KR950002615B1 - Method of producing polyamideresin - Google Patents

Abstract

The hot melt adhesive of polyamide copolymer resin is prepared by mixing and reacting 10-40 wt.% of ε-caprolactam of ε-amino caprone acid, 20-50 wt.% of amino dodekane acid or lauryl lactam, 10-40 wt.% of hexamethylene diamine and adipic acid or hexamethylene adiphate salt, and water in presence of catalyst; then inputting 20-50 wt.% of polycaprolactone of formula (I) and mixing-reacting, where n is 100-200. 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 copolyamides based on ε-amino capronic acid or ε-caprolactam and amino dodecanoic acid or lauryllactam and nucleated methylenediamine, adipic acid or nucleated methylenediamine adipate salt, and caprolactone as basic components. It relates to a method for producing a hot melt polyamide crab adhesive.

Commonly known nylon 6, nylon 66, nylon 12, etc. (HOMOPOLYMER) (Japanese Patent Publication Nos. 48-24812 and 48-25426), nylon 6, nylon 66, nylon 610 copolymer (US Pat. No. 4,420,455) ), And polyamide-based hot melt adhesives such as nylon 6, nylon 66, nylon 12 copolymers (UK Patent Nos. 1,168,404, Japanese Patent Publication Nos. 52-91040, 44-19868) and the like. Although it is widely used for adhesion of paper, etc., since it has a large amount of amide groups in the polymer structure, it is difficult to prevent the adhesive strength from decreasing over time due to its low resistance to moisture and solvents during washing or use. Many studies have been conducted to solve the problem, and in one method, a nylon copolymer made of polymer fatty acid and piperazine (PIPERAZIN) or diphenylidyl type diamine (US Pat. Nos. 3,377,303, 3,738,950) , Nylon copolymers made of polymer fatty acids and ether diamines (US Pat. No. 3,882,090, UK Pat. No. 1,319,807, US Pat. No. 3,499,853), Aliphaticetherdiamine and aliphatic dicarboxylic acid Polyamides, such as nylon polymers (Germany Patent No. 25,52,518,25,52,455, US Patent No. 4,299,567) The adhesive has a high melting point, a difficult manufacturing process, and many uses of the adhesive.

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

It is also a copolymer than Dalyl's polymer, and the melting point is lowered and the process is easier because the number of amide groups is reduced and the hydrogen bond is weakened.

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

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

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

And although the nylon polymer may be prepared from aliphatic ether diamine and aliphatic dibasic acid, the polyoxyalkylene diamine used herein may be subjected to cyano ethylation reaction with polyoxyalkylene glycol in the presence of ion exchange resin, and then There is a need for a production 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 high crystallinity, and thus have high elasticity and low crystallinity. .

Therefore, in the related art, a technique in which a copolymerized polyamide is known as a nylon adhesive has been known. However, as described above, there is a problem in that the adhesive strength is lowered at low temperatures due to poor water resistance and no elasticity.

Originally required for hot melt nylon adhesives, 1) low melting point (or flash point), strong adhesive strength, 2) good water resistance, so that the adhesive strength should not be reduced in the wet state, and 3) when used in fiber Excellent chemical resistance, 4) It is required that the adhesive strength does not decrease even at low temperatures.

The present inventors have completed the present invention as a result of studying the hot melt to improve the disadvantages of the prior art to provide a method for producing a hot melt nylon-based adhesive that satisfies the properties required for the hot melt adhesive.

That is, the present invention is an ε-cadrolactam or ε-amino capronic acid and amino dodecanoic acid or lauryl lactam, nucleated methylenediamine and adipic acid or nucleated methylenediamine adipate salt, and polycaprolactone, such as It is an object of the present invention to provide a method for producing a hot melt adhesive composed of copolymerized polyamide in which this mixed component is prepared in the presence of water and a catalyst.

Where n is 100-200

The present invention is described in detail as follows.

In the present invention, when the component of nylon-12 represented by ε-caprolactam or ε-aminocaproic acid, aminododecanoic acid or lauryllactam is 20% by weight or less, the adhesive stability is lowered and the adhesive strength is lowered. If is expected and more than 50% by weight can be a disadvantage in terms of cost.

In addition, when the nylon one 66 component, which is represented as nucleated methylene adipate salt, is less than 10% by weight, it is difficult to design the physical properties of the final resin, and thus, it is a factor of lowering the adhesive strength. If the content of lactone is less than 20% by weight is a factor of the increase in the density of the amide group has a significant impact on the lowering of the adhesive stability, if the weight is more than 50% the amide group density is too low to properly exhibit the adhesion.

Ε-caprolactam or ε-aminocaproic acid in the composition is a component that forms a Nile-6 structure in the final resin, and inodedocanoic acid or lauryllactam has a nylon-12 structure, and nuxamedylenediamine and adipic Acid or nucleated methylenediamine adipate salts are components that form the nylon-66 structure.

