KR102288463B1 - Hot-water elutable polyester resin having high heat-resistance and weight loss-rate, and Hot-water elutable polyester composite fiber - Google Patents

Abstract

The present invention relates to a water-soluble polyester resin and a composite fiber using the same. More specifically, it is prepared by applying a specific acid component and a specific diol in an optimal ratio, thereby providing a water-soluble polyester resin having excellent heat resistance and weight loss rate It relates to an invention capable of manufacturing a composite fiber having excellent mechanical properties and the like using the same.

Description

Hot-water elutable polyester resin having high heat-resistance and weight loss-rate, and Hot-water elutable polyester composite fiber

The present invention relates to a water-soluble polyester resin having a high glass transition temperature and having little or no sludge generation during fiber production and elution processing, and a composite fiber manufactured using the same.

Extraction-type composite yarn is manufactured by composite spinning of an extraction component, which is an alkali-soluble polymer, and a fiber-forming polymer, and is mainly produced for the purpose of manufacturing microfibers. In general, co-polyester is mainly used as the extracting component polymer, because it is extracted from alkali solution and weight reduction equipment widely applied to the reduction processing of general polyester without using special equipment and organic solvents that are expensive for recovery treatment. This is because the elution of the component is possible.

Polyamide and polyester are mainly used as the polymer of the fiber-forming component, and recently, cellulose ester, polytrimethylene terephthalate, polybutylene terephthalate, etc. are used for the purpose of imparting functionality.

Alkali-soluble polyesters used as extractable polymers are manufactured by various methods. First, a method of copolymerizing dimethyl isophthalate sulfonate salt or low molecular weight polyalkylene glycol during the polyester polymerization process, a second method of blending polyester with a high molecular weight polyalkylene glycol, and third, a method of blending dimethylisophthalate during the polyester polymerization process There is a method of copolymerizing or blending phthalate sulfonate salt and polyalkylene glycol. In addition, polystyrene or polyethylene is mainly used as the polymer dissolved by the above-mentioned solvent.

However, when the fiber-forming component is polyester, there is a problem in that the fiber-forming component is also taken out in the aqueous alkyli solution upon dissolution of the extract component, thereby reducing the physical properties.

Accordingly, research on an extractable component that can be extracted in water rather than alkali so that there is no effect on the fiber-forming component is continued, and a representative extraction component for this is water-soluble polyester.

The water-soluble polyester is a polycondensation product of ethylene glycol and terephthalic acid, and is prepared by polycondensing various diols, various dicarboxylic acids, and water-soluble components. Therefore, it had a low glass transition temperature (hereinafter referred to as 'Tg'). Such a low Tg causes problems in drying and processing, so that its use is very limited, and there is a problem in that storage and inventory management are difficult due to changes over time after processing.

In addition, in the prior art, 1,4-cyclohexanedimethanol (1,4-cyclohexanedimethanol, hereinafter referred to as 'CHDM') was used to increase the low Tg of the water-soluble polyester, but there is practically no effect _{on the T g and rather the elution and} In the weight reduction process, there was a problem that the weight reduction rate was lowered.

In International Patent Publication No. WO 2002-57334, "a) preparing an aqueous or methanolic slurry comprising 1,4-cyclohexanedimethylol (CHDM) and dicarboxylic acid, wherein the slurry is maintained at a temperature below the melting point of CHDM. Step, b) feeding the slurry to the reactor, c) esterifying the slurry at a temperature and pressure sufficient to effect esterification, optionally in the presence of a suitable catalyst, d) forming a prepolymer, and e) polycondensing a prepolymer in the presence of a suitable catalyst at a temperature and pressure sufficient to effect polycondensation to form a polyester. A manufacturing method is proposed. However, the disclosed technique is to increase the Tg by adding CHDM, but _{it does not substantially affect the T g} , and there is a problem in that the dissolution and the reduction rate are lowered when the dissolution and weight reduction processing are performed. In addition, in the case of the polyester manufactured by the above method, _{there was a problem in that the T g} could not be increased, and there was a problem in that there was a problem in storage and inventory management due to the change over time after processing. In addition, there was a problem in that the economic feasibility of the product was lowered due to the input of additional equipment and manpower for contamination of post-processing equipment due to the generation of sludge during elution processing for the production of fibers using polyester.

Most water-soluble polyesters have _{problems in drying and processing due to their low T g} , and also have been pointed out as disadvantages because there is a problem in that sludge is generated during elution processing and the post-processing equipment is contaminated. _{A novel water-soluble polyester that can improve the T g} of the resin by introducing the polyester resin by introducing the optimal acid component and diol component and these in the optimal composition ratio during resin production, as well as significantly reducing the generation of sludge during dissolution processing An object of the present invention is to provide a resin and a composite fiber using the same.

The present invention for solving the above problems relates to a water-soluble polyester resin having excellent heat resistance and weight loss ratio, and may include a polymer obtained by polycondensation of an oligomer obtained by esterification reaction of a mixture of a specific acid component and a specific diol. .

In a preferred embodiment of the present invention, the acid component is an aromatic polyhydric carboxylic acid having 6 to 14 carbon atoms, a polyvalent dicarboxylic acid having 5 to 14 carbon atoms including a heterocycle, and an aliphatic polyhydric carboxylic acid having 4 to 20 carbon atoms. and at least one selected from compounds represented by the following formula (1).

