the form of an oligomer in which DMS is first reacted with EG, at the end or start of the esterification step, During the preparation of bis(hydroxyethyl)isophthalate-5-sulfonate, there is a problem of poor spinability due to the formation of trimers, tetramers and oligomers.

In particular, in order to produce a regenerated polyester resin that can be dyed with cationic dye, BHT is generated by glycolysis depolymerization under nitrogen pressure with flakes supplied from the bottle in the esterification polymerization step, and then in the polypolymerization step. Bis (hydroxyethyl) isophthalate-5-sulfonate must be added, but as mentioned above, the amount of DEG generated increases, which leads to problems with poor spinning performance due to lowering of the melting point and formation of oligomers.

As such, in the case of modified copolyester, that is, flame-retardant polyester, polyester containing high concentration of TiO ₂ , polyester with latent crimping performance, and recycled polyester, the amount of DEG generated increases when DMS is applied to enable cationic dye dyeing. Or, aggregation with TiO ₂ occurs due to acidity, or it cannot be added during the ester reaction and must be added only in the form of bis (hydroxyethyl) isophthalate-5-sulfonate. will be accompanied by

In order to improve the above problems, it is possible to manufacture CD-PET fibers and recycled CD polyester by applying a composite resin (or masterbatch) for manufacturing CD-PET fibers. Application No. 10-2019-7009748 describes a modified polyester masterbatch for textile applications and a method for preparing the same. It relates to a polyester masterbatch selected from aromatic and/or aliphatic dicarboxylic acids, and describes a method for polycondensation by adding polyglycol having a maximum molecular weight with up to 40% DMS. However, when polyols such as polyethylene glycol of high concentration and high molecular weight are added, moisture adsorption increases in the chip drying process for manufacturing CD-PET, causing problems such as yarn breakage and unwinding.

Korean Patent Publication No. 10-2019-0076960 (published on July 2, 2019) Korean Patent Publication No. 10-2010-0073419 (published on July 1, 2010)

The present invention was devised in consideration of the above problems, and the optimal composition and composition ratio of the polyester resin for CD-PET production, which can ensure excellent dyeability of cationic dyes for recycled PET resins, was completed to complete the present invention. became The CD-PET resin prepared by using the polyester resin for producing CD-PET can minimize the moisture adsorption rate, and can provide a yarn with an improved cationic dye dyeing rate. That is, the present invention is to provide a polyester resin for producing CD-PET, a CD-PET resin including the same, and a yarn manufactured using the same.

The polyester resin for producing CD (cation dye)-PET of the present invention is a polymer obtained by polycondensation of an ester compound obtained by esterifying an acid component and a diol component, wherein the acid component is a compound represented by the following Chemical Formula 1, a fatty acid and a carboxylic acid Including, the diol component is ethylene glycol (EG); or a glycol mixture comprising a linear glycol and a pulverized glycol represented by the following formula (2).

[Formula 1]

In Formula 1, R ¹ and R ² are each independently a C ₁ to C ₅ linear alkyl group or a C ₃ to C ₅ pulverized alkyl group, and K is a monovalent cation.

[Formula 2]

In Formula 2, each of R ¹ and R ⁴ is independently a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₅ alkylene group, a C ₅ to C ₆ cycloalkyl group or a phenyl group, R ² and Each of R ³ is independently a C ₁ to C ₅ alkylene group, with the proviso that R ¹ and R ⁴ are both hydrogen atoms, except for the case.

In a preferred embodiment of the present invention, the acid component may include 7 to 15 mol% of the compound represented by Formula 1, 7 to 10 mol% of the fatty acid, and the remainder of the carboxylic acid.

As a preferred embodiment of the present invention, the fatty acid may include at least one selected from adipic acid, succinic acid, and glutaric acid.

As a preferred embodiment of the present invention, the carboxylic acid may be at least one selected from C ₆ to C ₁₄ aromatic polyvalent carboxylic acid and C ₂ to C ₁₆ aliphatic polyvalent carboxylic acid.

As a preferred embodiment of the present invention, the C ₆ to C ₁₄ aromatic polyhydric carboxylic acid may include terephthalic acid alone, or two types of terephthalic acid and isophthalic acid.

As a preferred embodiment of the present invention, the glycol mixture among the diol components may include 4 to 10 mol% of the pulverized glycol and the remaining amount of the linear glycol.

As a preferred embodiment of the present invention, the straight-chain glycol may include C ₁ to C ₅ straight-chain glycol.

As a preferred embodiment of the present invention, the polyester resin for producing CD-PET of the present invention may be a polymer having a polymerization degree of 120 to 180.

