KR100369848B1 - Water dispersion copolyester resin composition - Google Patents

Abstract

PURPOSE: A water dispersion copolyester resin composition having excellent water dispersion, printing stability, water resistance, adhesion and flexibility is provided to obtain a film having improved printing performance, gloss and thermal adhesive property. CONSTITUTION: The water dispersible copolyester resin composition comprises a copolymer obtained by the copolymerization of a dicarboxylic acid or derivatives thereof containing a metal sulfonate, another dicarboxylic acid or derivatives thereof and a dihydric alcohol. The water dispersible copolyester composition is characterized in that the copolymerization is performed by adding 0.5 to 30 parts by weight of an alkylphenol polymer based on 100 parts by weight of the total carboxylic acid compounds consisting of the dicarboxylic acid or derivatives thereof containing a metal sulfonate and the another dicarboxylic acid or derivatives thereof.

Description

Water Dispersible Copolyester Resin Composition

The present invention relates to a water dispersible copolyester resin composition, and more particularly, to an alkylphenol polymer, a dicarboxylic acid containing a sulfonic acid metal base or a derivative thereof, another dicarboxylic acid or a derivative thereof, and a dihydric alcohol. The present invention relates to a water-dispersible copolyester resin composition copolymerized with water, and the water-dispersible copolyester resin composition of the present invention has excellent physical properties such as water dispersibility, printing stability, water resistance, adhesiveness, and flexibility. It has the property of imparting excellent printing performance, gloss and heat adhesiveness to the film without sticking or sticking, and also depositing a metal such as aluminum on the surface of the film coated with the water dispersible copolyester resin composition of the present invention. When the above water-dispersible copolyester resin composition is applied, its vapor deposition property is improved while It can protect the membrane.

In general, the film is used for packaging, such as packing the inner condensation after printing and then finishing by heat bonding. However, most of the film is composed of a resin composition, so it is impossible to print directly on the film surface, and heat adhesion by itself is difficult. Therefore, in order to solve this problem, a method of coextrusion of another resin composition or coating another resin composition on the surface of a film has been used in manufacturing a film. However, according to the above method, wrinkles are formed on the film due to co-extrusion with the film or shrinkage difference between the resin composition and the film applied to the film, and the film has insufficient physical properties such as affinity with the printing ink composition and thermal adhesion performance. The surface is broken, the coated film is poor in transparency or gloss, and the coated resin composition is impossible to be reprocessed such as melting, which makes it impossible to regenerate the film and also causes environmental pollution problems due to the use of organic solvents. Problems were pointed out.

Korean Patent Publication No. 93-5141, Japanese Patent Publication No. 47-40873, Japanese Patent Publication No. 56-5476, Japanese Patent Publication No. 56-88454, and Japanese Patent Publication No. 4-226562, etc. In order to improve the problems in the resin composition, a dicarboxylic acid or derivative thereof containing a sulfonic acid metal base is copolymerized with another dicarboxylic acid or a derivative thereof and a dihydric alcohol to prepare a water dispersible copolyester resin composition. By dispersing this alone or in combination with other additives in water or a mixed solvent of water and alcohol, water-dispersible copolyester resin compositions for film coating were prepared. However, if the glass transition temperature (Tg) of the resin produced by such a manufacturing method is sufficiently high, coating it on a film or the like may cause the coating bug to easily crumble or lack heat adhesiveness, and the resin may have a low glass transition temperature (Tg). When the coated film is stacked or rolled up after being coated on a film or the like, the films may stick to each other.

Therefore, in the present invention, as a result of research efforts to solve the problems appearing in the conventional resin composition for coating, the dicarboxylic acid or derivatives thereof containing sulfonic acid metal base and another dicarboxylic acid or derivatives thereof and dihydric alcohol and The present invention was completed by copolymerizing together an appropriate amount of alkylphenol polymer when preparing a water-dispersible copolyester resin composition by copolymerization.

The present invention provides a water-dispersible copolyester resin composition which is easily dispersed in water or a mixed solvent of water and alcohol, and has excellent water resistance, printability, and heat adhesiveness, so that the coated surface does not stick or chip when coated on various films. The purpose is.