[Formula 1]

In Formula 1, R ¹ and R ² are independently an alkyl group having 1 to 10 carbon atoms, an alkylene group having 2 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a phenyl group.

In a preferred embodiment of the present invention, the acid component may include at least two selected from the group consisting of the aromatic polyhydric carboxylic acid, the aliphatic polyhydric carboxylic acid, and the compound represented by Chemical Formula 1.

As a preferred embodiment of the present invention, the acid component may include 90 to 95 mol% of the aromatic polyvalent carboxylic acid and 5 to 10 mol% of the compound represented by Chemical Formula 1.

As a preferred embodiment of the present invention, the compound represented by Chemical Formula 1 may be a compound represented by the following Chemical Formula 1-1.

[Formula 1-1]

In Formula 1-1, R ¹ and R ² are independently an alkyl group having 1 to 5 carbon atoms, an alkylene group having 2 to 3 carbon atoms, or a phenyl group.

In a preferred embodiment of the present invention, the diol is an aliphatic diol having 2 to 20 carbon atoms, a diol represented by the following formula (2), a diol represented by the following formula (3), 2,5-furandimethanol, and 1,4-cyclohexane It may be characterized in that it comprises at least one selected from dimethanol.

[Formula 2]

[Formula 3]

In Formula 3, n is 1 or 2.

As a preferred embodiment of the present invention, the compound represented by Formula 2 may be a compound represented by Formula 2-1 below.

[Formula 2-1]

As a preferred embodiment of the present invention, the compound represented by Chemical Formula 3 may be a compound represented by the following Chemical Formula 3-1.

[Formula 3-1]

In a preferred embodiment of the present invention, the diol includes at least two selected from an aliphatic diol having 2 to 20 carbon atoms, a diol represented by Formula 2, a diol represented by Formula 3, and 1,4-cyclohexanedimethanol. It may be characterized by including.

As a preferred embodiment of the present invention, the diol may include 65 to 90 mol% of an aliphatic diol having 2 to 20 carbon atoms, and 10 to 35 mol% of the diol represented by Formula 2 above.

As a preferred embodiment of the present invention, the water-soluble polyester resin of the present invention may include the acid component and the diol in a molar ratio of 1:1.1 to 1.3.

As a preferred embodiment of the present invention, the polymer may be characterized by mixing 5 to 10 parts by weight of polyethylene glycol having a weight average molecular weight of 200 to 900 with respect to 100 parts by weight of the oligomer, followed by polycondensation.

As another preferred embodiment of the present invention, the water-soluble polyester resin of the present invention may further include at least one selected from a metal catalyst, a flame retardant, an antifoaming agent, an antioxidant, and a heat stabilizer.

As a preferred embodiment of the present invention, the metal catalyst may further include a metal catalyst represented by the formula (4).

[Formula 4]

In Formula 4, R ² is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a phenyl group.

As a preferred embodiment of the present invention, the flame retardant may be characterized in that the compound represented by the following formula (5).

[Formula 5]

In Formula 5, R ¹ is -OH, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH, -CH ₂ CH ₂ CH ₂ COOH, or -CH ₂ CH ₂ CH ₂ CH ₂ COOH.

As a preferred embodiment of the present invention, in the water-soluble polyester resin of the present invention, the heat stabilizer is trimethylphosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate. (Tributoxyethyl phosphate), tricresyl phosphate (Tricresyl phosphate), triaryl phosphate isopropylated (Triaryl phosphate isopropylated), hydroquinone bis- (diphenyl phosphate) (Hydroquinone bis- (diphenyl phosphate)) at least one selected from It may be characterized in that it comprises a.

The polyester resin of the present invention described above may have a glass transition temperature (Tg) of 65°C to 85°C, and a weight loss rate of 98.6% to 100% based on Equation 1 below.

[Equation 1]

Loss rate (%) = (A-B)/A × 100

In Equation 1, A is the weight before dissolving the water-soluble polyester resin in hot water of 90, and B is the weight of the insoluble material after dissolving the water-soluble polyester resin in hot water of 90°C. In addition, the weight loss ratio is measured by measuring the weight loss of the water-soluble polyester resin in hot water at 90° C. for 5 minutes with a bath ratio of 40:1.

In addition, the polyester resin can be characterized in that the transmittance is 90% to 98% when the weight loss rate is evaluated and the collected solution is removed, and then ^{measured with a UV-vis spectrometer at 380 cm- 1 wavelength intensity.} there is.

Another object of the present invention relates to a water-soluble polyester (chip) using the water-soluble polyester resin of various types described above.

Another object of the present invention relates to a composite fiber using the water-soluble polyester resin of various types described above, wherein the composite fiber is a sheath-core type, an Island in the Sea type, and a side-by-side type. It may be a side by side type or a segmented pie type.

As a preferred embodiment of the present invention, the water-soluble polyester composite fiber of the present invention may be characterized in that it further comprises a polyester-based resin, a polyamide-based resin, or a polyethylene terephthalate resin.

As a preferred embodiment of the present invention, the water-soluble polyester composite fiber of the present invention is a sheath-core type composite fiber, and may be characterized in that it contains the water-soluble polyester resin as a sheath component or a core component.

As a preferred embodiment of the present invention, the water-soluble polyester composite fiber of the present invention is a sea-island type composite fiber, and may be characterized in that it contains a water-soluble polyester resin as a sea component.

