KR20050039125A - A copolymerized polyester resin with excellent water dispersion property under alkali condition, and a process of preparing for the same - Google Patents

Abstract

The present invention relates to an alkali water-dispersible copolyester resin and a method for manufacturing the same, and an object of the present invention is excellent in the adhesiveness, flexibility, and strength with yarns, and excellent in water dispersibility and alkali water dispersibility. It is to provide a copolyester resin which can be used zero, and its manufacturing method. In order to achieve this object, in the present invention, (i) an aromatic difunctional carboxylic acid compound, (ii) a difunctional alcohol compound, and (iii) -SO ₃ M (M is a hydrogen atom or an alkali metal atom) functional group Aromatic difunctional carboxylic acid compound, (iv) aliphatic difunctional carboxylic acid compound, and (iii) polyethylene glycol were introduced into the reactor, followed by esterification reaction or transesterification reaction, followed by polycondensation reaction to obtain a number average molecular weight. An alkali water dispersible copolyester resin having 5,000 to 15,000 and a glass transition temperature (Tg) of 30 to 60 ° C is prepared.

Description

Alkaline water dispersible copolymer polyester resin and method for preparing the same {A copolymerized polyester resin with excellent water dispersion property under alkali condition, and a process of preparing for the same}

The present invention relates to an alkali water-dispersible co-polyester resin useful as an auxiliary agent used when sizing warp yarns in a weaving preparation process of a synthetic fiber fabric, and a manufacturing method thereof.

In general, when weaving fabrics with synthetic fiber yarns, warp is cut during weaving due to friction between the loom and the yarns. In order to prevent this, a sizing to give a warp to the warp in the preparation process before weaving. It goes through the process. Up to now, the warp sizing agents have been mainly used water-dispersible polyvinyl alcohol, polyvinylacetate, vinyl acrylate resins, but they have weak adhesive strength with synthetic fibers, especially polyester yarns, and have low flexibility and adhesive strength. There is. As a result, the amount of use of the agent is increased, and manufacturing costs are increased, and the weaving operation rate and the fabric passing rate are lowered due to poor sizing. In addition, in the case of these hoes, there is a difficulty in the work that must be used for the jet jet loom, air jet loom, repier loom, shuttle loom according to their manufacturing process.

Conventional water-dispersible polyester resin production techniques for solving such problems are known in the United States Patent Nos. 3,546,008, 3,853,820, 4,156,073 and the like. These U.S. Pat. In order to impart water solubility or water dispersibility to a polyester resin, a method of adding an aromatic compound having a -SO ₃ M (M is a hydrogen atom or an alkali metal) functional group is described.

However, the conventional water-dispersible polyester resin manufacturing technology has solved the problem of weak adhesive strength with the yarn in the sizing process, and inferior flexibility and adhesive strength. I have a problem. Generally, the decanting process includes alkali components such as caustic soda (usually 0.5-1%) or sodium carbonate (1-2.5%), but water-dispersible polyvinyl alcohol, polyvinylacetate, and vinyl acrylate resins have no problem. The water dispersible polyester resins provided in the prior US patent technology are not water dispersible under alkaline conditions. Therefore, it cannot be used as a catalyst because it cannot be removed under alkaline triggering conditions.

The present invention aims to provide a copolyester resin and a method for producing the same, which are particularly useful as an inclination sizing agent because of excellent adhesion and flexibility with synthetic fiber yarns, and excellent water dispersibility even during the invoking process under alkaline conditions.

Hereinafter, the copolymer polyester resin which is excellent in water dispersibility also is called "alkali water dispersible copolymer polyester resin" also in the decal process under alkaline conditions.

Method for producing an alkali water-dispersible polyester resin of the present invention for achieving such a problem, the aromatic difunctional carboxylic acid compound of the general formula (I) below, the difunctional alcohol compound of the general formula (II), An aromatic difunctional carboxylic acid compound having a -SO ₃ M (M is a hydrogen atom or an alkali metal atom) functional group of the general formula (III), an aliphatic difunctional carboxylic acid compound of the general formula (IV), and Polyethylene glycol of the general formula (V) is introduced into a reactor to perform an esterification reaction or a transesterification reaction, followed by a polycondensation reaction.

ROOC-C ₆ H ₄ -COOR (Ⅰ)

HO-(CH ₂ ) n-OH (II)

_{C 6 H 3 - (COOR)} 2 · SO 3 M (Ⅲ)

HOOC-(CH ₂ ) n-COOH (Ⅳ)

H-(OCH ₂ CH ₂ ) m -OH (Ⅴ)

In formulas (I) to (V), R is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, n is an integer of 2 to 5, M is a hydrogen atom or an alkali metal atom, and m is an integer of 2 to 10 .