In addition, another object of the present invention is to provide a coating film coated with a dispersion in which the water dispersible copolyester resin compositions are dispersed in a dispersion medium.

Hereinafter, the present invention will be described in detail.

The present invention relates to a dicarboxylic acid or derivative thereof containing a sulfonic acid metal base, another dicarboxylic acid or a derivative thereof, and a dicarboxylic acid containing the sulfonic acid metal base in a resin composition copolymerized with a dihydric alcohol. Or a water-dispersible nose copolymerized by adding 0.5 to 30 parts by weight of an alkylphenol polymer represented by the following structural formula (I) based on 100 parts by weight of the total amount of carboxylic acid compound composed of derivatives thereof and another dicarboxylic acid or derivatives thereof: It is characterized by a polyester resin composition.

Where

X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

m and n are each an integer of 0 to 20, except that m + n ≠ 0.

The present invention will be described in more detail as follows.

The present invention is a water dispersibility useful for coating various films because it is excellent in dispersibility in water or water-soluble solvents and other various physical properties by copolymerizing the addition of alkylphenol polymer in the preparation of known water dispersible copolyester resin composition for coating It relates to a copolyester resin composition.

The alkylphenol polymer represented by the above formula (I), which may be a feature of the present invention, was used by purchasing a commercially available product. In addition, the alkylphenol polymer represented by the above formula (I) is used with respect to 100 parts by weight of the total amount of carboxylic acid compounds comprising the dicarboxylic acid or derivatives thereof containing the sulfonic acid metal base and another dicarboxylic acid or derivatives thereof. When the copolymerization is performed by adding 0.5 to 30 parts by weight, if the amount is less than 0.5 parts by weight, the effect of addition cannot be obtained. If the amount is more than 30 parts by weight, the reactant is gelled due to excessive crosslinking reaction during the copolymerization reaction.

Referring to the manufacturing process of the water-dispersible copolyester resin composition of the present invention in detail.

First, an alkylphenol polymer represented by the above formula (I) in a reactor equipped with a column and a condenser, dicarboxylic acid or derivative thereof containing an appropriate amount of sulfonic acid metal base, another dicarboxylic acid or derivative thereof, and divalent After adding the alcohol component, the temperature of the reactor is gradually increased, and when the temperature of the reactor reaches 130 ° C. to 150 ° C., a reaction catalyst is added. Then, the temperature of the reactor is raised to about 200 ° C. to 270 ° C. to proceed with the esterification reaction. In order not to evaporate or sublimate the reactant, the column temperature is maintained at 100 ° C. or lower so that only reaction by-products such as water and methanol are released. When the esterification reaction proceeds for about 1 hour to 10 hours, the reaction is terminated, and reaction by-products such as water and methanol no longer come out, and the white slurry reactant becomes a pale yellow transparent oligomer. The oligomer obtained in the esterification reaction is heated to about 220 ° C. to 300 ° C. and the pressure is gradually reduced while being careful not to scatter the reactant so that the porosity is 0.01 to 5 torr. In this process, the reaction proceeds for about 30 minutes to 10 hours while removing the dihydric alcohol component flowing out as a reaction by-product to obtain the water-dispersible copolyester resin composition of the present invention. In addition, if necessary, a catalyst selected from antimony oxide, dibutyl tin oxide, germanium dioxide, and the like may be added in an amount of 0.01 to 1.0% by weight based on the total weight of reactants, and a stabilizer selected from phosphorus and phenyl thermal stabilizers may be added in an amount of 0.01% by weight. To 1.0% by weight may be added.