As a preferred embodiment of the present invention, the polyester resin for producing CD-PET of the present invention has an intrinsic viscosity of 0.40 to 0.80 dl/g, a glass transition temperature (Tg) of 58°C to 75°C, and a melting temperature (Tm) It may be 180 ℃ ~ 220 ℃.

Another object of the present invention is to provide a masterbatch chip for producing CD-PET comprising the above-described polyester resin for producing CD-PET.

In addition, another object of the present invention is a CD-PET composite resin, including the aforementioned polyester resin and PET resin for producing CD-PET.

In a preferred embodiment of the present invention, the CD-PET composite resin may include 10 to 35% by weight of the polyester resin and the remaining amount of the PET resin.

In a preferred embodiment of the present invention, the PET resin among the CD-PET composite resin components may include recycled PET resin derived from waste products.

Another object of the present invention is to provide a CD-PET fiber and/or a CD-PET yarn manufactured using the CD-PET composite resin.

In a preferred embodiment of the present invention, the CD-PET fiber may include a CD-PET resin, a cation dye, and an additive.

As a preferred embodiment of the present invention, the CD-PET fiber is a yarn in which the PET fiber prepared from the CD-PET composite resin is dyed with a cationic dye, and the fiber dyed with the cationic dye has a surface dye concentration (K /S) 9.0 ~ 15.0 can be satisfied.

Another object of the present invention is to provide a circular knitted fabric comprising the CD-PET fiber and/or the CD-PET yarn.

Another object of the present invention relates to a method for manufacturing the CD-PET fiber and/or CD-PET yarn, comprising a chip containing the above-described various types of CD-PET manufacturing polyester resin and a non-ionic PET resin. Step 1 of preparing each chip; a second step of forming fibers by mixing the masterbatch in which the chip containing the polyester resin is melted and the resin in which the chip containing the nonionic PET resin is melted and spinning with a spinneret; And after dyeing the fiber with cationic dye, the third step of reducing washing; by performing a process comprising a CD-PET fiber and / or yarn can be prepared.

As a preferred embodiment of the present invention, the cationic dye may include at least one selected from Kayacryl yellow 3RL, Kayacryl Red GRL, and Kayacryl Blue GSL.

In a preferred embodiment of the present invention, the spinning may be performed under a temperature of 250 ~ 330 ℃ and a spinning speed of 1,500 ~ 4,500 MPM.

The polyester resin for cation dye-polyethyleneterephthalate (CD-PET) fiber production of the present invention can greatly increase the dyeing rate when a cation dye is added to a fiber and/or yarn manufactured using a recycled PET resin regenerated from waste PET. It is possible to increase the properties of the yarn by controlling the moisture content.

1 is a schematic diagram of a process for producing fibers and/or yarns by mixing and spinning a molten polyester resin (master batch) for producing CD-PET and recycled PET resin.

Hereinafter, the present invention will be described in more detail.

Fibers manufactured using recycled PET resin from recycled PET had a problem with a very low dyeing rate for cationic dyes. was used, but there was a problem in that the productivity was very low or the physical properties of the fibers manufactured using the recycled PET resin were lowered.

When manufacturing fibers using recycled PET resin, mixing and spinning the polyester resin for CD-PET production of the present invention (hereinafter referred to as “PE resin” or “master batch”) prevents deterioration of the physical properties of the fiber while preventing degradation of cationic dyes. It relates to an invention capable of increasing the dyeing rate.

The PE resin of the present invention includes a polymer obtained by polycondensation of an ester compound obtained by esterifying an esterification product, and the esterification product includes an acid component and a diol component.

In addition, the acid component of the ester compound includes a compound represented by the following Chemical Formula 1, a fatty acid, and a carboxylic acid.

[Formula 1]

In Formula 1, R ¹ and R ² are each independently a C ₁ to C ₅ linear alkyl group or C ₃ to C ₅ pulverized alkyl group, preferably a C ₁ to C ₅ linear alkyl group, More preferably, it is a C ₁ ~ C ₃ straight-chain alkyl group. And, K is a monovalent cation, preferably Na ⁺ or K ⁺ .

The content of the compound represented by Formula 1 among the total mol% in the acid component may include 5 to 15 mol% (mol%), preferably 6 to 13 mol%, more preferably 7 to 12 mol%, , If the compound represented by Formula 1 contains less than 5 mol%, an excess of master batch (or PE resin) must be added to enable cationic dye expression when preparing CD-PET composite resin for fiber or yarn production If it is used in excess of 15 mol%, the molecular weight of the polymer (or PE resin) is too high and there may be a problem of rapid viscosity increase, so it is better to use it within the above range.

