KR950002616B1 - Method of producing poly-amide copolymer resin - Google Patents

Abstract

The hot melt adhesive of polyamide copolymer resin is prepared by mixing the copolymer component which comprises 10-40 wt.% of ε-caprolactam or ε-amino caprone acid, 20-50 wt.% of aminododekane acid or lauryl lactam, 10-40 wt.% of hexamethylene diamine and adipic acid or hexamethylene diamine adiphate salt and 20-50 wt.% of ester component; and copolymerising the copolymer component with water in presence of catalyst. Pref. the ester component is prepd. by esterification of 1:1-2 mole ratio of C2-6 glycol and C6-12 dicarbonic acid. The obtd. polyamide copolymer resin has excellent adhesiveness and broad usage because of lower melting point, and is useful for adhesive fabrics, unwoven fabrics and metallic adhesion, or elastic sealant.

Description

Method for producing polyamide copolymer resin capable of hot melt adhesion

The present invention relates to ε-aminocapronic acid or ε-caprolactam and amino dodecanoic acid or lauryl lactam and nuxamethylenediamine, adipic acid or hexamethylenediamine adipate salt, aliphatic glycols having 2 to 8 carbon atoms and 6 carbon atoms The present invention relates to a method for producing a hot-melt polyamide adhesive composed of a copolyamide having an ester chain composed of -12 dicarboxylic acids as a basic component.

Commonly known homopolymers (homopolymers) such as nylon-6, nylon-66, nylon-12 (Japanese Patent Publication Nos. 48-24812 and 48-25426), nylon-6, nylon-66, nylon-610 copolymers (U.S. Patent No. 2,420,455), and polyamide-based hot melting such as nylon-6, nylon-66, nylon-12 copolymer (UK Patent No. 1,168,404, Japanese Patent Publication No. 52-91040, 44-19868) Although adhesives are widely used for adhesives such as fibers, wood, metals, and paper, they have a large amount of amide groups in the polymer structure, which prevents the adhesive strength from deteriorating over time due to their low resistance to moisture and solvents during cleaning and use. Many studies have been conducted to solve this problem because it is difficult to do so, and in one method, a nylon copolymer made of polymer fatty acid and piperazine or diperidyl type diamine (US Pat. 3 77,303, 3,738,950), a nylon copolymer made of polymer fatty acid and ether diamine (US Pat. No. 3,882,090, UK Pat. No. 1,319,807, US Pat. No. 3,499,853), made of aliphatic ether diamine. Polyamide adhesives such as nylon polymers (German Patent Nos. 25,52518, 25,52455, and U.S. Patent No. 4,229,567) have a high melting point, a difficult manufacturing process, and many applications thereof.

As can be seen from the following nylon structure (formula), the larger the chemical repeating unit, that is, the smaller the number of amide groups, and the confused the structure, the lower the crystallinity.

The reason is that the hydrogen bonding force is weakened, so that the crystallinity is lowered and the melting point is lowered.

In addition, when the copolymer is a homopolymer, the number of amide groups is reduced and the hydrogen bond is weakened, so that the melting point is lowered and the process is easy.

The homopolymer or copolymer is limited in its use because of its high crystallinity.

In particular, the polyamides to be used in the fields required for hot melt bonding, for example, fiber adhesion by heating press, metal adhesion, etc., are generally high in crystallinity, and thus a rapid freezing process is required after adhesion. Because of its high crystallinity, if it is not quenched, there is less amorphous part, less elasticity and low adhesive strength.

In practice, however, this process is extremely complicated from an industrial point of view.

And it is possible to prepare nylon polymer with aliphatic ether diamine and aliphatic dibasic acid, but the polyoxyalkylene diamine used here is subjected to cyano ethylation reaction of polyoxyalkylene glycol in the presence of ion exchange resin and then There is a need for a process for hydrogenation under a nickel catalyst.

As described above, various conventional copolymerized polyamides have a lot of amide bonds, that is, hydrogen bonds have a high melting point and crystallinity. .

Therefore, the conventional copolymer polyamide is known to be a nylon-based adhesive, but as described above, there is a problem in that the adhesive strength is lowered at low temperatures due to poor water resistance and lack of elasticity.

Originally required properties for hot melt nylon adhesives;

1) Low melting point (or flash point) and strong adhesive strength:

2) water resistance is good and adhesion strength should not be reduced in the wet state;

3) good chemical resistance when used in textiles;

4) It is required that the adhesive strength does not decrease at low temperatures.

The present inventors have made a long study on the hot melt adhesive to improve the disadvantages of the prior art to provide a method for producing a hot melt nylon adhesive that satisfies the properties required for the hot melt adhesive, the present invention Was completed.

That is, the present invention relates to ε-caprolactam or ε-aminocaproic acid and aminododecanoic acid or lauryllactam, hexamethylenediamine and adipic acid or hexamethylenediamine adipate salts, and aliphatic glycols having 2 to 8 carbon atoms; It is an object of the present invention to provide a method for producing a hot melt adhesive composed of copolymerized polyamide in which an ester chain composed of dicarboxylic acids having 6 to 12 carbon atoms is used as a basic component, and the mixed component is prepared in the presence of water and a catalyst. have.

