TWI782605B - 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, a cationic dye (CD, cation dye)-polyethylene terephthalate (PET) composite resin using it, and relates to a non-ionic polyethylene terephthalate resin that can ensure Polyester resin for cationic dye-polyethylene terephthalate with excellent dyeability of cationic dye, cationic dye-polyethylene terephthalate composite resin prepared therefrom, and preparation thereof Cationic dyes with excellent dyeing rate Cationic dyes-polyethylene terephthalate fiber, raw silk, circular knitted fabric, etc.

Description

Polyester resin for preparing cationic dye-polyethylene terephthalate and cationic dye-polyethylene terephthalate composite resin containing same

The present invention relates to a cationic dye (CD)-polyethylene terephthalate composite resin prepared by recycling polyethylene terephthalate (PET, polyethyleneterephthalate) resin and when it is used to prepare fibers and/or precursors Cationic dyeable polyester resins for the preparation of cationic dyes-polyethylene terephthalate, and cationic dyeable fibers and/or raw yarns, circular knitted fabrics, etc.

Generally, as a fiber preparation method capable of cationic dyeing, when terephthalic acid (TPA) and ethylene glycol (EG) are used to prepare polyester fibers, a known modifier capable of ion-bonding cationic dyes is combined with terephthalic acid (TPA) Diformic acid and ethylene glycol are mixed for direct esterification.

In order to impart cationic dyeability to modified polyester products such as recycled polyester, flame retardant polyester, high shrinkage polyester, modified polyester containing high _TiO2 content, etc., it is necessary to add modifiers to Each polymerization process is prepared by transesterification.

In order to produce conventional recycled polyester, first, ethylene glycol is added to flakes (Flake) prepared in a bottle, and after melting at a temperature of 180°C to 240°C, glycolysis reaction is carried out under nitrogen pressurized conditions After preparing bishydroxyethyl terephthalate (BHT, bishydroxyethyl Terephthalate), the recycled polyester is prepared by polycondensation reaction. Among them, since nitrogen pressurization is carried out during the ES reaction, it is necessary to add dimethyl sulfide (DMS) to enable cationic dyeing during the polymerization reaction. The diol undergoes first reacted oligomer form addition. Due to the above-mentioned process, the amount of diethylene glycol (DEG, Diethylene glycol) produced is larger than that of conventional polyester products that can be dyed cationic, thereby improving spinning operability and dyeability after final dyeing different questions.

Also, in the case of conventional polyester, there are no sites for ion interaction with ionic dyes, and therefore, only disperse dyes are used for dyeing. Disperse dyes not only cannot provide bright and deep colors, but are also less reliable for sublimation processing.

The sodium salt of 5-sulfoisophthalic acid (Na-SIPA) is usually used as a cationic comonomer to prepare cationic dyeable polyesters (cationic dye-polyethylene terephthalate (CD-PET)) by copolymerization, This enables the use of cationic dyes on fibers and threads.

The sodium salt of 5-sulfoisophthalate used in the preparation of cationic dye-polyethylene terephthalate has acidic properties, and the formation of diethylene glycol increases during the esterification step of polyethylene terephthalate , lowers the melting point, promotes the aggregation of _TiO2 due to the acidic nature, and thus has difficulty in preparing fibers. In order to solve this kind of problem, when at the end or start of the esterification step, it was tried by providing bis(hydroxyethyl)isophthalate-5-sulfonate, i.e., dimethyl sulfide with ethylene glycol The oligomer form of the first reaction was used to solve the problem, but in the process of preparing bis(hydroxyethyl)isophthalate-5-sulfonate, due to the trimer, tetramer and oligomer Formation has the problem of poor spinnability (Spinability).

In particular, in order to prepare recycled polyester resins capable of being dyed with cationic dyes, bishydroxyethyl terephthalate is produced by glycolytic depolymerization with flakes supplied from bottles under nitrogen pressurized conditions in the esterification polymerization step Finally, in the polymerization step, bis(hydroxyethyl)isophthalate-5-sulfonate needs to be added, but as mentioned above, the yield of diethylene glycol increases, the melting point decreases and oligomers are formed, thereby There was a problem of poor spinnability.

As mentioned above, in the case of modified copolyesters, i.e., flame retardant polyesters, polyesters with high _TiO2 concentration, polyesters with latent curling properties, recycled polyesters, etc., when dimethyl sulfide is used to When it is possible to dye with cationic dyes, the production of diethylene glycol increases, and due to the acidic nature, aggregation with _TiO2 occurs, or it cannot be added and can only be added with bis(hydroxyethyl)isophthalate when performing esterification - Addition in the form of 5-sulfonate ester has the problem of poor spinnability due to the excessive generation of oligomers.

In order to improve the above-mentioned problems, cationic dye-polyethylene terephthalate fiber can be prepared by using composite resin (or masterbatch) for preparing cationic dye-polyethylene terephthalate fiber and recycled Cationic dyed polyester. Korean Application No. 10-2019-7009748 describes a polyester masterbatch for use in fabric modification and its preparation method. It relates to polyester masterbatches selected from dicarboxylic aromatic and/or aliphatic acids, and describes the preparation of polycondensation with the addition of up to 40% dimethyl sulfide and maximum high molecular weight polyglycols. However, when polyalcohols such as polyethylene glycol and the like are added at a high concentration and high molecular weight, the water adsorption rate in the sheet drying process for producing cationic dye-polyethylene terephthalate increases, and there is a tendency for the fiber to be broken during the production of the precursor. Yarn, unwinding and other issues.