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

In the present invention, the monomers of the general formulas (I) to (V), which are the main raw materials, are introduced into the reactor at a constant weight ratio, and the esterification or transesterification is carried out stepwise so that the number average molecular weight is 5,000 to 15,000 at 100 to 260 ° C. Reaction and polycondensation reaction. Hereinafter, "esterification reaction or transesterification reaction" is abbreviated as "ester exchange reaction." In the reaction, one or more reactors are used, and the transesterification and polycondensation reactions are carried out simultaneously or sequentially. The aromatic difunctional carboxylic acid compound of the general formula (I), which is used as a raw material for imparting strength, wear resistance and flexibility to the coating of the coating agent, is selected from the first group consisting of dimethyl terephthalate and ester-forming derivatives of dimethyl terephthalate. One or two or more compounds selected from the second group consisting of one or more selected compounds and ester forming derivatives of dimethylisophthalate and dimethylisophthalate are used. Glass transition temperature, which is one of the thermal properties of polymers, is important for the use of fiber sizing agents. The ratio of the use of the first group compound to the second group compound greatly affects the glass transition temperature. The use ratio of the compound is 70 to 90% by weight: 30 to 5% by weight, more preferably 80 to 90% by weight: 20 to 10% by weight.

Meanwhile, as the bifunctional alcohol compound of the general formula (II), one or two or more compounds selected from the group consisting of ethylene glycol, propanediol, butanediol and pentanediol are used. These usage-amounts are 40-80 weight part with respect to 100 weight part of aromatic difunctional carboxylic acid compounds of the said general formula (I), More preferably, 55-70 weight part is good.

Examples of the aromatic difunctional carboxylic acid compound of the general formula (III) which impart water dispersibility to the resin include 5-sodiumsulfodimethylisophthalate, 4-sodiumsulfodimethylisophthalate, 5-sodiumsulfodimethylterephthalate and their Alkali metal salts are used. More preferably, 5-sodiumsulfodimethylisophthalate is used. When the amount of the aromatic difunctional carboxylic acid compound of the general formula (III) is too small, there is a problem in water dispersibility, and when too large, the moisture absorption rate, which is one of the important physical properties of the coating agent, becomes high, resulting in a problem such as a decrease in weaving operation rate. These usage-amounts are 10-30 weight part with respect to 100 weight part of said aromatic bifunctional carboxylic acid compound of the said general formula (I), More preferably, 15-25 weight part is good.

As the aliphatic bifunctional carboxylic acid compound of the general formula (IV) introduced to impart alkali water dispersibility, one or two or more selected from the group consisting of succinic acid, adipic acid and sebacic acid are used. As polyethyleneglycol of the said General formula (V), the thing of 100-500 molecular weight is used, More preferably, it is 200-400 molecular weight. The aliphatic difunctional carboxylic acid compound of the general formula (IV) is used in an amount of 9 to 15 parts by weight based on 100 parts by weight of the aromatic difunctional carboxylic acid compound of the general formula (I), and the general formula (V) It is preferable to use 1-5 weight part of polyethylene glycols.

The alkali water-dispersible copolyester resin of the present invention prepared in this manner has a number average molecular weight of 5,000 to 15,000, and a glass transition temperature (Tg) of 30 to 60 ° C.

If the number average molecular weight is less than 5,000, not only water dispersion but also alkali water dispersion, but the required impact strength and adhesive strength is not expressed, and if the molecular weight exceeds 15,000, the impact strength and adhesion is excellent, but the water dispersion and alkali dispersion Since there is no problem, the number average molecular weight should be 5,000 to 15,000, and more preferably 8,000 to 12,000.

If the glass transition temperature (Tg) is too low due to the thermal properties of the resin itself, it is advantageous for water dispersibility and alkali water dispersibility, but it may cause the yarn and yarn to stick during weaving, and if too high, water dispersibility and alkali water dispersibility Since there is a problem, the glass transition temperature is 30 ~ 60 ℃, more preferably 40 ~ 50 ℃. Since the glass transition temperature (Tg) is a property of the resin itself and is determined by the use ratio of each copolymerized monomer, the use ratio of the monomers is preferably within the above-mentioned range.