The present invention is described in detail as follows.

The present invention is 10-40% by weight of ε-caprolactam or ε-aminocaproic acid, 20-50% by weight of aminododecanoic acid or lauryllactam, hexamethylenediamine and adipic acid or hexamethylenediamine adipate salt 10-40 Weight%, 20-50% by weight of the ester component as a basic component, 2-15% by weight of this mixed copolymer component, 0-0.2% by weight of inorganic acid as catalyst, 0.01-0.5% by weight of titanium organic compound The present invention relates to a method for preparing a hot melt adhesive copolymerizable polyamide resin prepared by pressurizing or heating at 200-300 ° C. under normal pressure, wherein a component of nylon-6 represented by ε-caprolactam or ε-aminocaproic acid is 10 If it is less than or equal to% by weight, it is disadvantageous in terms of the cost of the final product, and if it is more than or equal to 40% by weight, a decrease in adhesion stability is expected due to an increase in the density of the amide group, and is represented by aminododecanoic acid or lauryl lactam. If the component is 20% by weight or less, a decrease in adhesive stability and a decrease in adhesive strength are expected, and if it is 50% by weight or more, it may be an adverse factor in terms of cost.

In addition, when the nylon-66 component represented by hexamethylene adipate salt is 10 wt% or less, it becomes difficult to design the physical properties of the final resin, and it becomes a factor of lowering the adhesive strength, and when it is 40 wt% or more, it becomes a deterioration factor of the adhesion stability and the adhesive strength. If the content of the ester is less than 20% by weight is a factor of the increase in the amide group density, it has a significant effect on the lowering of the adhesive stability, when the content of more than 50% by weight of the amide group is too low to properly exhibit the adhesive force.

Ε-caprolactam or ε-aminocaproic acid in the composition is a component that forms a nylon-6 structure in the final resin, and aminododecanoic acid or lauryllactam has a nylon-12 structure, and hexamethylenediaine and ah Dipic acid or hexamethylenediamine adipate salt is a component that forms a nylon-66 structure.

In addition, the ester component plays a role of mainly reducing the density of the amide group in the final resin, thereby preventing the deterioration of adhesion force due to water or other factors, and also improving the initial adhesive strength due to its low glass transition temperature. have.

Titanium-based organic materials that can be used as catalysts include tetrairopropoxy titanium, tetra n-butoxy titanium, tributyl titanate, tetrakis-2'-ethylhexoxytitanium, tetrasteaoxy titanium, tetramethylene titanate, Di-isopropoxybis cetylacetonate titanate, magnesium bistetra butoxide titanate, etc. can be used, and other antimony organic compounds can also be used.

The method of obtaining the copolymerized polyamide roll by polymerizing the basic components of the present invention can usually be prepared by a known method, which will be described below.

First, there is a method for preparing an ester component to be introduced into an amide chain, which is added at 1.0-2.0 molar ratio of dicarboxylic acid component to the glycol component similar to the conventional polyester reaction.

The reason for reacting the molar ratio of glycol component: dicarboxylic acid component in the molar ratio of 1: 1-2 when preparing the ester component is that the reactivity of the terminal when the pure -OH terminal polyester component is added during the preparation of the copolyamide This may be lowered, and most preferably, the glycol component: dicarboxylic acid component is prepared in a molar ratio of 1: 2, and the polyester terminal is -COOH, and the reactivity is most excellent.

In the present invention, in order to increase the weight average molecular weight (Mw) of the polyester, a glycol component: dicarbon component was prepared in a molar ratio of 1: 1-2.

The reaction tube may be heated to about 150-230 degrees to react to remove low molecular weight condensation by-products such as water, thereby preparing an ester component having a suitable degree of polymerization.

In this case, when using the component of the carboxyl terminal as the dicarboxylic acid, the reaction tube is sealed at the beginning of the reaction, and an autocatalyst that uses the reactant dicarboxylic acid as its own catalyst while applying a pressure of 1.5-3.0 Kg / cm ² . When the carboxyl terminus of dicarboxylic acid is a low molecular weight alkyl esterified product using a direct esterification reaction, a metal acetate water, an oxide, an organic titanium compound, or the like is introduced from the outside as a catalyst for transesterification and pressurized. The ester component can only be prepared by heating at normal pressure without pressure.

And the raw material of the amide basic component of the basic component of the present invention is added and the inorganic acid is added as a molecular weight regulator.

As an inorganic acid, although an ordinary inorganic acid can be used, phosphoric acid is preferable. The organic titanate or antimony oxide may be added as a reaction accelerator, and additionally various additives such as dyes or antioxidants, antifoaming agents and antistatic agents may be added.

This component may be added and pressurized at a temperature of 200-300 ° C. in the presence of water, or the initial polymerization may be carried out at atmospheric pressure, and then the ester component prepared above may be added and the reaction may be continued under vacuum to prepare polyamide having a degree of copolymerization. .