The problem to be solved by the invention

The present invention is proposed in view of the above-mentioned problems, by grasping the excellent dyeability of cationic dyes for recycled polyethylene terephthalate resin, which is used to prepare cationic dye-polyethylene terephthalate resin. The optimal composition and composition ratio of ester resin have completed the present invention. The cationic dye-polyethylene terephthalate resin prepared using the above-mentioned polyester resin for the preparation of cationic dye-polyethylene terephthalate can minimize the water adsorption rate and can improve the dyeing rate of the cationic dye The original silk that can be improved. That is, the present invention intends to provide a polyester resin for producing cationic dye-polyethylene terephthalate, a cationic dye-polyethylene terephthalate resin containing the polyester resin, and a precursor produced using the polyester resin.

technical means to solve problems

The polyester resin used to prepare the cationic dye-polyethylene terephthalate of the present invention is a polymer formed by polycondensation of an ester compound. The ester compound is formed by esterifying an acid component and a diol component. The above-mentioned The acid component includes a compound represented by the following chemical formula 1, a fatty acid, and a carboxylic acid. The diol component includes ethylene glycol or a diol mixture, and the diol mixture further includes a straight-chain diol and a branched chain represented by the following chemical formula 2. diol.

Chemical formula 1:

In the above chemical formula 1, the above R ¹ and R ² are each independently a C ₁ -C ₅ linear alkyl group or a C ₃ -C ₅ branched chain alkyl group, and K is a monovalent cation.

Chemical formula 2:

In the above chemical formula 2, R ¹ and R ⁴ are each independently a hydrogen atom, a C ₁ -C ₁₀ alkyl group, a C ₂ -C ₅ alkylene group, a C ₅ -C ₆ cycloalkyl group or a phenyl group, R ² and R ³ are each independently a C ₁ -C ₅ alkylene group, but the case where both R ¹ and R ⁴ are hydrogen atoms is excluded.

As a preferred embodiment of the present invention, the above-mentioned acid component may include 7 mol%-15 mol% of the compound represented by the above chemical formula 1, 7 mol%-10 mol% of the above-mentioned fatty acid and the remaining amount of carboxylic acid.

According to a preferred embodiment of the present invention, the above-mentioned fatty acid may contain at least one selected from the group consisting of adipic acid, succinic acid and glutaric acid.

As a preferred embodiment of the present invention, the above-mentioned carboxylic acid may include at least one selected from the group consisting of C ₆ -C ₁₄ aromatic polycarboxylic acids and C ₂ -C ₁₆ aliphatic polycarboxylic acids.

As a preferred embodiment of the present invention, the above-mentioned C ₆ -C ₁₄ aromatic polycarboxylic acid may include terephthalic acid alone, or both terephthalic acid and isophthalic acid.

According to a preferred embodiment of the present invention, the above-mentioned diol mixture in the diol component may include 4 mol%˜10 mol% of the above-mentioned branched diols and the remaining amount of straight-chain diols.

According to a preferred embodiment of the present invention, the above-mentioned linear diols may include C ₁ -C ₅ linear diols.

As a preferred embodiment of the present invention, the polyester resin used to prepare the cationic dye-polyethylene terephthalate of the present invention may be a polymer with a degree of polymerization of 120-180.

As a preferred embodiment of the present invention, the intrinsic viscosity (intrinsic viscosity) of the polyester resin used to prepare the cationic dye-polyethylene terephthalate of the present invention can be 0.40 dl/g～0.80 dl/g, glass The conversion temperature (Tg) may be 58°C to 75°C, and the melting temperature (Tm) may be 180°C to 220°C.

Another object of the present invention is to provide a masterbatch for preparing cationic dye-polyethylene terephthalate comprising the above-mentioned polyester resin for preparing cationic dye-polyethylene terephthalate sample.

And, in another object of the present invention, including the polyester resin and polyethylene terephthalate resin mentioned earlier for the preparation of cationic dye-polyethylene terephthalate as cationic dye-polyethylene terephthalate Ethylene phthalate composite resin.

In a preferred embodiment of the present invention, the cationic dye-polyethylene terephthalate composite resin may comprise 10% by weight to 35% by weight of the polyester resin and the remainder of the polyethylene terephthalate resin .

In a preferred embodiment of the present invention, the above-mentioned polyethylene terephthalate resin in the cationic dye-polyethylene terephthalate composite resin component may contain recycled polyethylene terephthalate derived from waste products Diester resin.

Another object of the present invention is to provide cationic dye-polyethylene terephthalate fiber and/or cationic dye-polyethylene terephthalate fiber prepared by using the above-mentioned cationic dye-polyethylene terephthalate composite resin Ethylene glycol raw silk.

As a preferred embodiment of the present invention, the above-mentioned cationic dye-polyethylene terephthalate fiber may include cationic dye-polyethylene terephthalate resin, cationic dye and additives.

As a preferred embodiment of the present invention, the above-mentioned cationic dye-polyethylene terephthalate fiber is polyethylene terephthalate prepared by using the above-mentioned cationic dye-polyethylene terephthalate composite resin to be dyed with cationic dye. For the precursor of diester fiber, the fiber dyed with the above-mentioned cationic dye can satisfy the surface dye concentration (K/S) of 9.0-15.0.

Still another object of the present invention is to provide a circular knitted fabric comprising the above-mentioned cationic dye-polyethylene terephthalate fiber and/or cationic dye-polyethylene terephthalate precursor.