In addition, polycaprolactone is a component that forms an aliphatic ester structure in the final resin as shown in the above formula. The polycaprolactone may be introduced into a monomeric caprolactone state and copolymerized, but then decomposed by an amide-forming coagulant. Since the reactivity is poor, it is advantageous to add a polycaprolactone in the polymer state having a molecular weight of 10,000-20,000.

Such polycaprolactone has a lot of commercialized products worldwide, and representative manufacturers include Union Carbide Co., Japan's Daicel and Japan Ink Co., Ltd.

Titanium-based organic materials that can be used as catalysts include detraisopropoxy titanium, detra n-butoxy titanium, tetrakis-2-ethylnuclear titanium, detrasteoxy titanium, tetramethylene titanate and di-isopro Foxy-bis cetyl acedonate titanate, magnesium bistetra butoxide titanate, tributyl titanate, etc. can be used, and its antimony organic compound etc. can also be used.

As a method of obtaining the copolymerized polyamide by polymerizing the basic components of the present invention, a known polymerization method may be applied. In the catalyst to be added, inorganic acid may be added as a molecular weight control system and phosphoric acid may be used as the inorganic acid.

The organotitanate or antimony oxide may be added as a reaction accelerator, and additionally various additives such as dyes or antioxidants may be added.

In addition, the mixed copolymer component is added to the above catalyst, pressurized at a temperature of 200-300 ℃ in the presence of water or polymerized under normal pressure to obtain a polyamide.

The obtained polyamide is used as an adhesive, and the adhesive may be used by mixing a plasticizer with a copolymerized polyamide according to the purpose of use, and usually, the copolymerized polyamide alone is used as a processed product according to various uses such as film, powder, pellet, filament, etc. It can be molded and used as an adhesive.

The copolymerized polyamide of the present invention thus prepared has a structure of high polyester amide which is basically a copolymerized form of polyamide and polyester, and the copolymerized polycaprolactone has no amide group in the structure, so that the copolymerization content is increased. The lower the density of the amide group in the overall structure, the lower the decomposition rate by water or solvent, and improve the chemical resistance by water or solvent during washing, and not only reduce the adhesive strength in the long term. Polyamide resin copolymerized with polycaprolactone with excellent flexibility and low melting point due to the degree of freedom has excellent adhesion and low melting point, so that it can be applied to a wide range of applications. I can use it easily and buy it as an elastic sealant This is possible.

Example 1

25% by weight of caprolactam, 30% by weight of aminododecanoic acid, 25% by weight of nucleated methylenediamine 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, and the reaction product was heated at 260 ° C. and reacted for 3 hours while pressurizing the pressure to 15 Kg / cm ³ at atmospheric pressure.

Thereafter, the pressure in the tube was gradually reduced to the normal pressure state for 2 hours, 20 wt% of polycaprolactone was added and mixed well while stirring for 30 minutes, followed by condensation for 3 hours without pressure, and then the reaction was stopped. It discharged and obtained the granulated polyamide copolymer.

The resulting granular material was measured by Ostwald viscometer in a 0.1% solution of 98% sulfuric acid at 25 ° C. and showed a relative solution viscosity of 1.84. The obtained copolymer polyamide was mixed with methanol and methylchloroform in a weight ratio of 1: 1. Was dissolved in and coated on a release sheet in a knife coat to produce a film with a thickness of 60.

The film was put in cotton float No. 100 and bonded at 150 ° C. for 10 seconds with a compression time of 0.3 Kg / cm ³ .

The initial adhesive strength, the adhesive strength after washing, and the adhesive strength after dry cleaning were measured for the adhesive thus bonded to obtain respective results.

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 ° C. to measure the adhesive strength after repeated 5 times, and after dry cleaning. The adhesive strength was deposited on a mixed solution of 100 ml of chloroethylene, 1 g of dodecyl benzenesilfonate, 1 g of polyoxyethylene nonylphenyl ether, and 1 g of purified water, and then rotated for 5 minutes and dried at 65 ° C. for 30 minutes. Measured after repeated times, all the measured results are shown in Table-1.

Example 2-5; Comparative Example 1-4

In Example 1), the ratio of the basic components was carried out at the ratio shown in Table-1, and the other conditions were carried out in the same manner as in Example 1).

Comparative Example 5-6

In Example 1), the ratios of the basic components are as shown in Table-1, and were performed in the same manner, without adding polycaprolactone.

Comparative Example 7

The same composition as in Example 1) was carried out, but the four components as basic components were initially added and carried out. As a result, the polymerization degree of the reactants did not increase, and thus a high molecular weight resin could not be obtained.

Table 1

Claims (1)

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 nucleated methylenediamine and adipic acid or nuxaedylenediamine adipate salt After mixing and reacting in the presence of water and a catalyst, 20-50% by weight of polycaprolactone of the formula (I) is added to the reaction mixture for producing a hot melt adhesive copolymerizable polyamide resin. an integer with n = 100-200