Existing water-soluble polyester resins had to give up thermal properties in order to obtain high water-soluble properties, and because of the low Tg properties of water-soluble polyester resins, there are difficulties in drying and processing when manufacturing products such as fibers using them, and after processing Although there was a disadvantage in that inventory management was difficult due to the observation of changes over time, the novel water-soluble polyester resin of the present invention has a high T _g , so it can solve the difficulties in drying and processing, and it can also improve the change with time after processing. In addition, conventionally, there is an environmental pollution problem by using ESP (easy soluble polymer) that uses a loss of alkali during elution processing, and the cost of wastewater treatment generated during post processing is high, but the polyester of the present invention Resin is an invention that can provide highly economical processed products by remarkably reducing the generation of sludge during elution processing for fiber production because of its high weight loss.

1 to 6 each show a schematic view of a preferred embodiment of the composite fiber of the present invention.

로 표현된 화학식에서, R¹은 독립적으로 수소원자, 메틸기 또는 에틸기이며, a는 1 ~ 3이다"라고 치환기에 대해 표현되어 있을 때, a가 3인 경우, 복수의 R¹, 즉 R¹ 치환기가 3개가 있고, 이들 복수 개의 R¹들 각각은 서로 같거나 다른 것으로서, R¹들 각각은 모두 수소원자, 메틸기 또는 에틸기일 수 있으며, 또는 R¹들 각각은 다른 것으로서, R¹ 중 하나는 수소원자, 다른 하나는 메틸기 및 또 다른 하나는 에틸기일 수 있음을 의미하는 것이다. 또한, R¹의 위치를 특별하게 언급하지 않는 한, 메타(meta), 파라(para) 또는 오쏘(ortho) 중 R¹이 치환되는 위치를 한정한 것이 아니다. 그리고, 상기 내용은 본 발명에서 표현된 치환기를 해석하는 일례로서, 다른 형태의 유사 치환기도 동일한 방법으로 해석되어야 할 것이다.In the present invention "

In the formula represented by When R ¹ is independently a hydrogen atom, a methyl group, or an ethyl group, and a is 1 to 3”, when a is 3, a plurality of R ¹ , that is, R ^{1 There} are three substituents, and these Each of a plurality of R ¹ is the same as or different from each other, ^{and each of R 1} may be a hydrogen atom, a methyl group, or an ethyl group, or ^{each of R 1} is different, one of ^{R 1 is} It means that a hydrogen atom, the other one may be a methyl group, and the other one may be an ethyl group. In addition, ^{unless the position of R 1} is specifically mentioned, the position at which R ¹ is substituted among meta, para, or ortho is not limited. In addition, the above content is an example of interpreting the substituents expressed in the present invention, and similar substituents of other types should be interpreted in the same way.

"로 표현된 화학식에서 "*"표시는 치환기가 연결되는 부위를 의미한다.
In addition, in the present invention "

In the formula represented by ", "*" means a site to which a substituent is connected.

Hereinafter, the present invention will be described in detail.

The water-soluble polyester resin of the present invention is, unlike the water-soluble polyester resin having a low glass transition temperature (Tg) of less than 65°C, 65°C to 85°C, preferably 67°C to 80°C, more preferably 68°C to It has a high glass transition temperature of 75°C.

In addition, the water-soluble polyester resin of the present invention may have an excellent weight loss rate of 98.6% to 100%, preferably 99% to 100%, based on the following Equation 1.

[Equation 1]

Loss rate (%) = (A-B)/A × 100

In Equation 1, A is the weight before dissolving the water-soluble polyester resin in hot water of 90°C, and B is the weight of the insoluble material after dissolving the water-soluble polyester resin in hot water of 90°C. In addition, the weight loss ratio is measured by measuring the weight loss of the water-soluble polyester resin in hot water at 90° C. for 5 minutes with a bath ratio of 40:1.

In addition, the water-soluble polyester resin of the present invention evaluates the weight loss rate and removes insoluble substances from the collected solution, and then, ^{when measured with a UV-vis spectrometer at 380 cm - 1} wavelength, transmittance of 90% to 98% , Preferably it may have a transmittance of 92% to 98%, more preferably a transmittance of 94% to 98%.

And, the water-soluble polyester resin of the present invention may have an intrinsic viscosity (IV) of 0.75 to 0.90, preferably 0.75 to 0.85, at this time, the intrinsic viscosity is measured by pressing the start part of the Visco clock, and then measuring the number of falling seconds. Measurements were made using the Huggins formula or by extrapolation using a graph.

Hereinafter, the composition and composition ratio of the water-soluble polyester resin of the present invention having such excellent physical properties will be described in detail.

The water-soluble polyester resin of the present invention includes a polymer prepared by preparing an oligomer by esterifying a mixture of an acid component and a diol, and then performing a polycondensation reaction with the oligomer and polyethylene glycol.

In the present invention, the acid component is an aromatic polyhydric carboxylic acid having 6 to 14 carbon atoms, a polyhydric dicarboxylic acid having 5 to 14 carbon atoms including a heterocycle, an aliphatic polyhydric carboxylic acid having 4 to 20 carbon atoms, and the following Chemical Formula 1 at least one selected from the compounds represented by It may include a carboxylic acid and a compound represented by Formula 1.