In addition, the fatty acid of the acid component may include at least one selected from adipic acid, succinic acid, and glutaric acid, preferably adipic acid. The amount of fatty acid used in the total mol% in the acid component is 7 to 10 mol%, preferably 7.2 to 9.5 mol%. At this time, if the fatty acid content is less than 5 mol%, it is impossible to control the increase in the viscosity of the polymer, so there is a problem that the polymerization reaction is terminated without meeting the intrinsic viscosity (IV) of 0.40 ~ 0.80 dl/g level of the PE resin to be prepared. When the fatty acid content exceeds 10 mol%, the glass transition temperature (Tg) and melting temperature (Tm) of the PE resin are too low to chip the PE resin, and then, when manufacturing the fiber or yarn, the chip melting and discharging process Discharge failure may occur during medium discharging, and when the PE resin is chipped, it has to be dried at a low temperature of 60° C. or less for a long time, so drying operability is poor.

Among the acid components, the carboxylic acid may include at least one selected from C ₆ to C ₁₄ aromatic polyvalent carboxylic acid and C ₂ to C ₁₆ aliphatic polyvalent carboxylic acid, preferably C ₆ to C ₁₄ aromatic polyhydric carboxylic acids.

The aromatic polyhydric carboxylic acid is terephthalic acid; or terephthalic acid and isophthalic acid; and when using isophthalic acid mixed, terephthalic acid and isophthalic acid are used in a molar ratio of 1: 0.02 to 0.15, preferably 1: 0.04 to 0.10 to ensure low chip moisture content during chipping; It is advantageous in terms of securing a high glass transition temperature for polymerization.

The aliphatic polyhydric carboxylic acid is oxalic acid, malonic acid, succinic acid, glutaric acid, suberic acid, citric acid, pimeric acid, azelaic acid, sebacic acid, nonanoic acid, decanoic acid, dodecanoic acid and hexanodecanoic acid It may include one or more selected from among.

In addition, at least one selected from linear glycol and pulverized glycol may be used as a diol component for reducing crystallinity for improving dyeability in the preparation of the esterified compound, preferably ethylene glycol (EG); Or a glycol mixture comprising a linear glycol and a pulverized glycol represented by the following formula (2); may be used.

[Formula 2]

In Formula 2, each of R ¹ and R ⁴ is independently a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₅ alkylene group, a C ₅ to C ₆ cycloalkyl group or a phenyl group, preferably Each of R ¹ and R ⁴ is independently a hydrogen atom or a C ₁ to C ₅ alkyl group, more preferably each of R ¹ and R ⁴ is independently a hydrogen atom or a C ₁ to C ₃ alkyl group, provided that R ¹ and R ⁴ are all hydrogen atoms.

And, in Formula 2, each of R ² and R ³ is independently a C ₁ to C ₅ alkylene group, preferably R ² and R ³ are each independently a C ₁ to C ₃ alkylene group, more preferably Each of R ² and R ³ is independently a C ₁ to C ₂ alkylene group.

And, as the straight-chain glycol in the glycol mixture, C ₂ to C ₆ straight-chain glycol, preferably C ₂ to C ₄ straight-chain glycol, more preferably C ₂ to C ₃ straight-chain glycol can be used

The glycol has high crystallinity when blended with recycled PET or copolyester chips during the yarn manufacturing process, so that there may be a problem that the dye does not sufficiently penetrate into the fiber polymer to reduce crystallinity. The mixture may include 4 to 10 mol% of the pulverized glycol and the balance of the linear glycol, preferably 4 to 8 mol% of the pulverized glycol and the balance of the straight-chain glycol. At this time, when the content of the pulverized glycol in the glycol mixture is less than 4 mol%, the crystallinity control effect is insufficient and the dyeing increase effect is insufficient, and when the pulverized glycol content exceeds 10 mol%, the crystallinity is very There may be a problem in that the discharging processability of the PE resin decreases, or a bridge between chips occurs during drying for manufacturing chips of the PE resin.

The PE resin of the present invention includes a polymer obtained by polycondensation of an ester compound obtained by esterification of an acid component and a diol component, wherein the diol component is a carboxylic acid and a diol component 1:1. After mixing at a molar ratio of ~ 1.4, preferably 1:15 ~ 1.30 molar ratio, an esterification reaction and a polycondensation reaction are performed. At this time, if the molar ratio of the diol component is less than 1:1, there may be a problem that the ester reaction does not sufficiently occur. There may be a problem of lowering the quality of the yarn by lowering it.

In addition, the PE resin is prepared by performing an esterification reaction on an esterification product containing an acid component and a diol component in the first step of preparing an ester compound; and a second step of preparing a polycondensed reactant by polycondensation of the ester compound.