A plasticizer etc. can be mixed and used for the copolymerization polyamide obtained in this way, and it can be used as an adhesive by shape | molding into a processed product according to various purposes of use, such as a film, a pellet, a filament, with the usual copolymerization polyamide alone.

The copolymerized polyamide of the present invention thus prepared has a structure of high polyester amide in the form of copolymerization of polyamide and polyester, and the ester component to be copolymerized does not have any amide group in the structure, and as the copolymerization content thereof increases, The density of the amide groups in the overall structure is lowered, so that the decomposition rate by water or solvent is lowered, and the chemical resistance by water or solvent is improved during washing, which prevents a decrease in adhesive strength in the long term, and also increases the degree of freedom of the ester chain. Due to its excellent flexibility and low melting point, these copolymerized polyamide resins have excellent adhesion, high stability, and high durability. It has a low melting point and can be applied to a wide range of applications. In particular, it can be widely used for metal bonding such as wicks, adhesive fabrics, and nonwoven fabrics, and can also be used as an elastic sealant.

Next, the present invention will be described in more detail by way of examples.

Example 1:

1) Preparation of ester component:

50 mol% of 1,4-butylene glycol and 50 mol% of adipic acid were added to a conventional polyester reaction tube, and the pressure was increased to 2.0Kg / cm ² while sealing the reaction tube and raising the temperature of the tube to 210 degrees in 1 hour. After the addition, the reaction was carried out for 1.5 hours, and then the pressure was slowly removed for 30 minutes, thereby removing the generated water out of the system to obtain an esterified product.

2) Preparation of Copolyamides:

15% by weight of caprolactam, 45% by weight of aminododecanoic acid, 15% by weight of hexamethylenediamine adipate salt are mixed with 5% by weight of water, 0.05% by weight of phosphoric acid as a catalyst and 0.2% by weight of tributyl titanate. % Was added to an autoclave equipped with a stirrer, and oxygen was repeatedly removed from the tube using nitrogen, followed by reaction for 3 hours while pressurizing the pressure to 15 Kg / cm ² at atmospheric pressure while heating the reaction at 260 degrees.

Thereafter, the pressure in the tube was gradually reduced to atmospheric pressure for 2 hours, 25 wt% of the esterification prepared in Preparation Example 1 was added thereto, mixed well with stirring for 30 minutes, and the postcondensation was performed for 3 hours without pressure. Proceed.

The reaction was stopped and the polyamide copolymer granulated by discharging was obtained.

The resulting granular material was measured as an Ostwald viscometer in a 0.1% solution of 98% sulfuric acid at 25 ° C., and showed a relative solution viscosity of 1.87. It was dissolved in and coated on a release paper in a knife coat and bonded at 150 ° C. for 10 seconds at a compression time of 0.3 Kg / cm ² .

Initial adhesive strength, adhesive strength after washing, and adhesive strength after dry cleaning were measured for the adhesive thus bonded, and the respective results were obtained.

Here, the adhesive strength after washing was measured by immersing the bonded product in an aqueous solution of 0.5% of high tie, rotating for 5 minutes, and then drying for 1 hour at a temperature of 65 degrees to measure the adhesive strength after repeated 5 times. The strength was adhered to a mixed solution of 100 ml of perchloroethylene, 1 g of dodecyl benzenesulfonate, 1 g of polyoxyethylene nonyl ether, and 1 g of purified water, and then rotated for 5 minutes and dried at 65 degrees for 30 minutes. After the measurement, all the results thus measured are shown in Table 1.

Example 2-5 and Comparative Example 1-7

1) Preparation Example of Ester Components:

An ester component was prepared in the same manner as in Example 1, but the input composition thereof is as shown in Table 1.

2) The same method as in Example 1 was carried out, the composition of the input was added and carried out as shown in Table 2, the physical properties are also shown in Table 2.

TABLE 1

Comparative Example 8-9:

In Example 1), the ratio of the basic components is as shown in Table 2, and carried out in the same manner, but without adding the ester component.

TABLE 2

In Comparative Examples 1, 2, and 3, the degree of polymerization did not increase, so that no copolymerized polyamide resin was obtained.

Claims (2)

10-40% by weight of ε-caprolactam or ε-aminocaproic acid, 20-50% by weight of aminododecanoic acid or lauryllactam, 10-40% by weight of hexamethylenediamine and adipic acid or hexamethylenediamineadipate salt, A method for producing a hot melt adhesive copolymerizable polyamide resin, comprising copolymerizing a copolymer component having 20 to 50% by weight of an ester component in the presence of a catalyst with water. The method of claim 1, wherein the ester component is a hot melt adhesive, characterized in that the preparation by the esterification of the glycol having 2-6 carbon atoms and dicarboxylic acid having 6-12 carbon atoms so that the molar ratio of 1: 1-2 Method for producing this possible copolymerized polyamide resin.