Still another object of the present invention is to relate to the preparation method of the above-mentioned cationic dye-polyethylene terephthalate fiber and/or cationic dye-polyethylene terephthalate precursor, which can be performed by performing a process comprising the following steps To prepare cationic dye-polyethylene terephthalate fibers and/or precursors: the first step, respectively prepare the polyesters for the preparation of cationic dye-polyethylene terephthalate containing the various forms previously described A sheet of resin and a sheet comprising nonionic polyethylene terephthalate resin; the second step is mixing a masterbatch made by melting the sheet comprising the above-mentioned polyester resin and a sheet comprising nonionic polyethylene terephthalate Sheets of ethylene glycol resin are melted and spun through a spinneret to form fibers; and the third step is to perform reduction cleaning after dyeing the above fibers with cationic dyes.

As a preferred embodiment of the present invention, the above-mentioned cationic dye may contain one or more selected from Kayacryl yellow 3RL, Kayacryl Red GRL and Kayacryl Blue GSL.

In a preferred embodiment of the present invention, the above-mentioned spinning can be performed at a temperature of 250° C. to 330° C. and a spinning speed of 1500 MPM to 4500 MPM.

Efficacy compared to prior art

In the polyester resin used to prepare cationic dye-polyethylene terephthalate (CD-PET, cation dye-polyethyleneterephthalate) fiber of the present invention, when cationic dye is used for dyeing and recycling waste polyethylene terephthalate When recycling polyethylene terephthalate resin into fiber and/or raw silk, the dyeing rate can be greatly improved, and the physical properties of the raw silk can be improved by controlling the moisture content.

Hereinafter, the present invention will be described more specifically.

Fibers prepared from recycled polyethylene terephthalate resins using recovered waste polyethylene terephthalate resins have a problem that the dyeing rate of cationic dyes is very low, so in the past, in order to increase the dyeing rate of cationic dyes , using a method of modifying recycled polyethylene terephthalate resin, etc., but there is a problem that the productivity is significantly lowered or the physical properties of fibers prepared by using recycled polyethylene terephthalate resin are lowered.

The present invention relates to the following invention: when the recycled polyethylene terephthalate resin is used to prepare fibers, if the polyester resin for producing cationic dye-polyethylene terephthalate (hereinafter referred to as Spinning as "PE resin" or "masterbatch") can prevent the physical properties of the fiber from deteriorating, and can also improve the dyeing rate of cationic dyes.

The above-mentioned PE resin of the present invention includes a polymer obtained by subjecting an ester compound to a polycondensation reaction. The ester compound is obtained by subjecting an esterification reaction product to an esterification reaction. The esterification reaction product includes an acid component and a diol component. .

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

Chemical formula 1:

In the above chemical formula 1, the above-mentioned R ¹ and R ² are each independently a straight chain alkyl group of C ₁ to C ₅ or a branched chain alkyl group of C ₃ to C ₅ , preferably a straight chain alkyl group of C ₁ to C ₅ , more preferably a C ₁ -C ₃ linear alkyl group. In addition, the aforementioned K is a monovalent cation, preferably Na ⁺ or K ⁺ .

In the total mol% of the above-mentioned acid components, 5 mol% to 15 mol% of the compound represented by Chemical Formula 1 may be included, preferably, 6 mol% to 13 mol% of the compound represented by Chemical Formula 1 may be included, more preferably , can contain 7 mol%～12 mol% of the compound represented by the chemical formula 1, if it contains less than 5 mol% of the compound represented by the above chemical formula 1, when the cationic dye-polyphenylene used in the preparation of fibers or precursors is prepared In the case of ethylene diformate composite resin, cationic dyeing can be expressed, thus having the problem of adding an excessive amount of masterbatch (or PE resin), if more than 15 mol% of the compound represented by the above chemical formula 1 is used, the polymer ( Or PE resin) molecular weight is too high, so there is a problem that the viscosity rises sharply, so it is better to use a value within the above range.

Moreover, the said fatty acid in an acid component may contain 1 or more types selected from the group which consists of adipic acid, succinic acid, and glutaric acid, Preferably, adipic acid may be contained. In the total mol% of the above-mentioned acid components, 7 mol% to 10 mol% of fatty acid may be contained, preferably, 7.2 mol% to 9.5 mol% of fatty acid may be contained. At this time, if the fatty acid content is less than 5 mol%, the increase in the viscosity of the polymer cannot be controlled, so that the polymerization reaction does not reach the intrinsic viscosity (IV) level of 0.40 dl/g to 0.80 dl/g of the PE resin to be prepared. The problem of termination, if the fatty acid content used is greater than 10 mol%, the glass transition temperature (Tg) and melting temperature (Tm) of the PE resin are too low, so when the PE resin is sheeted to prepare fibers or precursors, Discharge failure may occur in the sheet melting and discharging process, and when PE resin is formed into a sheet, it needs to be dried at a low temperature of 60° C. or lower for a long time, which has the disadvantage of poor drying workability.

The above-mentioned carboxylic acid in the acid component may contain at least one selected from the group consisting of C ₆ -C ₁₄ aromatic polycarboxylic acids and C ₂ -C ₁₆ aliphatic polycarboxylic acids. Preferably, C ₆ to C ₁₄ aromatic polycarboxylic acid.

The above-mentioned aromatic polycarboxylic acid may include terephthalic acid, or terephthalic acid and isophthalic acid. When isophthalic acid is used in combination, terephthalic acid and isophthalic acid are used in a molar ratio of 1:0.02 to 1:0.15. For phthalic acid, preferably, terephthalic acid and isophthalic acid are used at a molar ratio of 1:0.04 to 1:0.10, which is more conducive to ensuring a low sheet moisture content and a high polymerization process. glass transition temperature.