The type and amount of the acid component and the diol component in step 1 are the same as described above. In addition, the esterification reaction may be performed at a temperature of 200 to 265°C, preferably at a temperature of 220 to 245°C. If the temperature is less than 200 ℃, there may be a problem that the reaction does not proceed because the raw material does not melt well, and if it exceeds 265 ℃, there may be problems such as decomposition due to deterioration or inability to obtain a desired degree of polymerization.

In addition, the esterification reaction can be carried out under a stirring speed of 40 to 80 rpm, preferably 50 to 70 rpm, and if the speed is less than 40 rpm or exceeds 80 rpm, sufficient esterification reaction is achieved. There may be unsolved issues.

In addition, the esterification reaction of the first step may be performed after adding and mixing an antifoaming agent and/or an esterification catalyst in addition to the acid component and the diol component.

In this case, the antifoaming agent may be a general one used in the art, and its amount may be used in an amount of 0.005 to 0.02% by weight, preferably 0.008 to 0.012% by weight, based on the total weight% of the ester reactant.

In addition, the esterification catalyst may include at least one of lithium acetate, magnesium acetate, and calcium acetate, preferably lithium acetate. In addition, the amount of the esterification catalyst used is 0.01 to 0.03% by weight, preferably 0.015 to 0.025% by weight, based on the total weight% of the ester reactant.

Next, the polycondensation reaction of the second step may be carried out at a temperature of 250 to 300 °C, preferably at a temperature of 260 to 290 °C. In addition, the polycondensation reaction may be performed under a stirring speed of 45 to 70 rpm, preferably 50 to 65 rpm.

In addition, the polycondensation reaction may be performed after adding and mixing one or more additives selected from an antioxidant, a heat stabilizer, and a polycondensation catalyst in addition to the ester compound, and then performing the polycondensation reaction.

Among the additives, the heat stabilizer is trimethylphosphate, triethyl phosphate, tributylphosphate, tributoxyethyl phosphate, tricresyl phosphate, triaryl phosphate isopropyl Rated (Triaryl phosphate isopropylated), hydroquinone bis- (diphenyl phosphate) (Hydroquinone bis- (diphenyl phosphate)) and ortho- may include at least one selected from phosphoric acid (Ortho-phosphoric acid). In addition, the amount of the heat stabilizer may be used in an amount of 0.05 to 0.15% by weight, preferably 0.07 to 0.13% by weight, based on the total weight% of the polycondensation reactant.

In addition, the antioxidant may be included in the form of pentaerythritol tetrakis (Pentaerythritol tetrakis, (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)) alone or in a mixed form with other antioxidants, The amount of the inhibitor used may be 0.05 to 0.15 wt%, preferably 0.07 to 0.13 wt%, based on the total weight of the polycondensation reactant.

Antimony trioxide is preferably used as the polycondensation catalyst, and the amount of the polycondensation catalyst used is 0.05 to 0.15 wt%, preferably 0.07 to 0.13 wt%, based on the total weight of the polycondensation reactant.

The PE resin of the present invention prepared by this composition, composition ratio and manufacturing method has an intrinsic viscosity (I.V) of 0.40 to 0.80 dl/g, preferably 0.45 to 0.78 dl/g, more preferably 0.55 to 0.75 dl/g can be

In addition, the PE resin of the present invention of the present invention may have a glass transition temperature (Tg) of 58 ~ 75 ℃, preferably 60 ~ 72 ℃, more preferably 60 ~ 68 ℃.

In addition, the PE resin of the present invention may have a melting point (Tm) of 180 to 220 ℃, preferably 185 to 220 ℃, more preferably 190 to 215 ℃.

The PE resin of the present invention may be provided in the form of chips by chipping. For a preferred embodiment, the PE resin is dried in multiple stages from 70° C. to 130° C. for 5 to 7 hours to undergo preliminary crystallization, and then dried at 140 to 160° C. for 4 to 6 hours to reduce the moisture content of the PE resin to 100 ppm or less. manufactures chips. At this time, if the moisture content of the PE resin chip exceeds 100 ppm, it may be hydrolyzed during spinning for fiber and/or yarn production using it, and thus there may be a problem in spinning operability is poor.

By using the PE resin of the present invention, CD-PET fibers and/or yarns can be manufactured by the following method.

Step 1 of preparing PE resin (polyester resin for CD-PET manufacturing) chips and nonionic resin chips, respectively; A second step of forming a fiber by mixing the masterbatch in which the PE resin chip is melted and the resin in which the nonionic resin chip is melted to prepare a CD-PET composite resin, and then spinning it with a spinneret; And after dyeing the fiber with cationic dye, the third step of reducing washing; by performing a process comprising a CD-PET fiber can be prepared.