[Formula 1]

In Formula 1, R ¹ and R ² are independently an alkyl group having 1 to 10 carbon atoms, an alkylene group having 2 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms or a phenyl group, preferably an alkyl group having 1 to 5 carbon atoms. , an alkylene group having 2 to 3 carbon atoms or a cycloalkyl group having 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

And, as an acid component, when a mixture of the aromatic polyhydric carboxylic acid and the compound represented by Formula 1 is used, 90 to 95 mol% of the aromatic polyhydric carboxylic acid and 5 to 10 mol% of the compound represented by Formula 1 As a result, it is preferable to use 90.5 to 93 mol% of the aromatic polyhydric carboxylic acid and 7 to 9.5 mol% of the compound represented by Formula 1. At this time, if the amount of the compound represented by Formula 1 is less than 5 mol%, the glass transition temperature improvement effect may be reduced, or water solubility may be reduced, and if the amount of the compound represented by Formula 1 exceeds 10 mol%, Since there may be a problem that the reduction rate is lowered, it is recommended to use it within the above range.

In the present invention, the aromatic polyhydric carboxylic acid may include an aromatic polyvalent carboxylic acid having 6 to 14 carbon atoms, preferably one or two selected from terephthalic acid and dimethyl terephthalate, more preferably terephthalic acid. can be used alone.

In addition, as the polyvalent dicarboxylic acid including a heterocycle, a polyvalent dicarboxylic acid having 5 to 14 carbon atoms including a heterocycle may be used, preferably 2,5-furandicarboxylic acid, 2,5- It may include at least one selected from thiophene dicarboxylic acid and 2,5-pyrrole dicarboxylic acid.

In addition, the aliphatic polyhydric carboxylic acid may be an aliphatic polyhydric carboxylic acid having 4 to 20 carbon atoms, preferably oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, citric acid, and pimer. acid, azelaic acid, sebacic acid, nonanoic acid, decanoic acid, dodecanoic acid, and hexanodecanophosphoric acid may include one or two or more selected from the group consisting of, and when introducing an aliphatic polyhydric carboxylic acid, hardness improvement and water May increase solubility.

In addition, the compound represented by the formula (1) may preferably be a compound represented by the following formula (1-1).

[Formula 1-1]

In Formula 1-1, R ¹ and R ² are independently an alkyl group having 1 to 10 carbon atoms, an alkylene group having 2 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, or a phenyl group, preferably having 1 to 5 carbon atoms. of an alkyl group, an alkylene group having 2 to 3 carbon atoms, or a cycloalkyl group having 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

When explaining the diol component used in the preparation of the water-soluble polyester resin of the present invention, in the present invention, the diol is an aliphatic diol having 2 to 20 carbon atoms, a diol represented by the following formula (2), a diol represented by the following formula (3), 2 ,5-furandimethanol and 1,4-cyclohexanedimethanol may include at least one selected from, preferably an aliphatic diol having 2 to 20 carbon atoms, a diol represented by the formula 2, and a diol represented by the formula 3 It may include two or more selected from diol and 1,4-cyclohexanedimethanol, more preferably, an aliphatic diol having 2 to 20 carbon atoms, and a diol represented by Formula 2 may be mixed and used.

And, as the diol component, when a mixture of an aliphatic diol having 2 to 20 carbon atoms and a diol represented by Formula 2 is used, 65 to 90 mol% of an aliphatic diol having 2 to 20 carbon atoms and a diol represented by Formula 2 10 to 35 mol %, preferably 70 to 85 mol % of an aliphatic diol having 2 to 20 carbon atoms, and 15 to 30 mol % of the diol represented by Formula 2 are mixed and used. In this case, when the amount of the diol represented by Formula 2 is less than 10 mol%, there may be a problem that the glass transition temperature improvement effect is greatly reduced, and when the amount of the diol represented by Formula 2 exceeds 35 mol%, the amount of the resin There is a problem in that the intrinsic viscosity is increased and the moldability is deteriorated, so it is preferable to use it within the above range.

[Formula 2]

[Formula 3]

In Formula 3, n is 1 or 2, preferably n is 1.

Among the diol components, aliphatic diols having 2 to 20 carbon atoms are ethylene glycol, diethylene glycol, propylene glycol, trimethyl glycol, tetramethylene glycol, pentamethyl glycol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene. It may include one or more selected from glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol and tridecamethylene glycol, preferably ethylene glycol, propylene glycol, trimethyl glycol and tetramethylene glycol. , may include one or two or more selected from pentamethyl glycol, and more preferably, one or two or more selected from ethylene glycol, diethylene glycol and propylene glycol.

And, among the diol components, the diol represented by the formula (2) may preferably be a diol represented by the following formula (2-1).

[Formula 2-1]

In addition, among the diol components, the diol represented by Formula 3 may preferably be a diol represented by the following Formula 3-1.

[Formula 3-1]

The water-soluble polyester resin of the present invention is a mixture of the acid component and the diol component described above in a molar ratio of 1: 1.0 to 1.4, preferably in a molar ratio of 1: 1.1 to 1.3, more preferably in a molar ratio of 1:15 to 1.25. An esterification reaction may be performed to prepare an oligomer. In this case, if the diol component is less than 1.0 molar ratio, there is a problem in that the polymer yield is lowered, and if it is used in excess of 1.4 molar ratio, there is a problem in that a lot of unreacted diol components are generated.

And, a polymer can be prepared by polycondensation of the oligomer and polyethylene glycol. At this time, 5 to 10 parts by weight of polyethylene glycol, preferably 6 to 9 parts by weight of polyethylene glycol, are mixed with respect to 100 parts by weight of the oligomer. Polymers can be prepared by polymerization.