In the manufacturing process of the water-dispersible copolyester resin composition of the present invention as described above, as dicarboxylic acid containing sulfonic acid metal base or derivatives thereof, 5-sodiosulfodimethyl isophthalate and 5-sodiosulfoiso Or a mixture of two or more selected from phthalic acids. As another dicarboxylic acid or derivatives thereof, terephthalic acid, isophthalic acid, adipic acid, succinic acid, azelaic acid and the like, and a single or a mixture of two or more selected from the derivatives thereof may be used. As the dihydric alcohol component, one or two selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and neopentyl glycol Mixtures of species or more may be used. If necessary, polyfunctional carboxylic acids such as trimellitic anhydride, pyromellitic acid and the like, and polyfunctional alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol and the like may also be used in the above components.

The reaction molar ratio of the dihydric alcohol component is 1: 1.1 to 2.0 with respect to the total amount of carboxylic acid consisting of dicarboxylic acid or derivative thereof containing sulfonic acid metal base, another dicarboxylic acid or derivative thereof, and polyfunctional carboxylic acid. The molar ratio range is preferred, and if the reaction molar ratio of the dihydric alcohol component is less than 1.1 molar ratio, it is difficult to obtain a reactant in a desired state, and it is uneconomical to use an excess dihydric alcohol component exceeding 2.0 molar ratio.

In addition, the use of dicarboxylic acid or derivatives thereof containing sulfonic acid metal base is preferably in the range of 100: 5 to 10 molar ratio with respect to another dicarboxylic acid or derivatives thereof. The prepared water-dispersible copolyester resin composition is well dispersed in water or a mixed solvent of water and alcohol at a temperature of 50 ° C. or higher, but excellent water resistance that is not dispersed in water at a temperature below room temperature can be obtained. Suitable for use for coating. However, when dicarboxylic acid or a derivative thereof containing a sulfonic acid metal base is used in less than 5 molar ratios, it is difficult to disperse in water or is impossible to disperse, and when it exceeds 20 molar ratios, water resistance becomes weak.

In the esterification reaction, one or more selected from butyl stenophosphoric acid, zinc acetate and tetrabutyl titanate may be used, and the amount of the catalyst is about 0.01 to 0.1% by weight based on the total weight of the reactants. At this time, the use of excess catalyst is unnecessary, if too little, there is a problem that the reaction is impossible or slow.

Molecular weight measurement of the water-dispersible copolyester resin composition of the present invention prepared by the composition and content as described above is replaced by the measurement of Intrinsic Viscosity at 30 ° C. using an Ostwald Viscometer. The intrinsic viscosity of the water-dispersible copolyester resin composition prepared in is in the range of 0.25 to 0.7 dl / g , which is in the range of 2,000 to 60,000 in terms of molecular weight. If the intrinsic viscosity of the water-dispersible copolyester resin composition is less than 0.25 dl / g , there is a problem of poor physical properties and brittleness. If the intrinsic viscosity is greater than 0.7 dl / g , the viscosity of the aqueous solution of the resin composition is increased. Not only is it too large to be suitable for use, but it is also difficult to disperse the resin composition in water or a mixed solvent of water and alcohol.

In addition, the glass transition temperature (Tg) measured by the differential scanning calorimeter (DSC) of the water-dispersible copolyester resin composition, if the glass transition temperature is less than 15 ℃ after coating When the film is rolled up or stacked in a roll, the films adhere to each other, and when the temperature exceeds 60 ° C., the adhesion and affinity with the ink composition may be degraded, and the coating layer may be easily broken during coating.

The water-dispersible copolyester resin composition prepared by the above method is added to a water or a mixed solvent of water and alcohol, stirred and dispersed at 50 ° C. to 100 ° C. to prepare a dispersion, and an appropriate amount of emulsifier and wax as necessary. And antistatic agents may be added to improve physical properties.

In the present invention, water is used alone or a mixed solvent of water and alcohol is used. When alcohol is used alone as the dispersion medium, the water-dispersible copolyester of the present invention is not dispersed at all, and water is used alone. It was not easily dispersed at temperatures below room temperature. Therefore, the use of a mixed solvent of water and alcohol as a dispersion medium rather than using a single component can improve the dispersibility of the polyester resin composition of the present invention to the dispersion medium, and also more surface tension than when used alone By lowering the adhesion and coating property with the film can be improved. Alcohols used as the dispersion medium in the present invention include monohydric alcohols having 1 to 15 carbon atoms such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol and normal butyl alcohol; Ethylene glycols or diethylene glycols such as ethylene glycol monobutyl ether and diethylene glycol monobutyl ether; Ketones such as acetone and methyl ethyl ketone.