The PE resin and the PE resin chip in step 1 are the same as described above.

In addition, the nonionic resin chip of step 1 may include at least one of a polyester-based resin, a polyamide-based resin, an acrylic resin, an olefin-based resin, and a polyurethane-based resin, preferably a polyester-based resin More preferably, the chip may be made of polyethyleneterephthalate (PET) resin, and even more preferably, recycled PET resin.

The CD-PET composite resin may include 10 to 35% by weight of the polyester (PE) resin and the remaining amount of the PET resin, preferably 10 to 28% by weight of the PE resin and the remaining amount of the PET resin. . At this time, if the PE resin content exceeds 35% by weight, spinning may be poor, so it is recommended to use it within the above range.

The spinning of the second step can be performed in the same way as schematically shown in FIG. 1 , and more specifically, by blending and spinning through a circular nozzle at a spinning speed of 1,500 to 5,000 MPM, preferably 3,000 to 4,500 MPM, fibers can be produced.

And, the spinning in the second step may be performed at a temperature of 250 ~ 330 ℃, preferably at a temperature of 270 ~ 320 ℃, if the temperature is less than 260 ℃, the melt flow is not smooth and brittle form There may be a problem in that the yarn is formed and the winding process cannot be performed, and when it exceeds 330°C, there may be a problem in that the yarn is not formed due to deterioration and flows in the form of a melt.

Salting of the cationic dye in three steps can be performed by a general method used in the art, and a general cationic dye used in the art can be used, and preferably, the cationic dye is Kayacryl yellow 3RL, Kayacryl Red One or a mixture of two or more selected from GRL and Kayacryl Blue GSL may be used.

Cationic dyeable PET (CD-PET) fiber of the present invention prepared by this composition and method has a fineness of 50 to 600 De, preferably a fineness of 50 to 300 De, more preferably a fineness of 50 to 260 De. can have

In addition, the prepared CD-PET fiber of the present invention may have a strength of 2.50 to 4.50 g/de, preferably a strength of 3.00 to 4.30 g/de, and more preferably a strength of 3.60 to 4.25 g/de.

In addition, the prepared CD-PET fiber of the present invention may have an elongation of 30 to 45%, preferably 30 to 42%, more preferably 32.0 to 40.0%.

And, the CD-PET fiber of the present invention dyed with a cationic dye may have a surface dye concentration (K/S) of 9.0 to 15.0, preferably 10.0 to 14.5, more preferably 10.0 to 13.5.

In the above, the present invention has been mainly described with respect to the embodiment, but this is only an example and does not limit the embodiment of the present invention. It can be seen that various modifications and applications not exemplified above are possible without departing from the scope. For example, each component specifically shown in the embodiment of the present invention can be implemented by modification. And differences related to such modifications and applications should be construed as being included in the scope of the present invention defined in the appended claims.

[Example]

Example 1: Preparation of polyester resin for CD-PET production

(1) An acid component, a diol component, an antifoaming agent (silicone-based TSF-433) and lithium acetate (esterification catalyst) are added as an esterification reactant, and the temperature is raised from 200°C to 250°C and mixing and esterification reaction at a speed of 60 rpm to prepare an ester compound (reaction product).

상기 화학식 1-1에 있어서, 상기 R¹ 및 R²는 메틸기이며, K는 Na⁺이다.At this time, based on the total mol% of the acid component as an acid component, 7.5 mol% of a compound represented by the following formula 1-1 (bis(methyl)isophthalate-5-sulfonate), 8 mol% of adipic acid as a fatty acid, and carboxylic acid Two types of terephthalic acid and isophthalic acid were used in the remaining amount.
[Formula 1-1]

In Formula 1-1, R ¹ and R ² are a methyl group, and K is Na ⁺ .

In addition, ethylene glycol was used alone as the diol component, and the diol component was used in a molar ratio of 1:1.2 based on the carboxylic acid of the acid component.

In addition, the antifoaming agent was used in an amount of 0.01% by weight based on the total weight% of the prepared ester reactant, and the esterification catalyst was used in an amount of 0.2% by weight based on the total weight% of the prepared ester reactant.

(2) Antioxidant (IR-1010, Pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)), heat stabilizer (ORTHO-PHOSPHORIC ACID) and polycondensation to the prepared ester compound Antimony trioxide, which is a catalyst, was added, and the mixture and polycondensation reaction were performed at a temperature of 275° C. and a speed of 56 rpm to prepare a polyester resin (PE resin) for producing CD-PET, which is a polymer.