The above-mentioned aliphatic polycarboxylic acid may comprise a compound selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, suberic acid, citric acid, pimelic acid, azelaic acid, sebacic acid, nonanoic acid, capric acid, dodecanoic acid, One or more species selected from the group consisting of alkanoic acid and hexadecanoic acid.

And, when preparing the esterified compound, one or more selected from the group consisting of straight-chain diols and branched-chain diols can be used as diol components to reduce crystallinity and improve dyeability. Preferably, ethylene glycol can be used. an alcohol or a diol mixture, the diol mixture including a linear diol and a branched diol represented by the following chemical formula 2.

Chemical formula 2:

In the above chemical formula 2, R ¹ and R ⁴ are each independently a hydrogen atom, a C ₁ -C ₁₀ alkyl group, a C ₂ -C ₅ alkylene group, a C ₅ -C ₆ cycloalkyl group or a phenyl group, Preferably, R ¹ and R ⁴ are each independently a hydrogen atom or a C ₁ -C ₅ alkyl group, more preferably, R ¹ and R ⁴ are each independently a hydrogen atom or a C ₁ -C ₃ alkyl group, but The case where R ¹ and R ⁴ are both hydrogen atoms is excluded.

Moreover, the above-mentioned R ² and R ³ in Chemical Formula 2 are each independently a C ₁ -C ₅ alkylene group, preferably, R ² and R ³ are each independently a C ₁ -C ₃ alkylene group, more preferably , R ² and R ³ are each independently a C ₁ -C ₂ alkylene group.

And, the above-mentioned linear diols in the diol mixture can use C ₂ -C ₆ linear diols, preferably, C ₂ -C ₄ linear diols can be used, more preferably, C ₂ -C 6 linear diols can be used. _C3 straight chain diol.

In the process of preparing raw silk, when mixed with recycled polyethylene terephthalate or copolyester sheets, due to high crystallinity, there is a problem that dyes cannot fully penetrate into the interior of fiber polymers, so the above diol mixture Can contain 4 mol%～10 mol% of the above-mentioned branched diols and the remaining amount of linear diols, preferably, can contain 4 mol%～8 mol% of the above-mentioned branched diols and the remaining amount of linear diols , thereby reducing crystallinity. At this time, when the content of the branched diol in the above-mentioned diol mixture is less than 4 mol%, since the crystallinity control effect is very little, there may be a problem that the effect of improving the dyeability is very small. If the content of the branched diol is more than If the content is 10 mol%, the crystallinity is remarkably reduced, which may lead to a decrease in the discharge process of the PE resin, or a problem of blocking between the sheets during the drying process of the sheets used to prepare the PE resin.

The PE resin of the present invention includes a polymer obtained by polycondensing an ester compound obtained by esterifying an acid component and a diol component. At this time, among the diol components, carboxylic acid of the acid component is Based on mixing the carboxylic acid and diol components at a molar ratio of 1:1.1 to 1:1.4, preferably after mixing the carboxylic acid and diol components at a molar ratio of 1:1.15 to 1:1.30, the esterification reaction is carried out and polycondensation reactions. At this time, if the molar ratio of the diol component is less than the molar ratio of 1:1.1, there is a problem that the esterification reaction cannot be sufficiently performed, and if the molar ratio of the diol component is greater than the molar ratio of 1:1.4, the cost There is a problem of raising or increasing the generation of diethylene glycol and lowering the melting point, thereby lowering the quality of the raw silk.

In addition, the above-mentioned PE resin can be prepared by performing a process including the following steps: the first step is to perform an esterification reaction on an esterification reaction product containing an acid component and a diol component to prepare an ester compound; and the second step is to make the above-mentioned ester The compounds undergo polycondensation reactions to prepare polycondensed reactants.

The types and amounts of the acid component and diol component used in the first step are as described above. Also, the above esterification reaction may be performed at a temperature of 200°C to 265°C, preferably, the above esterification reaction may be performed at a temperature of 220°C to 245°C. If the temperature is lower than 200°C, the raw materials are not easily soluble, and thus the reaction cannot proceed. If the temperature is higher than 265°C, there is a problem that decomposition occurs due to deterioration or a desired degree of polymerization cannot be obtained.

Moreover, the above-mentioned esterification reaction can be performed at a stirring speed of 40 rpm to 80 rpm. Preferably, the above-mentioned esterification reaction can be carried out at a stirring speed of 50 rpm to 70 rpm. If the speed is less than 40 rpm or greater than 80 rpm, then There is a problem that sufficient esterification reaction cannot be performed.

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

At this time, the above-mentioned defoamer can use a conventional defoamer used in this field, relative to the total weight percentage of the esterification reactant, 0.005% by weight to 0.02% by weight of the defoamer can be used, preferably, 0.008% by weight can be used % by weight - 0.012% by weight of defoamer.

In addition, the esterification catalyst may contain one or more of lithium acetate, magnesium acetate, and calcium acetate, preferably lithium acetate. Moreover, relative to the total weight percentage of the esterification reactants, the esterification catalyst can be used in an amount of 0.01% by weight to 0.03% by weight, preferably, the esterification catalyst can be used in an amount of 0.015% by weight to 0.025% by weight.

Afterwards, the above polycondensation reaction of the second step may be performed at a temperature of 250°C to 300°C, preferably, may be performed at a temperature of 260°C to 290°C. And, the polycondensation reaction may be performed at a stirring speed of 45 rpm to 70 rpm, preferably, may be performed at a stirring speed of 50 rpm to 65 rpm.

In addition, in addition to the ester compound, one or more additives selected from antioxidants, heat stabilizers, and polycondensation catalysts may be added and mixed to perform the polycondensation reaction described above.