In addition, it is advantageous to use polyethylene glycol having a weight average molecular weight of less than 1,000 in terms of improving the reduction rate, preferably polyethylene glycol having a weight average molecular weight of 200 to 900, and more preferably polyethylene glycol having a weight average molecular weight of 200 to 800 It is recommended to use , and if the weight average molecular weight exceeds 1,000, the intrinsic viscosity may be too high, and there may be a problem of poor moldability.

The water-soluble polyester resin of the present invention may further include at least one selected from a metal catalyst, a flame retardant, an antifoaming agent, an antioxidant, and a heat stabilizer in addition to the polymer.

In the present invention, as the metal catalyst, a catalyst used in the esterification reaction in the art may be used, and preferably, a metal catalyst represented by Chemical Formula 4 may be used.

[Formula 4]

In Formula 4, R ² is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a phenyl group, preferably an alkyl group having 1 to 3 carbon atoms or 5 carbon atoms. to 6 cycloalkyl groups.

In the present invention, the flame retardant may use a general flame retardant used in the art, but in consideration of compatibility with the polymer of the present invention, it is preferable to use a compound represented by the following formula (5).

[Formula 5]

In Formula 5, R ¹ is -OH, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH, -CH ₂ CH ₂ CH ₂ COOH or -CH ₂ CH ₂ CH ₂ CH ₂ COOH, preferably is —CH ₂ CH ₂ COOH or —CH ₂ CH ₂ CH ₂ COOH.

In the present invention, the antifoaming agent is not particularly limited, and a general one used in the art may be used, and the amount used in addition is 100 to 500 ppm, preferably 150 to 300 ppm of the total weight of the polyester resin. good to use

In the present invention, the antioxidant is not particularly limited, and a general one used in the art may be used, and in addition, the amount used is 300 to 900 ppm, preferably 400 to 700 ppm.

In the present invention, the heat stabilizer is not particularly limited, but trimethylphosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, tricrezyl One or two or more selected from phosphate (Tricresyl phosphate), triaryl phosphate isopropylated, hydroquinone bis- (diphenyl phosphate) may be used, The amount used is 50 to 1,000 ppm of the total weight of the resin, preferably 100 to 400 ppm, and at this time, if the amount is less than 50 ppm, the thermal stability effect may hardly be seen, and it exceeds 1,000 ppm Since there is almost no increase in the thermal stability effect compared to the input amount, it is uneconomical, and it is better to use it within the above range because the weight loss rate can be lowered.

In addition, the polycondensation reaction may be performed by stirring at a speed of 40 to 80 rpm for 120 to 180 minutes at 240° C. to 290° C.

The present invention can provide a water-soluble polyester ??(chip) that is easy to dry and melt process and has little change over time after processing by using the water-soluble polyester resin described above.

In addition, the present invention can manufacture a composite fiber using the water-soluble polyester resin described above, and the composite fiber of the present invention is a sheath-core type as shown in FIG. 1, a sea-island type as shown in FIG. 2, and a side-by-side type as shown in FIG. It can be used in the manufacture of composite fibers having a shape, such as a divided pie type as shown in FIG. 4, as well as a mosaic type as shown in FIG. 5, or a matrix-dispersion type, nebula type, and the like as shown in FIG.

More specifically, the composite fiber of the present invention may include a fiber-forming component typically included in the composite fiber in addition to the water-soluble polyester resin according to the present invention as an extractable component, The fiber-forming component may preferably include a polyester-based resin, a polyamide-based resin, or a polyethylene terephthalate resin, and more preferably a polyethylene terephthalate resin.

The fineness of the composite fiber of the present invention is preferably 0.5 to 3 De, and when it is less than 0.5 De, there may be a problem of reduced cross-section and workability, and when it exceeds 3 De, there is a problem of deterioration of yarn sensitivity and poor dissolution. there may be

1 is a cross-sectional view of a sheath-core type composite fiber according to a preferred embodiment of the present invention. As shown in FIG. 1, in the case of a sheath-core type composite fiber, more preferably, the first component may serve as the core component 21 and the second component as the sheath component 20 . Conversely, when spinning with the second component as the core component and the first component as the sheath component, a yarn having a target fineness can be obtained.

In addition, FIG. 2 is a cross-sectional view of an Island in the Sea type composite fiber according to a preferred embodiment of the present invention, and more preferably, the first component is a sea component, rather than an Island in the Sea type fiber. (30) and may be an Island in the Sea type fiber having the second component as the island component (31). In this case, the number of island components 31 is preferably 5 to 1,000, and the fineness of the island components 31 may be 0.2 to 0.8 De. And, by including the first component as the sea component 30, microfibers including the island component can be obtained. On the other hand, when spinning with the second component as the sea component and the first component as the island component, multi-pore fibers can be obtained after elution, and the effect of light weight and heat retention can be obtained according to the amount of air content of the hollow.

The present invention will be described in more detail through the following examples, but the following examples are not intended to limit the scope of the present invention, which should be construed to aid understanding of the present invention.

[ Example ]

Example 1: Preparation of water-soluble polyester resin

An acid component was prepared by mixing 91.35 mol% of terephthalic acid and 8.65 mol% of a compound represented by the following Chemical Formula 1-1.

Next, a diol component was prepared by mixing 70 mol% of ethylene glycol, 10 mol% of diethylene glycol, and 20 mol% of a compound represented by the following Chemical Formula 2-1.