(3) Then, the prepared polyester (PE) resin was dried in multiple stages at a temperature of 70 to 130° C. for 6 hours, and then dried at 150° C. for 5 hours to prepare a masterbatch chip for CD-PET production with a moisture content of 100 ppm or less.

Examples 2 to 6 and Comparative Examples 1 to 4

In the same manner as in Example 1, a polyester resin for producing CD-PET and a masterbatch chip obtained by chipping the same were prepared, but as shown in Tables 1 to 2, by changing the acid component and/or the diol component, respectively, Examples 2 to 6 and Comparative Examples 1 to 4 were performed, respectively.

As the pulverized glycol among the diol components, glycols represented by the following Chemical Formula 2-1 or 2-2 were used.

[Formula 2-1]

In Formula 2-1, R ¹ is a methyl group, R ⁴ is a hydrogen atom, and R ² and R ³ are a methylene group.

[Formula 2-2]

In Formula 2-2, R ¹ and R ⁴ are a methyl group, and R ² and R ³ are a methylene group.

Experimental Example 1: Measurement of physical properties of polyester resin for CD-PET production

Each of the masterbatch chips for producing CD-PET prepared in Examples and Comparative Examples were subjected to physical property tests using the following methods, and the results measured through these tests are shown in Tables 1 to 2 below.

(1) Intrinsic Viscosity (I.V)

Ortho-chlorophenol (Ortho-Chloro Phenol) as a solvent is melted at 110°C, 2.0 g/25m concentration for 30 minutes, then at 25°C for 30 minutes, and analyzed from an automatic viscometer connected to a CANON viscometer. did

(2) Glass transition temperature (Tg) and melting point (Tm)

The glass transition temperature was measured using a differential calorimeter, and the analysis condition was a temperature increase rate of 20 °C/min.

(3) Evaluation of discharging workability

When chipping the PE resin prepared in Examples and Comparative Examples, the cutting operation is carried out while passing through cold water at a level of 10 to 15 ° C. At this time, whether elution occurs in cold water and whether or not the sticking between chips (Bridge) occurs was confirmed.

(4) Chip dry evaluation

When manufacturing the masterbatch chips prepared in Examples and Comparative Examples, it was checked whether a bridge phenomenon occurred and whether surface crystallization occurred during the drying process.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 mountain
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minute adipic acid 8 mol% 8 mol% 8 mol% 8 mol% 8 mol% 9.5 mol% Formula 1-1 7.5 mol% 7.5 mol% 7.5 mol% 7.5 mol% 7.5 mol% 7.5 mol% isophthalic acid 5 mol% - - 5 mol% 5 mol% 5 mol% terephthalic acid remaining balance mol% diol ingredient ethylene glycol 100 mol% 95 mol% 95 mol% 90 mol% 90 mol% 95 mol% Formula 2-1 - 5 mol% - 9 mol% - 5 mol% Formula 2-2 - - 5 mol% - 9 mol% - Diol usage
(based on 1 molar ratio of carboxylic acid) 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio Ester compound (parts by weight) 100 100 100 100 100 100 Polyethylene glycol (parts by weight) - - - - - - Intrinsic Viscosity (I.V, dl/g) 0.71 0.68 0.67 0.65 0.64 0.69 Glass transition temperature (Tg, ℃) 61 64 63 60 58 58 Melting Point (Tm, ℃) 200 207 205 193 190 185 chip solubility no elution no elution no elution no elution no elution no elution Chip Moisture 50 ppm 140 ppm 120 ppm 90 ppm 70 ppm 80 ppm Initial bridging temperature during drying 70℃ 68℃ 68℃ 66℃ 65℃ 63℃ Whether the surface can crystallize possible possible possible possible possible possible

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 mountain
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minute adipic acid - 8 mol% 8 mol% 12 mol% Formula 1-1 7.5 mol% 7.5 mol% 7.5 mol% 7.5 mol% isophthalic acid 5 mol% 5 mol% 5 mol% 5 mol% terephthalic acid remaining balance mol% diol ingredient ethylene glycol 100 mol% 88 mol% 88 mol% 95 mol% Formula 2-1 - 12 mol% - 5 mol% Formula 2-2 - - 12 mol% - Diol usage
(based on 1 molar ratio of carboxylic acid) 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio 1.2 molar ratio Ester compound (parts by weight) 100 100 100 100 polyethylene glycol
(parts by weight) 10 - - - Intrinsic Viscosity (I.V, dl/g) 0.80 0.59 0.57 0.60 Glass transition temperature (Tg, ℃) 60 57 55 53 Melting Point (Tm, ℃) 210 186 182 178 chip solubility some dissolution some elution some elution some elution Chip Moisture 590 ppm 350 ppm 400 ppm 800 ppm Initial bridging temperature during drying 50℃ 62℃ 58℃ 56℃ Whether the surface can crystallize impossible possible impossible possible

Looking at the physical properties of the PE resins in Tables 1 and 2, in the case of Examples 1 to 6, the intrinsic viscosity of 0.64 to 0.71 dl / g, the glass transition temperature of 58 to 64 ° C., and the melting point of 189 to 207 ° C. It was confirmed that there was no discharge, and overall, it had a low moisture content of 140 ppm or less, and had a high bridge generation temperature of 65° C. or more.