When the alkali water-dispersible copolyester resin according to the present invention is described in detail, the condenser, the column, and the reactor (installation) of the components (monomers) of the general formula (I) to (V) is installed together, The reaction catalyst was introduced when the temperature of the reactor was increased to 120 to 150 ° C., and then the ester exchange reaction was performed while the internal temperature was raised to 200 ° C. over 1 to 5 hours. At this time, by-products generated as the reaction proceeds are discharged out of the system through a condenser. At the point when the theoretical by-products are sufficiently released, a thermal stabilizer, an antioxidant, a reaction catalyst, an antifoaming agent, etc. are added as necessary, and the polycondensation reaction is carried out by inducing a temperature increase and a necessary vacuum at 240 to 270 ° C, and the number average molecular weight is 5,000. When the reaction reaches ˜20,000, the reaction is terminated to obtain an alkali water dispersible polyester resin.

The alkali water dispersible copolyester resin of the present invention thus prepared is placed in water, and then heated and stirred to be used as an inclination sizing agent or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited only to the following examples.

Example 1

65 kg of dimethyl terephthalate, 10 kg of dimethyl isophthalate, 45 kg of ethylene glycol, 15 kg of 5-sodium sulfodimethyl isophthalate, 1.5 kg of adipic acid and 9 kg of polyethylene glycol with 200 molecular weight Thereafter, the reaction catalyst was introduced when the temperature of the reactor was raised to 140 ° C., and then the transesterification reaction was carried out while the internal temperature was raised to 200 ° C. over 1 to 5 hours. At this time, by-products generated as the reaction proceeds are discharged out of the system through a condenser. When the theoretical by-products are sufficiently released, a small amount of ordinary heat stabilizer, antioxidant, reaction catalyst and antifoaming agent are added, and the polycondensation reaction is carried out by raising the temperature to 260 ° C. and inducing the required vacuum, and when the number average molecular weight reaches 10,000, Then, the copolyester resin is produced. The results of evaluating various physical properties of the prepared copolyester resin are shown in Table 2.

Examples 2 to 3 and Comparative Examples 1 to 4

A copolymer polyester resin was prepared in the same process and conditions as in Example 1 except that the number average molecular weight of the monomer (main raw material) and the number average molecular weight of the copolymer polyester resin at the end of the reaction were changed as shown in Table 1. The results of evaluating various physical properties of the prepared copolyester resin are shown in Table 2.

Manufacture conditions division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Usage (kg) Dimethyl terephthalate 65 60 70 65 65 70 70 Dimethylisophthalate 10 15 5 10 10 10 10 Ethylene glycol 45 45 45 45 45 48 48 5-sodiumsulfodimethylisophthalate 15 15 15 15 15 16 6 Adipic acid 1.5 1.5 3 1.5 1.5 0.8 1.6 Polyethylene Glycol (Molecular Weight 200) 9 12.8 5.3 9 9 1.6 9.7 Number average molecular weight of copolymerized polyester resin at the end of reaction 10,000 10,000 10,000 4,000 20,000 10,000 10,000

Property evaluation result division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Number average molecular weight 10,000 10,000 10,000 4,000 20,000 10,000 10,000 Glass transition temperature 44 38 56 42 47 52 42 Water dispersibility Full dispersion Full dispersion Full dispersion Full dispersion Full dispersion Full dispersion precipitate Alkali water dispersion Full dispersion Full dispersion Full dispersion Full dispersion precipitate precipitate precipitate Adhesive force (kg / ㎠) 0.89 0.87 0.85 0.65 0.75 0.72 Impossible

In Table 2, the water dispersibility, alkali water dispersibility, and adhesive force are the results of evaluation in the following manner.

Water dispersibility

The water dispersibility is a result of visual observation of 20 g of the resin prepared in 80 g of pure water after stirring at 80 ° C. for 15 minutes and then left at room temperature for 10 hours.

Alkali water dispersibility

Alkaline water dispersibility is the result of visual observation of 20 g of resin in 80 g of 5% by weight caustic soda solution at 80 ° C. for 15 minutes and then left at room temperature for 10 hours.

Adhesive force (kg / ㎠)

The adhesion test was conducted using an Instron 4465 tensile tester manufactured by Instron based on the peel adhesion test described in JIS Z 0237. The corona treated polyester film was used as one support, and the prepared sample was made to coat a thickness of about 25 μm, dried at 90 ° C. for 5 minutes, and then bonded with a single layer of polyester film. The bonded film was dried in a constant temperature bath at 90 ° C. for 24 hours, and then aged at room temperature for 24 hours to use as an adhesion test specimen. Afterwards, the strength was measured when the sample was peeled off at a peel angle of 180 ° and a peel rate of 300 mm / min at a steady state of temperature 22 ± 2 ° C. and a relative humidity of 65 ± 5%.