Next, the acid component and the diol component were mixed in a molar ratio of 1: 1.2, and then an oligomer was prepared through an ester reaction while stirring at 250° C. for 160 minutes at a speed of 56 rpm.

Next, after mixing 7.53 parts by weight of polyethylene glycol having a weight average molecular weight of 400 with respect to 100 parts by weight of the oligomer and stirring at 56 rpm for 120 minutes at 275° C. ppm, 200 ppm of phosphoric acid was added as a heat stabilizer, stirred sufficiently, and then discharged to obtain a water-soluble polyester resin.

[Formula 1-1]

In Formula 1-1, R ¹ and R ² are methyl groups.

[Formula 2-1]

Example 2 ~ Example 4 and comparative example 1 ~ comparative example 6

A water-soluble polyester resin was prepared in the same manner as in Example 1, but by preparing a water-soluble polyester resin to have the composition and composition ratio of Table 1 below, Examples 2 to 4 and Comparative Examples 1 to 6 were prepared. Each was carried out.

division Example
One Example
2 Example
3 Example
4 comparative example
One comparative example
2 comparative example
3 comparative example
4 comparative example
5 comparative example
6
acid
(mol%) TPA 91.35 93 90.2 91.35 71.35 81.35 91.35 91.35 88 91.35 IPA - - - - 20 10 - - - - Formula 1-1 8.65 7.0 9.8 8.65 8.65 8.65 8.65 8.65 12 8.65 Dior
ingredient
(mol%) EG 70 70 70 67 90 80 70 70 70 85 DEG 10 10 10 5 10 10 10 10 10 10 CHDM - - - - - 20 - - - Formula 2-1 20 20 20 28 - 10 0 20 20 5 oligomer 100 parts by weight (acid component: diol component = 1:1.2 molar ratio)
polyethylene glycol PEG400 7.53 7.53 7.53 8.5 7.55 7.53 7.53 - 7.53 7.53 PEG1000 - - - - - 7.53 - - antifoam 200 ppm heat stabilizer 200 ppm TPA: terephthalic acid, IPA: isophthalic acid, EG: ethylene glycol
DEG: diethylene glycol, CHDM: 1,4-cyclohexanedimethanol
PEG400: Polyethylene glycol having a weight average molecular weight of 400
PEG1000: Polyethylene glycol having a weight average molecular weight of 1000
Experimental Example 1: Measurement of physical properties of water-soluble polyester resin

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The physical properties of the water-soluble polyester resins prepared in Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 2 below.

(One) intrinsic viscosity (IV) Measurement

After mixing phenol and trichlorethylene (TCE) as a solvent in the flask at a weight ratio of 60: 40, the polymer sample was read up to 0.1 mg and stirred on a hot plate at a level of 0.4 g/dl of the solution. Next, after introducing the water-soluble polyester resin, it was dissolved in a temperature range of 110 ~ 120 ℃ 40 minutes. Next, the prepared polymer solution was placed in a constant temperature water bath (water bath, set temperature of 25.0° C.) for 30 minutes to achieve equilibrium with a temperature of 25.0° C. of a viscosity bath. Next, the measurement sample was placed in a Ubbelohde-type capillary viscometer tube up to line d, and then the viscometer was matched to a Visco clock. Next, in the viscometer located in the Visco clock, part c was automatically packed, and the polymer solution was filled with a solution higher than the scale line e of tube b using a rubber aspirator. After pressing the start part of the Visco clock, the number of falling seconds was measured, and the intrinsic viscosity was measured using the Huggins calculation formula.

(2) glass transition temperature ( T _g ) measurement

Differential scanning calorimetry (DSC) was performed on the water-soluble polyester resin for glass transition

The degree (Tg) was measured.

(3) reduction rate ( % ) measurement

The bath ratio was fixed at 40:1 and the water-soluble polyester resin was dissolved in hot water at 90° C. for 5 minutes, and the change in weight loss of the water-soluble polyester resin was calculated based on Equation 1 below.

[Equation 1]

Loss rate (%) = (A-B)/A × 100

In Equation 1, A is the weight before dissolving the water-soluble polyester resin in hot water of 90°C, and B is the weight of the insoluble material after dissolving the water-soluble polyester resin in hot water of 90°C.

(4) transmittance ( % ) measurement

The transmittance was measured by collecting the solution generated during the measurement of the reduction rate, and then measuring the solution from which the insoluble matter was removed at a wavelength ^{of 380 cm - 1 wavelength using a UV-vis spectrometer.}

division intrinsic viscosity glass transition temperature
(℃) weight loss rate
(%) transmittance
(%) Example 1 0.81 68.7 100 94.2 Example 2 0.83 67.9 99.7 93.4 Example 3 0.83 73.2 98.9 92.1 Example 4 0.88 71.5 99.5 93.3 Comparative Example 1 0.76 60.03 98.4 73.5 Comparative Example 2 0.80 56.75 100 65.7 Comparative Example 3 0.70 51.57 97.7 76.8 Comparative Example 4 0.80 63.21 92.4 73.2 Comparative Example 5 0.79 68.6 96.5 88.7 Comparative Example 6 0.80 62.3 99.1 91.8

Looking at the experimental results of Table 2, in the case of Examples 1 to 4, it was confirmed that the bar had a high glass transition temperature of 65 ℃ or more, and had excellent thermal properties. And, it was confirmed that it had a high weight loss ratio of 98.6% or more and a high transmittance of 90% or more, and through this, it was confirmed that the solubility of the polyester resin of the present invention was excellent, and it was possible to prevent and/or minimize the generation of sludge after dissolution. could

However, in the case of Comparative Examples 1 and 2 using isophthalic acid, the transmittance was very low as 73.5%, and there was a problem in that a lot of sludge was generated. In addition, in the case of Comparative Example 2 in which the diol represented by Formula 2-1 was not used, compared with Example 1, the glass transition temperature was significantly lower, and thus there was a problem in that the thermal properties were poor.