In addition, when dispersing the water-dispersible copolyester resin composition in a dispersion medium by adding 0.5 to 20 parts by weight of a water-soluble resin such as polyethylene glycol to 100 parts by weight of the water-dispersible copolyester resin composition, the resin composition is plasticized. It lowers the thermal bonding temperature and improves the thermal adhesiveness. The polyethylene glycol is preferably in the range of 300 to 20,000 molecular weight. If the amount of polyethylene glycol is more than 20 parts by weight or the molecular weight is less than 300, problems such as adhesion of the films coated with the copolyester resin composition may occur, and if the molecular weight is more than 20,000, physical properties such as adhesion are low. There is a problem.

The water-dispersible copolyester dispersion prepared above is preferably 5 to 50% by weight of solids concentration, if the concentration of solids is less than 5% by weight is too thin to use for coating, 50% by weight If it exceeds, not only the dispersion is difficult, but also the viscosity is too high to coat.

The water-dispersible copolyester resin composition of the present invention as described above has excellent physical properties such as printability, heat adhesion, water resistance, solvent resistance, and flexibility, and is useful for coating various films such as polyester, polypropylene, and the like. By using these properties, it is useful not only for film but also for coating of papers.

When the present invention is described in more detail based on the embodiments as follows, it is not limited to the present invention.

Example 1:

Alkylphenol polymers (Arakawa Co., Tamanol; 10g), Terephthalic Acid (100g), Isophthalic Acid (230g), Adipic Acid (40g), 5-Sodium Sulfo in a reactor equipped with a temperature-controlled column and a condenser Dimethyl isophthalate (59 g), ethylene glycol (142 g) and neopentyl glycol (179 g) were added, and the temperature of the reactor was gradually raised to 150 ° C while stirring. And zinc acetate (0.5g) and tetrabutyl titanate (0.1g) were added as a catalyst, it heated up to 235 degreeC with stirring again, and then esterification reaction was continued at this temperature. When water and methanol began to flow out as reaction by-products during the reaction, the temperature of the column was maintained at 100 ° C. to prevent dicarboxylic acid or dihydric alcohol components from subliming or evaporating. When the reaction was continued for about 5 hours, water and methanol were no longer leaked, and the reaction product was confirmed to be terminated by the formation of a pale yellow transparent oligomer in a white opaque state.

After adding antimony oxide (0.3 g) as a catalyst to the reactant in the oligomer state, gradually applying vacuum and raising the temperature while being careful not to scatter the reactant to maintain a pressure of 1 torr in the reactor and the temperature of the reactant was The reaction was carried out for 2 hours at 265 ° C. to prepare a water dispersible copolyester resin composition. At this time, ethylene glycol, neopentyl glycol, and the like, which were added as dihydric alcohol components, were leaked as reaction byproducts. The water-dispersible copolyester resin composition thus obtained had an intrinsic viscosity of 0.36 dl / g measured at 30 ° C. using an Ostwald viscometer and a glass transition temperature (Tg) of 40 ° C. measured using a differential scanning calorimeter. .

Then, the water-dispersible copolyester resin composition (60 g) obtained above was added to a mixed solvent of water (105 g) and isopropyl alcohol (35 g), and stirred at 80 ° C. for 3 hours to give a pale yellow transparent water-dispersible copolyester dispersion. It was prepared, the intrinsic viscosity at 300 ℃ measured by Brookfield viscometer was 300 cps.

Example 2:

A water dispersible copolyester resin composition was prepared in the same manner as in Example 1, and the water dispersible copolyester resin composition (60 g) was placed in a mixed solvent of water (105 g) and butyl carbitol (35 g), and 80 ° C. After stirring for 3 hours to prepare a pale yellow transparent water-dispersible copolyester dispersion.