The above-mentioned heat stabilizer in the additive may include trimethylphosphate (trimethylphosphate), triethylphosphate (Triethylphosphate), tributylphosphate (Tributylphosphate), tributoxyethylphosphate (Tributoxyethylphosphate), toluenephosphate ( Tricresylphosphate), Triaryl phosphate isopropylated, Hydroquinone bis-(diphenyl phosphate) and Ortho-phosphoric acid more than one of them. In addition, relative to the total weight percentage of the polycondensation reactants, 0.05% to 0.15% by weight of the heat stabilizer may be used, preferably, 0.07% to 0.13% by weight of the heat stabilizer may be used.

And, the antioxidant can comprise tetrakis (3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester (Pentaerythritol tetrakis, (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate )) or in the form of tetra(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester mixed with other antioxidants, relative to the total weight percentage of the polycondensation reactants, 0.05% by weight to 0.15% by weight of antioxidant, preferably, 0.07% by weight to 0.13% by weight of antioxidant can be used.

It is better to use antimony trioxide as the above-mentioned polycondensation catalyst, relative to the total weight percentage of the polycondensation reactants, 0.05% by weight to 0.15% by weight of the polycondensation catalyst can be used, preferably, 0.07% by weight to 0.13% by weight of the polycondensation catalyst can be used.

The inherent viscosity (I.V) of the above-mentioned PE resin of the present invention prepared by such composition, composition ratio and preparation method is 0.40 dl/g-0.80 dl/g, preferably 0.45 dl/g-0.78 dl/g, more preferably 0.55dl/g～0.75dl/g.

In addition, the glass transition temperature (Tg) of the PE resin of the present invention may be 58°C to 75°C, preferably 60°C to 72°C, more preferably 60°C to 68°C.

In addition, the melting point (Tm) of the PE resin of the present invention is 180°C to 220°C, preferably 185°C to 220°C, more preferably 190°C to 215°C.

The PE resin of the present invention can be provided in a sheet form by being sheeted. As a preferred example, at a temperature of 70°C to 130°C, the above-mentioned PE resin is dried in multiple stages for 5 hours to 7 hours to perform pre-crystallization, and then dried at a temperature of 140°C to 160°C for 4 hours to 6 hours to prepare a PE resin sheet with a moisture content of 100 ppm or less. At this time, if the moisture content of the PE resin sheet is greater than 100 ppm, it will be hydrolyzed during the spinning process for producing fibers and/or precursors, resulting in poor spinning operability.

Cationic dye-polyethylene terephthalate fibers and/or filaments can be produced using the PE resin of the present invention as described above in the following manner.

The cationic dye-polyethylene terephthalate fiber can be prepared by performing a process comprising the following steps: In the first step, PE resins (polyester resins for preparing cationic dye-polyethylene terephthalate ) sheet and non-ionic resin sheet; the second step is to mix and melt the masterbatch of the above-mentioned PE resin sheet and the resin of the molten non-ionic resin sheet to prepare cationic dye-polyethylene terephthalate composite resin, and then spray Spinning it to form fibers; and the third step, after dyeing the above fibers with cationic dyes, performing reduction cleaning.

The aforementioned PE resin and PE resin sheet in the first step are as described above.

And, the above-mentioned non-ionic resin sheet of the first step can comprise more than one in polyester resin, polyamide resin, acrylic resin, olefin resin and polyurethane resin, preferably, can comprise polyester resin, more preferably, can It contains polyethylene terephthalate resin, and more preferably, may be a sheet composed of recycled polyethylene terephthalate resin.

The cationic dye-polyethylene terephthalate composite resin may contain 10% by weight to 35% by weight of the above-mentioned polyester resin and the remaining amount of polyethylene terephthalate resin, preferably, may contain 10% by weight to 35% by weight. 28% by weight of the above-mentioned PE resin and the remaining amount of polyethylene terephthalate resin. At this time, if the content of the above-mentioned PE resin exceeds 35% by weight, spinning failure may occur, so it is preferable to use it within the above-mentioned range.

The spinning of the second step can be carried out by the method shown in the schematic diagram of Figure 1, more specifically, the fiber can be prepared by mixing and spinning through a circular die at a spinning speed of 1500 MPM to 5000 MPM, preferably, Fibers were prepared by mixing and spinning through a circular die at spinning speeds ranging from 3000 MPM to 4500 MPM.

Also, the spinning in the second step can be performed at a temperature of 250°C to 330°C, preferably at a temperature of 270°C to 320°C, if the temperature is less than 260°C, the flow of the melt is not smooth, thus The precursor yarn in a brittle form has a problem that the winding process cannot be performed. If the temperature exceeds 330° C., the yarn cannot be formed due to deterioration, and thus there is a problem of flowing in a melt form.

The dyeing of the cationic dye of the third step can be carried out by the routine method used in this field, can use the conventional cationic dye used in this field, preferably, cationic dye can be selected from Kayacryl yellow 3RL, Kayacryl Red GRL and Kayacryl Blue GSL One of them or a mixture of two or more are used.

The cationic dyeable polyethylene terephthalate (cationic dye-polyethylene terephthalate) fiber of the present invention prepared by this composition and method can have a fineness of 50 De to 600 De, preferably , may have a fineness of 50 De to 300 De, more preferably, may have a fineness of 50 De to 260 De.

And, the prepared cationic dye-polyethylene terephthalate fiber of the present invention may have a strength of 2.50 g/de to 4.50 g/de, preferably, may have a strength of 3.00 g/de to 4.30 g/de , more preferably, may have a strength of 3.60 g/de˜4.25 g/de.