In addition, in the case of Comparative Example 3 using 1,4-cyclohexanedimethanol (CHDM) as a diol, compared with Example 1, not only the glass transition temperature, but also the weight loss rate and the transmittance were poor. , in the case of Comparative Example 4 using polyethylene glycol having a weight average molecular weight of 1000, the glass transition temperature was high, but the weight loss rate and transmittance were significantly reduced. In addition, in the case of Comparative Example 5, in which the compound represented by Formula 1-1 was used in excess of 10 mol%, there was no significant change in the glass transition temperature and intrinsic viscosity, compared to Example 1, but the reduction rate and transmittance were rather greatly reduced. showed a tendency to And, in the case of Comparative Example 6 using less than 10 mol% of the diol represented by Chemical Formula 2-1, compared with Example 1, the glass transition temperature improvement effect was very low.

manufacturing example One

A polyethylene terephthalate resin having an intrinsic viscosity (IV) of 0.65 (prepared by polymerizing 100 mol% terephthalic acid and 100 mol% ethylene glycol, Resin 2) was prepared.

Then, the water-soluble polyester resin (Resin 1) prepared in Example 1 and the resin 2 were prepared as an island-in-the-sea yarn type composite fiber in which Resin 1 was used as a sea component and Resin 2 was used as an island component under the following conditions.

[Conditions for manufacturing composite fibers]

Resin 1 was put into a kneader in which the temperature from the input part to the spin block was set at 220°C - 255°C - 265°C - 280°C. In addition, Resin 2 was added to the kneader whose temperature from the input part to the spin block was set to 220°C - 275°C - 285°C - 280°C.

Then, an island-in-the-sea yarn type composite fiber was prepared by spinning from a sea-island yarn spinneret at a discharge ratio of Resin 1 and Resin 2 of 3:7 under the conditions of a draw temperature of 80° C., a heat setting temperature of 120° C., a draw ratio of 2.85 times, and a winding speed of 4,000 mpm.

Comparative Preparation Example 1 ~ Comparative Preparation Example 5

It was carried out in the same manner as in Preparation Example 1, but Comparative Preparation Examples 1 to 4 were prepared using each of the water-soluble polyester resins of Comparative Examples 1 to 4 instead of the water-soluble polyester resin of Example 1 to prepare sea-island yarn type composite fibers.

In Comparative Preparation Example 5, a biodegradable polyester resin (ECOWAY-B of Toray Chemical) was used instead of Resin 2 above.

Experimental example 2: Measurement of properties of composite fibers

The strength, elongation, weight loss, and transmittance of the composite fibers prepared in Preparation Examples 1 to 4 and Comparative Preparation Examples 1 to 5 were measured, and the results are shown in Table 3 below.

(1) Measurement of strength and elongation

Tensile strength and tensile elongation were measured using a universal test machine (Instron) for mechanical properties of fibers in accordance with ASTM D3217. Strength and elongation are defined as the value (g/de) obtained by dividing the applied load by the denier (g/de) when the fiber is stretched until it is cut by applying a constant force. did.

(2) reduction rate ( % ) measurement

The bath ratio was fixed at 40:1 and the water-soluble polyester resin was dissolved in hot water at 90° C. for 5 minutes, and the change in weight loss of the water-soluble polyester resin was calculated based on Equation 2 below.

[Equation 2]

Loss rate (%) = (A-B)/A × 100

In Equation 1, A is the weight before dissolving the composite fiber in 90°C hot water, and B is the weight of the insoluble matter after dissolving the composite fiber in 90°C hot water.

(4) transmittance ( % ) measurement

The transmittance was measured by collecting the solution generated during the measurement of the reduction rate, and then measuring the solution from which the insoluble matter was removed at a wavelength ^{of 380 cm - 1 wavelength using a UV-vis spectrometer.}

division form Mono Island
(de) robbery
(g/de) Shinto
(%) weight loss rate
(%) transmittance
(%) Preparation Example 1 Sea Islands 2.03 3.37 35.7 97.8 95.1 Preparation 2 Sea Islands 2.05 3.35 36.4 97.2 94.5 Preparation 3 Sea Islands 2.09 3.39 35.5 95.9 93.0 Preparation 4 Sea Islands 2.10 3.41 35.0 97.7 95.3 Comparative Preparation Example 1 Sea Islands 2.10 3.23 38.0 92.6 76.7 Comparative Preparation Example 2 Sea Islands 2.08 3.40 32.6 96.7 69.3 Comparative Preparation Example 3 Sea Islands 2.13 3.27 33.7 94.7 80.6 Comparative Preparation Example 4 Sea Islands 2.20 3.38 38.2 90.1 78.4 Comparative Preparation Example 5 Sea Islands 2.01 3.10 34.9 98.1 93.4

Looking at the experimental results of Table 3, it can be seen that the composite fiber of the present invention has excellent mechanical properties such as strength of 3.25 g/de or more and elongation of 34% or more, while having a weight loss ratio of 95% or more and a transmittance of 90% or more. could

However, in Comparative Preparation Examples 1 to 4, the transmittance was very poor, and Comparative Preparation Example 5 was superior to other Comparative Preparation Examples in terms of elongation, weight loss, and transmittance, but in Preparation Example 1 in terms of strength. When compared with ~4, it showed poor results.

