JPH0337570B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel polyamide copolymer, more specifically, a diamine dicarboxylic acid salt having bispiperidylalkane as a diamine component or an equimolar mixture thereof, a lactam having 8 or more carbon atoms in the methylene chain or its ω-aminocarboxylic acid, and /or consists of an aliphatic diamine and an aliphatic dicarboxylic acid, and at least one component of the diamine or dicarboxylic acid has 8 carbon atoms in the methylene chain.
The present invention relates to a higher polyamide copolymer having a piperidyl ring in its main chain, which contains the above nylon salt or an equimolar mixture as an essential component. The present invention provides a hot melt adhesive having even better adhesive properties. In particular, polyethylene, polyvinyl chloride resin, ethylene-vinyl acetate copolymer resin, polyester, and various polyamides have been used as resins for hot melt adhesives such as fiber base fabrics. Due to its strong adhesive strength and good dry cleaning resistance,
It is widely used as a permanent adhesive interlining. However, in recent years, there has been a growing trend in the clothing industry to make outer materials thinner, and hot melt adhesives for this purpose are also required to be low-temperature melting type and flexible in terms of texture. Various plasticizers,
For example, benzenesulfonebutyramide, 2-ethylhexyl-p-hydroxybenzoate, O
By adding appropriate amounts of - and p-toluenesulfonethylamide, etc., the softening temperature is lowered and flexibility is imparted. However, methods using these plasticizers have the disadvantage that they are likely to cause problems when applied to the processing steps of current adhesive interlining manufacturing methods. That is,
Hot melt adhesives applied to adhesive interlining are generally used in powder form, so if you add the above plasticizers that are liquid at room temperature as they are, the flow characteristics of the hot melt resin powder as a powder will improve. Therefore, it must be blended into the hot melt resin itself in a molten state and then ground into a powder, which poses an economical problem. Powdered plasticizers can be added directly to hot melt resin powder and blended, but mechanical vibrations during the process of transferring the plasticizer to the interlining using a processing machine tend to cause the resin and plasticizer to gradually separate, resulting in quality problems. There will be variations in In order to avoid these drawbacks, a method is used in which water is used as a medium, hot melt resin powder and plasticizer are dispersed in the medium, and the paste is made and transferred onto the core surface, but in order to obtain a stable paste, The addition of protective colloids and surfactants, as well as the addition of thickeners and antifoaming agents, are necessary to obtain stable workability, and these many additives have a more or less negative effect on adhesive strength, and There is a tendency for strength to deteriorate over time. Furthermore, hot melt adhesives that contain plasticizers themselves are applied to adhesive interlining and used for many years, and during washing and cleaning processes, the plasticizers are gradually extracted and the texture is lost. There are some drawbacks. The inventors of the present invention believed that it was necessary to modify the resin itself in order to eliminate these drawbacks, and as a result of extensive study, we determined that the number of carbon atoms in the methylene chain having a piperidyl ring in the main chain was 8. They have discovered a new polyamide copolymer containing the above nylon component as an essential component. That is, the present invention provides (1) a saturated aliphatic dicarboxylic acid that can be represented by HOOC-A-COOH; 5 to 80% by weight of a nylon salt consisting of a secondary diamine represented by or an equimolar mixture thereof (where A is a methylene chain represented by -(CH ₂ ) _l - or -(CH ₂ ) _l -) A divalent hydrocarbon group in which some of the hydrogens are substituted with any alkyl group having 1 to 4 carbon atoms, l is a positive integer of 4 to 20, m is a positive integer of 1 to 10) (2) Lactams having 8 or more carbon atoms in the methylene chain or their ω-aminocarboxylic acids and/or
or a nylon salt or equimolar mixture consisting of an aliphatic diamine and an aliphatic dicarboxylic acid, in which at least one component of the diamine or dicarboxylic acid has 8 or more carbon atoms in the methylene chain;
20% by weight and (3) a lactam with 7 or less carbon atoms in the methylene chain, or its ω-aminocarboxylic acid and/or an aliphatic diamine and an aliphatic dicarboxylic acid, at least one component of the diamine or dicarboxylic acid. is the number of carbon atoms in the methylene chain is 7
The present invention provides a novel polyamide copolymer obtained by polymerizing 0 to 40% by weight of at least one of the following nylon salts or equimolar mixtures. Here, the saturated aliphatic dicarboxylic acid represented by HOOC-A-COOH specifically includes dicarboxylic acids having up to 20 methylene chains, such as adipic acid, pimelic acid, corkic acid, and azelaic acid, but especially adipic acid, Sebacic acid and dodecanedicarboxylic acid are industrially advantageous. Higher dicarboxylic acids having 21 or more methylene chains are difficult to obtain industrially in pure form, and their use is not advantageous. Further, even if the hydrogen in the methylene chain of these dicarboxylic acids is substituted with a relatively short-chain alkyl group having 1 to 4 carbon atoms, the polymerizability can be used without any significant influence. The nylon salt or equimolar mixture of these dicarboxylic acids and bispiperidylalkane is 5 to 80
It is used in a composition range of % by weight, but if it is less than this range, the concentration of piperidyl in the main chain becomes too low and no improvement in adhesion, which is thought to be based on the piperidyl group, is obtained. This is not preferable because the hot water resistance of the copolymer produced by this process decreases. Next, lactams having a methylene chain of 8 or more carbon atoms or their ω-aminocarboxylic acids include ω-nonalactam, ω-decyllactam, ω-
Examples include undecyl lactam, ω-dodecyl lactam, and the corresponding ω-aminocarboxylic acids. In addition, nylon salts or equimolar mixtures thereof are nylon 6.10, nylon 10.10, and nylon 6.12, in which at least one component of the diamine or dicarboxylic acid is an aliphatic diamine having a methylene chain of 8 or more carbon atoms and an aliphatic dicarboxylic acid. , nylon salts such as nylon 12.12, or equimolar mixtures of their components. These components can be used in a wide range from 95 to 20% by weight of the total polyamide copolymer. The nylon component containing the methylene chain having 8 or more carbon atoms and the nylon component containing the piperidyl ring in the main chain are blended together in such a way that the total amount of the nylon component is 60% by weight or more of the total polyamide copolymer. The ratio of these two components is determined by the balance between adhesiveness and hot water resistance.The higher the ratio of the nylon component containing a component with 8 or more carbon atoms in the methylene chain, the better the hot water resistance, and the higher the ratio of the nylon component containing a piperidyl ring. This tends to improve adhesion. The remaining 40% by weight or less is occupied by nylon components containing components with methylene chain carbon atoms of 7 or less, specifically ω-caprolactam and nylon.