Moreover, the elongation of the prepared cationic dye-polyethylene terephthalate fiber of the present invention is 30%-45%, preferably 30%-42%, more preferably 32.0%-40.0%.

Furthermore, the surface dye concentration (K/S) at 600 nm of the cationic dye-polyethylene terephthalate fiber of the present invention dyed with a cationic dye is 9.0 to 15.0, preferably 10.0 to 14.5, more preferably 10.0 ~13.5.

Above, the present invention has been described centering on the example, but this is only an example, and does not limit the example of the present invention. As long as the embodiment of the present invention belongs to the ordinary knowledge of the technical field, it can be understood that it can be done without exceeding the scope of the present invention. Various modifications and applications not exemplified above can be carried out within the scope of the essential characteristics. For example, each structural element specifically shown in the examples of the present invention may be implemented in a modified manner. And, differences related to such modifications and applications are included in the scope of the present invention defined by the scope of claims of the invention.

[Example]

Embodiment 1: be used to prepare the preparation of the polyester resin of cationic dye-polyethylene terephthalate

(1) Add the acid component, diol component, defoamer (silicon TSF-433) and lithium acetate (esterification catalyst) to the esterification reaction product, and raise the temperature from 200°C to 250°C at 60 rpm Speed mixing and esterification reaction to prepare ester compound (reaction product).

At this time, 7.5 mol% of the compound represented by the following chemical formula 1-1 was used with respect to the total mol% of the acid component, 8 mol% of adipic acid was used as the fatty acid, and the remaining amount of terephthalic acid and isophthalic acid was used. Acid two as carboxylic acid.

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

And, relative to the total weight percentage of the prepared ester reactants, 0.01 weight percent of the antifoaming agent is used, and relative to the prepared ester reactants, 0.2 weight percent of the esterification catalyst is used.

(2) Add antioxidant (IR-1010, tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid) pentaerythritol ester), heat stabilizer (orthophosphoric acid) and polycondensation catalyst to the prepared ester compound Antimony trioxide, the temperature was raised to 275 ° C, mixed at a speed of 56 rpm and polycondensation reaction was carried out to prepare a polyester resin (PE resin for the preparation of cationic dye-polyethylene terephthalate) as a polymer ).

(3) In addition, at a temperature of 70 ° C to 130 ° C, the prepared polyester (PE) resin was dried in multiple stages for 6 hours, and then dried at a temperature of 150 ° C for 5 hours, thereby preparing a 100 Below ppm is used to prepare cationic dye-polyethylene terephthalate masterbatch.

Embodiment 2～6 and comparative example 1～4

Prepare the polyester resin used to prepare the cationic dye-polyethylene terephthalate and the masterbatch sheet by the same method as the above-mentioned Example 1, as shown in Table 1 to Table 2 below, and the acid composition can be changed and/or diol components to implement Examples 2-6 and Comparative Examples 1-4, respectively.

As the branched diol in the diol component, a diol represented by the following Chemical Formula 2-1 or the following Chemical Formula 2-2 is used.

Chemical formula 2-1:

In the above chemical formula 2-1, R ¹ is a methyl group, R ⁴ is a hydrogen atom, and R ² and R ³ are methylene groups.

Chemical formula 2-2:

In the above chemical formula 2-1, R ¹ and R ⁴ are methyl groups, and R ² and R ³ are methylene groups.

Experimental Example 1: Determination of physical properties of polyester resin used to prepare cationic dye-polyethylene terephthalate

The physical properties of the masterbatch sheets for the preparation of cationic dye-polyethylene terephthalate prepared in Examples and Comparative Examples were respectively subjected to physical property experiments by the following methods, and the results of the measurements are shown in the following Tables 1 to 2. 2.

(1) Intrinsic viscosity (I.V)

Ortho-Chloro Phenol (Ortho-Chloro Phenol) was used as a solvent, melted at a concentration of 2.0g/25m at a temperature of 110°C for 30 minutes, and then kept at a constant temperature of 25°C for 30 minutes, and connected to a Canon (CANON ) Viscometer automatic viscosity measurement device for analysis.

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

The glass transition temperature was measured by a differential thermal analyzer, and the analysis condition was that the heating rate was set at 20° C./min.

(3) Discharge workability evaluation

When the PE resins prepared in Examples and Comparative Examples are formed into sheets, pass cold water at a temperature of 10°C to 15°C and cut them. At this time, check whether dissolution occurs in the cold water and whether the sheets stick together. (Bridge).

(4) Sheet drying evaluation

When preparing the master batch sheets prepared in Examples and Comparative Examples, it was confirmed whether or not blocking between sheets occurred during drying and whether or not crystallization occurred on the surface.

Table 1 Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 acid component Adipic acid 8mol% 8mol% 8mol% 8mol% 8mol% 9.5mol% Chemical formula 1-1 7.5mol% 7.5mol% 7.5mol% 7.5mol% 7.5mol% 7.5mol% Isophthalic acid 5mol% - - 5mol% 5mol% 5mol% Terephthalic acid mol% of the remaining amount Diol component Ethylene glycol 100mol% 95mol% 95mol% 90mol% 90mol% 95mol% Chemical formula 2-1 - 5mol% - 9mol% - 5mol% Chemical formula 2-2 - - 5mol% - 9mol% - Amount of diol used (based on 1 mol 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 (IV, dl/g) 0.71 0.68 0.67 0.65 0.64 0.69 Glass transition temperature (Tg, °C) 61 64 63 60 58 58 Melting point (Tm, °C) 200 207 205 193 190 185 Tablet Water Dissolution No dissolution No dissolution No dissolution No dissolution No dissolution No dissolution Flake Moisture Rate 50ppm 140ppm 120ppm 90ppm 70ppm 80ppm Temperature at which initial sticking occurs during drying 70°C 68°C 68°C 66°C 65°C 63°C Possibility of surface crystallization possible possible possible possible possible possible