Example 3:

A water dispersible copolyester resin composition was prepared in the same manner as in Example 1, and the water dispersible copolyester resin composition (60 g) was placed in a mixed solvent of water (105 g) and butyl cellosolve (35 g), and 80 Proprietary at 3 ° C. for 3 hours to prepare a pale yellow transparent water dispersible copolyester dispersion.

Example 4:

A water dispersible copolyester resin composition was prepared in the same manner as in Example 1, and the water dispersible copolyester resin composition (60 g) was water (105 g), isopropyl alcohol (25 g), and butyl cellosolve (10 g). Was added to a mixed solvent and stirred at 80 ° C. for 3 hours to prepare a pale yellow transparent water dispersible copolyester dispersion.

Example 5:

A water dispersible copolyester resin composition was prepared in the same manner as in Example 1, and the water dispersible copolyester resin composition (60 g) was placed in a mixed solvent of water (105 g) and isopropyl alcohol (35 g), and 80 ° C. After stirring for 3 hours to prepare a pale yellow transparent water-dispersible copolyester dispersion. Then, water (100 g) was added to the water-dispersible copolyester dispersion (100 g) to prepare a water-dispersible copolyester dispersion in which the concentration was 20% and diluted to 15%.

Example 6:

A water dispersible copolyester resin composition was prepared in the same manner as in Example 1, and a water dispersible copolyester resin composition (60 g) and polyethylene glycol (1.8 g) having a molecular weight of 400 were water (105 g) and isopropyl alcohol ( 35 g) was mixed with a solvent, and stirred at 80 DEG C for 3 hours to prepare a pale yellow transparent water-dispersible copolyester dispersion.

Example 7:

Alkylphenol polymer (Arakawa, Japan, 5g), terephthalic acid (200g), isophthalic acid (130g), adipic acid (40g), 5-sodiosulfodimethyl isophthalate (59g), ethylene glycol (142g) and A water dispersible copolyester resin composition was prepared using neopentyl glycol (179 g). The water-dispersible copolyester resin composition thus obtained had an intrinsic viscosity of 0.41 dl / g measured at 30 ° C. using an Oswald viscometer and a glass transition temperature (Tg) of 41 ° C. measured using a differential scanning calorimeter. .

Then, the water dispersible copolyester resin composition was dispersed in the same dispersion medium as in Example 1 to prepare a water dispersible copolyester dispersion.

Example 8:

A water dispersible copolyester resin composition was prepared in the same manner as in Example 7, and the water dispersible copolyester resin composition (60 g) was placed in a mixed solvent of water (105 g) and butyl carbitol (35 g), and 80 ° C. After stirring for 3 hours to prepare a pale yellow transparent water-dispersible copolyester dispersion.

Comparative Example 1:

A water dispersible copolyester resin composition was prepared in the same manner as in Example 1 using terephthalic acid (115 g), isophthalic acid (220 g), adipic acid (40 g), and 5-sodiosulfodimethylisophthalate (59 g). It was. The water-dispersible copolyester resin composition thus obtained had an intrinsic viscosity of 0.44 dl / g measured at 30 ° C. using an Oswald viscometer and a glass transition temperature (Tg) of 42 ° C. measured using a differential scanning calorimeter. .

Then, the water dispersible copolyester resin composition was dispersed in the same dispersion medium as in Example 1 to prepare a water dispersible copolyester dispersion.

Experimental Example 1 :

Each water-dispersible copolyester dispersion prepared in Examples and Comparative Examples was measured for viscosity using a Brookfield viscometer. Each of the water-dispersible copolyester dispersions was coated with an appropriate thickness of a polypropene film using a bar coder, and then dried at 60 ° C., followed by coating, appearance, brittleness, Printability and heat adhesiveness were measured.

Coating property: Check whether the coating thin film is peeled off when the adhesive tape is attached to the coatingmin of the film coated with the water dispersible copolyester dispersion.

Appearance: Visually check the transparency and wrinkles of the coated film

Fragility: Check the coated film by hand.