Through the above Examples and Experimental Examples, the water-soluble polyester resin of the present invention has a high glass transition temperature, and has excellent thermal properties such as heat resistance and excellent weight loss and transmittance. Compared with the existing polyester resin, It was confirmed that, while drying and processing were easy, contamination of post-processing facilities due to sludge generated during dissolution processing could be minimized. In addition, it was confirmed that the composite fiber prepared from the water-soluble polyester resin of the present invention can provide a composite fiber having excellent mechanical properties such as strength and elongation, and excellent weight loss and transmittance.

Claims (19)

It is a polyester resin comprising a polymer, an antifoaming agent and a heat stabilizer,
The polymer includes a polymer obtained by polycondensation of 5 to 10 parts by weight of polyethylene glycol having a weight average molecular weight of 200 to 800 with respect to 100 parts by weight of an oligomer obtained by esterification of a mixture containing an acid component and a diol component,
The acid component includes 90 to 95 mol% of terephthalic acid and 5 to 10 mol% of the compound represented by Formula 1-1,
The diol component includes 15 to 30 mol% of a diol represented by the following Chemical Formula 2-1 and 70 to 85 mol% of an aliphatic diol,
The aliphatic diol includes an aliphatic diol having 2 to 20 carbon atoms,
Glass transition temperature (Tg) 65 ℃ ~ 85 ℃, heat-water-eluting polyester resin excellent in heat resistance and weight loss rate, characterized in that the weight loss rate is 98.6% ~ 100% based on Equation 1 below;
[Formula 1-1]

In Formula 1-1, R ¹ and R ² are independently an alkyl group having 1 to 5 carbon atoms, an alkylene group having 2 to 3 carbon atoms, or a phenyl group,
[Formula 2-1]

[Equation 1]
Loss rate (%) = (AB)/A × 100
In Equation 1, A is the weight before dissolving the hot water elutable polyester resin in hot water at 90 ° C. The weight loss of the hot water elutable polyester resin was measured in hot water at 90° C. for 5 minutes by fixing the bath ratio of 40:1.
[Claim 2] The hot-water leaching polyester resin having excellent heat resistance and weight loss ratio according to claim 1, wherein the acid component and the diol are contained in a molar ratio of 1:1 to 1.3.
delete delete delete [Claim 2] The hot-water leaching polyester resin having excellent heat resistance and weight loss ratio according to claim 1, further comprising at least one selected from a metal catalyst, a flame retardant, and an antioxidant.
[Claim 7] The method of claim 6, wherein the metal catalyst further comprises a metal catalyst represented by Chemical Formula 4;
[Formula 4]

In Formula 4, R ² is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or a phenyl group.
[Claim 7] The method of claim 6, wherein the flame retardant is a compound represented by the following Chemical Formula 5;
[Formula 5]

In Formula 5, R ¹ is -OH, -COOH, -CH ₂ COOH, -CH ₂ CH ₂ COOH, -CH ₂ CH ₂ CH ₂ COOH, or -CH ₂ CH ₂ CH ₂ CH ₂ COOH.
According to claim 1, wherein the heat stabilizer is trimethyl phosphate (trimethylphosphate), triethyl phosphate (Triethyl phosphate), tributyl phosphate (Tributyl phosphate), tributoxyethyl phosphate (Tributoxyethyl phosphate), tricresyl phosphate (Tricresyl phosphate) , triaryl phosphate isopropylated (Triaryl phosphate isopropylated), hydroquinone bis- (diphenyl phosphate) (Hydroquinone bis- (diphenyl phosphate)) excellent heat resistance and weight loss rate, characterized in that it comprises at least one selected from the group consisting of Hot water dissolvable polyester resin.
delete delete delete According to claim 1, wherein the heat resistance of the reduction rate as the evaluation and removal of the insoluble material was collected solution was measured to the next, 380 ㎝ ^-1 wavelength intensity by UV-vis spectroscopy, characterized in that the transmittance is 90% ~ 98%, and A hot water leaching polyester resin with an excellent weight loss rate.
The hot water leaching polyester (chip) which is a molded article of the hot water leaching polyester resin of claim 1.
The hot water leaching polyester composite fiber comprising the hot water leaching polyester resin of claim 1 .
The method of claim 15, further comprising a polyester-based resin or a polyamide-based resin,
Sheath-core (Sheath-Core) type, island in the Sea type, side by side (Side by side) type or segmented pie (segmented pie) type composite fiber, characterized in that the hot water leaching polyester composite fiber.
delete 16. The method of claim 15, wherein the composite fiber is a sheath-core type composite fiber,
Hot water leaching polyester composite fiber, characterized in that it comprises a sheath component or a core component as the hot water dissolving polyester resin.
16. The method of claim 15, wherein the composite fiber is a sea-island type composite fiber,
Hot water leaching polyester composite fiber, characterized in that it comprises the hot water leaching polyester resin as a sea component.

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