Table 2 Classification Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 acid component Adipic acid - 8mol% 8mol% 12mol% Chemical formula 1-1 7.5mol% 7.5mol% 7.5mol% 7.5mol% Isophthalic acid 5mol% 5mol% 5mol% 5mol% Terephthalic acid mol% of the remaining amount Diol component Ethylene glycol 100mol% 88mol% 88mol% 95mol% Chemical formula 2-1 - 12mol% - 5mol% Chemical formula 2-2 - - 12mol% - Amount of diol used (based on 1 mol 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 (IV, dl/g) 0.80 0.59 0.57 0.60 Glass transition temperature (Tg, °C) 60 57 55 53 Melting point (Tm, °C) 210 186 182 178 Tablet Water Dissolution Partial dissolution Partial dissolution Partial dissolution Partial dissolution Flake Moisture Rate 590ppm 350ppm 400ppm 800ppm Temperature at which initial sticking occurs during drying 50℃ 62°C 58°C 56°C Possibility of surface crystallization impossible possible impossible possible

According to the physical properties of the PE resin in Table 1 and Table 2 above, it can be confirmed that in the case of Examples 1 to 6, the intrinsic viscosity is 0.64 dl/g to 0.71 dl/g, the glass transition temperature is 58°C to 64°C, and the melting point is 189°C to 207°C, no water dissolution after flaking, overall low moisture content below 140 ppm, and high blocking occurrence temperature above 65°C.

On the contrary, in the case of the PE resin of Comparative Example 1 prepared using polyethylene glycol instead of adipic acid, when compared with other Examples and Comparative Examples, there is a problem that it has a high intrinsic Viscosity, when flaked, has a low temperature at which blocking occurs, has a high moisture content and has no surface crystallization.

In addition, in the case of Comparative Example 2 and Comparative Example 3 prepared using the diol represented by Chemical Formula 2-1 or Chemical Formula 2-2 in the diol component exceeding 10 mol%, when compared with Examples 4-5 When, there is a problem that the glass transition temperature is relatively too low, and when flaked, the moisture content increases greatly.

In addition, in the case of the PE resin of Comparative Example 4 using adipic acid as a fatty acid in the acid component exceeding 10 mol%, when compared with Example 6, there is a problem that the glass transition temperature and the melting temperature are rapid. decreased, the moisture content of the tablet increased greatly.

Preparation Example 1: Preparation of cationic dye-polyethylene terephthalate composite resin and cationic dye-polyethylene terephthalate fiber

(1) Preparation of cationic dye-polyethylene terephthalate composite resin

Using a spinneret with 2 holes in the O form, the masterbatch obtained by melting the previously prepared masterbatch sheet (PE resin sheet) of Example 1 and the recycled polyethylene terephthalate sheet using a side feeder After the molten resin was mixed to prepare cationic dye-polyethylene terephthalate composite resin, spinning was performed at a spinning temperature of 285°C and a spinning speed of 4000 MPM to prepare a cationic dye with a fineness of 150 De- Polyethylene terephthalate fibers.

At this time, when spinning, the mixing ratio of the masterbatch (PE resin) sheet and the recycled polyethylene terephthalate sheet is as follows: 20% by weight for polyester resin, 20% by weight for recycled polyethylene terephthalate resin 80% by weight.

(2) After that, Kayacryl Blke GSL, which is a cationic dye, was applied to the prepared fiber, dyed at a temperature of 110°C for 45 minutes at a concentration of 2% owf, and then reduced and washed at a temperature of 80°C to complete the dyeing.

Use a spectrophotometer (Konica Minolta (Konica Minolta) E-3000) to measure the reflectance (R: Reflectance) of the dyed matter dyed with the above cationic dye, and then substitute it into the formula K/S = (1-R) 2/2R to obtain the K/S value, and use the above K/S value to evaluate the dyeability.

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

The cationic dye-polyethylene terephthalate fiber was prepared by the same method as the above-mentioned Preparation Example 1, and the master batch sheet of the above-mentioned Example 1 was not used, but used in Examples 2-3 and Comparative Preparation Example 1 respectively Cationic dye-polyethylene terephthalate fibers were prepared using the prepared masterbatch sheets, and Preparation Examples 2-8 and Comparative Preparation Examples 1-5 were respectively implemented (see Table 2 below).

Experimental example 2: Determination of physical properties of cationic dye-polyethylene terephthalate fiber

(1) Determination of strength and elongation

The strength and elongation of the prepared fibers were measured using an automatic tensile tester (Textechno Company) at a speed of 50 cm/m and a holding distance of 50 cm. In terms of strength and elongation, the value (g/de) of dividing the load when a predetermined force is applied to the composite fiber until it breaks is defined as the value of denier (g/de), and the first value of the increased length is expressed as a percentage. The value (%) of the length is defined as elongation.