On the other hand, in the case of the PE resin of Comparative Example 1 prepared using polyethylene glycol without using adipic acid, it has a high intrinsic viscosity compared to other examples and comparisons, and a low bridge generation temperature when chipping. There was a problem in that high moisture content and surface crystallization did not occur.

In addition, in the case of Comparative Examples 2 and 3 prepared in which the diol represented by Formula 2-1 or Formula 2-2 was used in excess of 10 mol% among the diol components, compared with Examples 4 to 5, relatively too low It has a glass transition temperature, and there is a problem in that the moisture content of the chip greatly increases during chipping.

In addition, in the case of the PE resin of Comparative Example 4 in which adipic acid, a fatty acid among the acid components, was used in excess of 10 mol%, compared with Example 6, the glass transition temperature and the melting temperature were too abruptly lowered, and the chip moisture content was significantly increased. There was a problem.

Preparation Example 1: Preparation of CD-PET composite resin and CD-PET fiber

(1) Preparation of CD-PET composite resin and fiber

A CD-PET composite by using an O-shaped 2-hole spinneret and mixing the masterbatch in which the masterbatch chip (PE resin chip) of Example 1 prepared above is melted with the resin in which the recycled PET chip is melted using a side feeder After preparing the resin, spinning was performed at a spinning temperature of 285° C. and a spinning speed of 4,000 MPM to prepare a CD-PET fiber having a fineness of 150 De.

At this time, the mixing ratio of the master batch (PE resin) chip and the recycled PET chip during spinning was 20 wt% of polyester resin and 80 wt% of recycled PET resin.

(2) cationic staining

Next, the prepared fiber was dyed with a cationic dye, Kayacryl Blke GSL, at a concentration of 2% owf at 110° C. for 45 minutes, and then reduced and washed at 80° C. to complete the dyeing.

After measuring the reflectance (R: Reflectance) of the dyed material dyed with the cationic dye using a spectrophotometer (Konica Minolta E-3000), it is substituted into the formula K/S=(1-R)2 /2R, The K/S value was calculated and the dyeability was evaluated with this value.

Preparation Examples 2 to 8 and Comparative Preparation Examples 1 to 5

In the same manner as in Preparation Example 1, a CD-PET fiber was prepared, but instead of the masterbatch chip of Example 1, each of the masterbatch chips prepared in Examples 2 to 3 and Comparative Preparation Example 1 was used to produce CD-PET fibers. were prepared, respectively, and Preparation Examples 2 to 8 and Comparative Preparation Examples 1 to 5 were carried out, respectively (see Table 3 below).

Experimental Example 2: Measurement of physical properties of CD-PET fibers

(1) Measurement of strength and elongation

The steel and elongation of the manufactured fiber were measured by applying a speed of 50 cm/m and a gripping distance of 50 cm using an automatic tensile tester (Textechno). Strength and elongation are the value (g/de) obtained by dividing the applied load by the denier when the composite fiber is stretched until it is cut with a constant force. defined.

(2) Dyeability (deepness, K/S) evaluation

Measure the reflectance (R: Reflectance) of the dyed material using a spectrophotometer (Konica Minolta E-3000), and then substitute this into the formula K/S=(1-R)2 /2R to obtain the K/S value. was evaluated for dyeability.

division Preparation Example 1 Preparation 2 Preparation 3 Preparation 4 Preparation 5 Preparation 6 Masterbatch (polyester resin) Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 20% by weight 10% by weight 20% by weight 20% by weight 20% by weight 20% by weight Recycled PET resin 80% by weight 90% by weight 80% by weight 80% by weight 80% by weight 80% by weight CD-PET
fiber speedy 4,000 MPM fineness 150 De Intensity (g/de) 4.0 3.4 4.3 4.2 3.7 3.8 Elongation (%) 35 43 32 34 41 39 Uniformity (%) 1.00 0.8 0.9 0.9 1.0 1.0 dyeability Surface dye concentration (K/S) 10.5 9.6 12.5 11.8 13.5 13.2 spinning operability Great Great Great Great Great Great

division Preparation 6 Comparative Preparation Example 1 Comparative Preparation Example 2 Comparative Preparation Example 3 Masterbatch (polyester resin) Example 6 Example 1 Comparative Example 1 Comparative Example 1 20% by weight 40% by weight 6.5% by weight 20% by weight Recycled PET resin 80% by weight 60% by weight 93.5 wt% 80% by weight CD-PET
fiber speedy 4,000 MPM fineness 150 De Intensity (g/de) 3.7 radiation
error 2.8 3.5 Elongation (%) 40 55 32 Uniformity (%) 1.2 1.3 0.95 dyeability Surface dye concentration (K/S) 14.0 7.2 8.8 spinning operability Great Good Good