The alkali water-dispersible copolyester resin according to the present invention is particularly useful as an agent for water dispersible oblique sizing due to its excellent adhesion to the yarn, flexibility and strength. In addition, the alkali water-dispersible co-polyester resin according to the present invention is excellent in alkali water dispersibility even in the process of deicing under alkaline conditions after weaving the fabric, and exhibits sufficient callout performance.

Claims (12)

Aromatic difunctional carboxylic acid compound of the general formula (I) below, difunctional alcohol compound of the general formula (II) below, -SO ₃ M of the general formula (III) below (M is a hydrogen atom or an alkali metal atom) An aromatic difunctional carboxylic acid compound having a functional group, an aliphatic difunctional carboxylic acid compound of the following general formula (IV) and polyethylene glycol of the following general formula (V) are charged to a reactor, and an esterification reaction or a transesterification reaction is carried out. The polycondensation reaction is carried out after making it carry out, and the manufacturing method of the alkali water-dispersible copolymer polyester resin characterized by the above-mentioned. ROOC-C ₆ H ₄ -COOR (Ⅰ) HO-(CH ₂ ) n-OH (II) _{C 6 H 3 - (COOR)} 2 · SO 3 M (Ⅲ) HOOC-(CH ₂ ) n-COOH (Ⅳ) H-(OCH ₂ CH ₂ ) m -OH (Ⅴ) In formulas (I) to (V), R is a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, n is an integer of 2 to 5, M is a hydrogen atom or an alkali metal atom, and m is an integer of 2 to 10 . The method of claim 1, wherein the aromatic difunctional carboxylic acid compound of general formula (I) is one or two or more compounds selected from the first group consisting of dimethyl terephthalate and ester-forming derivatives of dimethyl terephthalate, dimethyl isophthalate and A method for producing an alkali water-dispersible copolyester resin, characterized by using together one or two or more compounds selected from the second group consisting of ester-forming derivatives of dimethylisophthalate. The compound according to claim 2, wherein the compound is selected from the group consisting of one or two or more compounds selected from the first group consisting of ester forming derivatives of dimethyl terephthalate and dimethyl lephthalate and ester forming derivatives of dimethyl isophthalate and dimethyl isophthalate. The use ratio is 70-95 weight% (1st group compound): 30-5 weight% (2nd group compound) The manufacturing method of the alkali water-dispersible copolyester resin characterized by the above-mentioned. The alkali water-dispersible copolymer according to claim 1, wherein one or two or more compounds selected from the group consisting of ethylene glycol, propanediol, butanediol and pentanediol are used as the difunctional alcohol compound of general formula (II). Method for producing a polyester resin. The alkali water dispersible poly according to claim 1, wherein 40 to 80 parts by weight of the difunctional alcohol compound of general formula (II) is used based on 100 parts by weight of the aromatic difunctional carboxylic acid compound of general formula (I). Process for producing ester resin. The aromatic difunctional carboxylic acid compound of formula (III) according to claim 1, consisting of 5-sodiumsulfodimethyl isophthalate, 4-sodiumsulfodimethylisophthalate, 5-sodiumsulfodimethylterephthalate and alkali metal salts thereof A method for producing an alkali water-dispersible copolyester resin, characterized by using one or two or more compounds selected from the group. The alkaline moisture according to claim 1, wherein the aromatic difunctional capoxane compound of the general formula (III) is used in an amount of 10 to 30 weight parts based on 100 parts by weight of the aromatic difunctional carboxylic acid compound of the general formula (I). Method for producing an acidic polyester resin. The alkali water dispersible agent according to claim 1, wherein the aliphatic difunctional carboxylic acid compound of the general formula (IV) uses one or two or more compounds selected from the group consisting of succinic acid, adipic acid and sebacic acid. Method for producing copolyester resin. 9. The aliphatic difunctional carboxylic acid compound of the general formula (IV) is used in an amount of 9 to 15 parts by weight based on 100 parts by weight of the aromatic difunctional carboxylic acid compound of the general formula (I). Method for producing alkali water dispersible polyester resin. The method for producing an alkali water-dispersible copolyester resin according to claim 1, wherein the polyethylene glycol of the general formula (V) is 100-500. The alkali water-dispersible polyester resin according to claim 1, wherein 1 to 5 parts by weight of polyethylene glycol of formula (V) is used based on 100 parts by weight of the aromatic difunctional carboxylic acid compound of formula (I). Manufacturing method. The alkali water-acid co-polyester resin produced by the method of Claim 1, whose number average molecular weight is 5,000-15,000, and glass transition temperature (Tg) is 30-60 degreeC.