Printability: Check whether the coating surface of the coated film can be written with an aqueous sine pen, and also apply to the surface of the film coated with amide and urinary ink composition, and then attach the adhesive tape and release the ink composition. Check whether it is peeling off.

Thermal adhesiveness: T- peel strength is measured after compressing the coated surfaces of the coated fins with each other at 150 ° C.

Table 1

Comparative Example 2: Printability and thermocompression measurement results for a polypropylene film not coated with a dispersion.

According to the experimental results of Table 1, the embodiment according to the present invention is suitable for use in coating applications as the viscosity measured by Brookfield viscometer is 100 ~ 350 cps. The surface of the dispersion-coated film prepared in Example according to the present invention was generally clean and transparent in appearance, and it could not be observed that the coating film peeled or chipped from the coated film by the adhesive tape. It can be seen that the appearance and coating properties are excellent. And it was possible to write with an aqueous sign pen directly on the surface of the film coated with the dispersion of the present invention, it can be seen that both amide and urethane-based ink composition is not peeled off by the coating tape gradually from the coated film, it is excellent in printability. . In addition, when the surfaces of the film are thermally compressed at 150 ° C., the thermocompression-bonded portions remain in the bonded state, but the film is ruptured at the non-compressed surface, indicating excellent thermal adhesion.

However, although the polyester film coated with the dispersion of the copolymerized resin composition without containing the alkylphenol polymer represented by the above formula (I) was transparent and clean in appearance, the coating film was peeled off from the coated film by the adhesive tape, The coating film crumbled when rubbed.

In the above, the dispersion of the present invention was coated on the polypropylene film, but excellent coating property, printability, and thermocompression property were obtained even when a polyester film other than the polypropylene film was used.

Experimental Example 2 :

The water dispersible polyester dispersion prepared in Example 8 was coated on a polypropylene film, and then deposited on aluminum, and the water dispersible polyester dispersion prepared in Example 8 was recoated. Then, when the adhesive tape was attached to and detached from the coated polypropylene film surface, the coating film was not peeled off by the adhesive tape. Thus, it was found that the deposition property of aluminum with respect to the water-dispersible polyester dull acid solution of the present invention was excellent. . It was also possible to write directly with an aqueous sign pen.

Experimental Example 3 :

In order to confirm the water resistance and solvent resistance of the water-dispersible polyester resin composition according to the present invention, after dispersing the dispersion medium on the Teflon plate to prepare a film of the resin composition, water or organic After immersion in a solvent at room temperature for 24 hours to confirm the phase, the results are shown in Table 2 below.

TABLE 2

According to the results of Table 2, the water-dispersible copolyester resin composition prepared in the present invention is easily dispersed in water or a mixed solvent of water and alcohol at a temperature of 50 ° C. or higher, but not dispersed in water at a temperature below room temperature. Therefore, it is very useful for coating various films with water dispersibility and excellent water resistance.

Claims (3)

In the dicarboxylic acid or derivative thereof containing a sulfonic acid metal base, another dicarboxylic acid or a derivative thereof, and a resin composition copolymerized with a dihydric alcohol, the dicarboxylic acid containing the sulfonic acid metal base or the like Water dispersibility, characterized in that copolymerization of an alkylphenol polymer represented by the following structural formula (I) by adding 0.5 to 30 parts by weight based on 100 parts by weight of the total amount of the carboxylic acid compound consisting of a derivative and another dicarboxylic acid or derivatives thereof Copolyester Resin Compositions. In the above formula, X is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, m and n are integers of 0-20, respectively, except that m + n ≠ 0. The dicarboxylic acid or derivatives thereof containing the sulfonic acid metal base are added in an amount of 5 to 10 parts by weight based on 100 parts by weight of the total amount of the carboxylic acid compound composed of another dicarboxylic acid or derivatives thereof. A water-dispersible copolyesher resin composition, characterized in that copolymerized. The water-dispersible copolyester resin of claim 1, wherein the water-dispersible copolyester resin composition has an intrinsic viscosity of 0.15 to 0.70 dl / g and a glass transition temperature of 15 to 70 ° C. Composition.