Looking at Tables 3 and 4 above, in the case of fibers made of the CD-PET composite resin of Preparation Examples 1 to 6, overall excellent mechanical properties (strength, elongation) and uniformity, and excellent dyeability with a surface dye concentration of 9.0 or higher was able to confirm that it has

On the other hand, in the case of Comparative Preparation Example 1 prepared with a CD-PET composite resin containing 40% by weight of polyester (PE) resin in an amount exceeding 35% by weight, there was a problem in that the spinnability was very poor.

And, in the case of Comparative Preparation Example 2 prepared with a CD-PET composite resin containing less than 10% by weight of polyester (PE) resin in an amount of 6.5% by weight, less than 10% by weight, strength and elongation were not good, and dyeability was also poor. .

In addition, in the case of Comparative Preparation Example 3 prepared using the PE resin of Comparative Example 1, there was a problem that the surface dye concentration (K/S) was not good as 9.0 or less.

Through the above Examples and Preparation Examples, it can be confirmed that the polyester resin for producing CD-PET of the present invention not only has an appropriate intrinsic viscosity, glass transition temperature and melting point, but also has a low chip moisture content and a high bridge temperature when it is chipped. there was. In addition, it was confirmed that the CD-PET fibers prepared using the CD-PET polyester resin and waste PET resin could secure excellent cationic dyeing properties while having excellent overall mechanical properties.

Claims (10)

A polymer obtained by polycondensation of an ester compound obtained by esterifying an acid component and a diol component,
The acid component includes 7 to 15 mol% of a compound represented by the following formula (1), 7 to 10 mol% of a fatty acid, and the remaining amount of carboxylic acid,
The diol component includes a glycol mixture comprising 4 to 10 mol% of the pulverized glycol represented by the following formula (2) and the remaining amount of the linear glycol;
The straight-chain glycol is C ₁ ~ C ₅ Polyester resin for producing CD-PET, characterized in that it comprises a straight-chain glycol;
[Formula 1]

In Formula 1, wherein R ¹ and R ² are each independently a C ₁ to C ₅ straight-chain alkyl group or a C ₃ to C ₅ pulverized alkyl group, K is Na+ or K+,
[Formula 2]

In Formula 2, each of R ¹ and R ⁴ is independently a hydrogen atom, a C ₁ to C ₁₀ alkyl group, a C ₂ to C ₅ alkylene group, a C ₅ to C ₆ cycloalkyl group or a phenyl group, R ² and Each of R ³ is independently a C ₁ to C ₅ alkylene group, with the proviso that R ¹ and R ⁴ are both hydrogen atoms, except for the case.
According to claim 1, wherein the fatty acid comprises at least one selected from adipic acid, succinic acid and glutaric acid,
The carboxylic acid is a polyester resin for producing CD-PET, characterized in that it comprises at least one selected from C ₆ ~ C ₁₄ aromatic polyhydric carboxylic acid and C ₂ ~ C ₁₆ aliphatic polyhydric carboxylic acid.
delete [Claim 2] The polyester resin for producing CD-PET according to claim 1, wherein the polymer has a polymerization degree of 120 to 180.
5. The method of claim 1, 2 or 4, wherein the intrinsic viscosity (intrinsic viscosity) 0.40 ~ 0.80 dl / g, glass transition temperature (Tg) 58 ℃ ~ 75 ℃, and melting temperature (Tm) 180 ℃ ~ 220 ℃ Polyester resin for CD-PET production, characterized in that
[Claim 5] A masterbatch chip for producing CD-PET comprising the polyester resin of claim 1, 2 or 4.
A CD-PET composite resin comprising the polyester resin of claim 1, 2 or 4 and a PET resin.
8. The CD-PET composite resin according to claim 7, wherein the PET resin comprises recycled PET resin derived from waste products.
A fiber comprising the CD-PET composite resin of claim 7, a cation dye and an additive.
The fiber according to claim 9, wherein the surface dye concentration (K/S) satisfies 9.0 to 15.0.

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