(2) Evaluation of dyeability (darkness, K/S)

Use a spectrophotometer (Konica Minolta (Konica Minolta) E-3000) to measure the reflectance (R: Reflectance) of the dyed matter, and substitute it into the formula K/S = (1-R)2/2R to obtain K/S value, and use the above K/S value to evaluate the dyeability.

table 3 Classification Preparation Example 1 Preparation example 2 Preparation example 3 Preparation Example 4 Preparation Example 5 Preparation example 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 polyethylene terephthalate resin 80% by weight 90% by weight 80% by weight 80% by weight 80% by weight 80% by weight Cationic Dyes - Polyethylene Terephthalate Fiber spinning speed 4000MPM Fineness 150De Strength (g/de) 4.0 3.4 4.3 4.2 3.7 3.8 Elongation (%) 35 43 32 34 41 39 Evenness(%) 1.00 0.8 0.9 0.9 1.0 1.0 Dyeing Surface dye concentration (K/S) 10.5 9.6 12.5 11.8 13.5 13.2 Spinning operability excellent excellent excellent excellent excellent excellent

Table 4 Classification Preparation example 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 polyethylene terephthalate resin 80% by weight 60% by weight 93.5% by weight 80% by weight Cationic Dyes - Polyethylene Terephthalate Fiber spinning speed 4000MPM 4000MPM 4000MPM 4000MPM Fineness 150De 150De 150De 150De Strength (g/de) 3.7 Poor spinning 2.8 3.5 Elongation (%) 40 55 32 Evenness(%) 1.2 1.3 0.95 Dyeing Surface dye concentration (K/S) 14.0 7.2 8.8 Spinning operability excellent good good

From the above Tables 3 and 4, it can be confirmed that in the case of fibers prepared using the cationic dye-polyethylene terephthalate composite resins of Preparation Examples 1 to 6, they have excellent mechanical properties (strength, elongation, etc.) as a whole. ) and uniformity, and has excellent dyeability with a surface dye concentration of 9.0 or more.

In contrast, in the case of Comparative Preparation Example 1 prepared using a cationic dye-polyethylene terephthalate composite resin containing more than 35% by weight of 40% by weight of polyester (PE) resin, there was spinnability Very bad question.

Also, in the case of Comparative Preparation Example 2 prepared using a cationic dye-polyethylene terephthalate composite resin containing less than 10% by weight of 6.5% by weight of polyester (PE) resin, it has strength, elongation, etc. The problem of good and poor dyeability.

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

Can confirm through above-mentioned embodiment and preparation example, the polyester resin that is used to prepare cationic dye-polyethylene terephthalate of the present invention not only has suitable inherent viscosity, glass transition temperature and fusing point, but also can be used for sheeting In this case, it has a low sheet moisture content and a high sticking temperature. And can confirm, utilize the above-mentioned cationic dye-polyethylene terephthalate polyester resin and the cationic dye-polyethylene terephthalate fiber prepared by waste polyethylene terephthalate resin to have excellent overall performance. Mechanical properties, and can ensure excellent cationic dyeability.

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Fig. 1 is the preparation of fiber and/or by mixing melted polyester resin (masterbatch) for cationic dye-polyethylene terephthalate and recycled polyethylene terephthalate resin and spinning Or a schematic diagram related to the process of raw silk.

Claims (9)

A kind of polyester resin that is used to prepare cationic dye-polyethylene terephthalate, is characterized in that, comprises the polymer that ester compound is polycondensed, and this ester compound makes acid component and diol component carry out esterification reaction to form Composition, the acid component includes 7mol% to 15mol% of the compound represented by the following chemical formula 1, 7mol% to 10mol% of fatty acid and the remaining amount of carboxylic acid, the diol component includes ethylene glycol or a mixture of diols, the two The alcohol mixture comprises 4mol% to 10mol% of branched diols represented by the following chemical formula 2 and the remaining amount of straight chain diols, the straight chain diols comprising C ₁ ~C ₅ straight chain diols:

In the chemical formula 1, R ¹ and R ² are each independently C ₁ ~ C ₅ straight chain alkyl or C ₃ ~ C ₅ branched chain alkyl, K is Na ⁺ or K ⁺ ,

In the chemical ^{formula 2} , R1 and R4 are each independently a hydrogen atom, _{a C1} - _C10 alkyl group, a C2 _{- C5} alkylene group, a _C5 - _C6 cycloalkyl group or a phenyl group, R ² and R ³ are each independently a C ₁ -C ₅ alkylene group, but the case where both R ¹ and R ⁴ are hydrogen atoms is excluded. The polyester resin used to prepare cationic dye-polyethylene terephthalate as described in claim 1, wherein the fatty acid comprises a group selected from the group consisting of adipic acid, succinic acid and glutaric acid The carboxylic acid contains at least one selected from the group consisting of C ₆ -C ₁₄ aromatic polycarboxylic acids and C ₂ -C ₁₆ aliphatic polycarboxylic acids. The polyester resin used to prepare cationic dye-polyethylene terephthalate as described in claim 1, wherein the degree of polymerization of the polymer is 120-180. The polyester resin used to prepare cationic dye-polyethylene terephthalate as described in any one of claim items 1 to 3, wherein the intrinsic viscosity of the polyester resin is 0.40dl/g~ 0.80dl/g, the glass transition temperature is 58℃~75℃, and the melting temperature is 180℃~220℃. A masterbatch sheet for preparing cationic dye-polyethylene terephthalate, characterized in that it contains the polyester resin described in any one of claims 1 to 3. A cationic dye-polyethylene terephthalate composite resin, characterized in that it comprises the polyester resin and polyethylene terephthalate resin described in any one of claims 1 to 3. The cationic dye-polyethylene terephthalate composite resin as described in claim 6, wherein the polyethylene terephthalate resin comprises recycled polyethylene terephthalate derived from waste products ester resin. A fiber characterized by comprising the cationic dye-polyethylene terephthalate composite resin described in claim 6, cationic dye and additives. The fiber according to Claim 8, wherein the fiber satisfies a surface dye concentration of 9.0 to 15.0.

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