6.6 salt or equimolar mixture which influences the melting point of the resulting polyamide copolymer. That is, when the composition ratio of this component is increased and the randomness of the polyamide copolymer is increased, the melting point tends to decrease. As a method for producing the polyamide copolymer, a known method used for producing polyamides can be used. Industrially, melt polymerization using water as an initiator is particularly advantageous. When a lactam is used as a component, a small amount of ω-aminocarboxylic acid and/or phosphoric acid effectively acts to promote polymerization. That is, a predetermined amount of a nylon salt or mixture consisting of a bispiperidylalkane and a saturated aliphatic dicarboxylic acid contains a lactam having 8 or more carbon atoms in the methylene chain, or its ω-aminocarboxylic acid and/or aliphatic diamine as an essential component. A predetermined amount of a nylon salt or an equimolar mixture consisting of an aliphatic dicarboxylic acid in which at least one component of the diamine or dicarboxylic acid has 8 or more carbon atoms in the methylene chain is added, and if necessary, carbon atoms in the methylene chain are added. Add polyamide-forming components in number up to 7. Water is added to this as an initiator. When adding phosphoric acid as a polymerization accelerator, it may be added after being dissolved in this water. The above system is heated to around 250°C under nitrogen pressure to form an initial condensate, and then the desired polyamide copolymer is obtained by heating and condensing it under atmospheric pressure while expelling the water produced by the reaction with a nitrogen stream. Further, as the copolymer, a ternary or quaternary copolymer composition can also be provided. The preferred relative viscosity of the m-cresol solution of the copolyamide of the present invention at a concentration of 0.5 g/100 ml is from 1.4 to 2.5, more preferably from 1.5 to 2.3. The bispiperidylalkane-containing polyamide copolymer obtained in this way exhibits excellent adhesive properties, and can be applied to metals such as steel and aluminum, as well as cardboard, boards, etc., depending on the melting point, which changes depending on the copolymer composition ratio. It can be used as an adhesion promoter for a wide range of materials such as fibers. The present invention will be specifically explained below with reference to Examples. Example 1 First, dodecanedicarboxylic acid HOOC (CH ₂ ) ₁₀ −
Place 276g of COOH in a 3-volume flask, add 900g of isopropyl alcohol, and heat at 65 to 70℃.
The mixture was heated and stirred to completely dissolve. 1.3 to this warming solution
-di-(4-piperidyl)propane 258g and 630g of isopropyl alcohol at room temperature in advance.
was added dropwise under stirring.
Almost simultaneously with the addition, the dicarboxylic acid and diamine salt (hereinafter abbreviated as DP salt) becomes crystalline and precipitates out. After completion of the addition, the precipitated white crystals were left overnight at room temperature, washed with cold isopropyl alcohol, air-dried and dried under vacuum to obtain about 530 g of DP salt. 400 g of the DP salt thus obtained, 400 g of lauryllactam monomer, and 400 g of caprolactam monomer were placed in a 3-volume stainless steel autoclave, and 87.7 g of pure water was added as an initiator, 19.1 g of ω-aminododecanoic acid was added as a polymerization accelerator, and fluorescent light was added. After adding 0.0115 g of the dye Uvitex MD (manufactured by Ciba Geigy), the system was completely purged with nitrogen, and the internal pressure was then increased to 4 kg/cm ² G by nitrogen pressurization, followed by raising the temperature. The temperature reached 260°C and the internal pressure reached 19 kg/cm ² G in about 3 hours.
This state was maintained for 4 hours, and the temperature of the system was lowered to 200°C for a further 5 hours. At the same time, the pressure was gradually released to atmospheric pressure. The mixture was then heated and stirred at 200° C. for 5 hours while flowing nitrogen at a flow rate of 150 ml/min. After the reaction was completed, the molten resin was extruded into a strand by applying nitrogen pressure, cooled in a water bath, and pelletized using a pelletizer. 25 of a metacresol solution with a concentration of 0.5 g/100 ml of the resulting polymer.
The relative viscosity at °C was 1.45, and the peak melting temperature by differential scanning calorimetry (DSC) was 95 °C. Next, the pellets were cooled using liquid nitrogen, and crushed using a pin-type crusher while adding liquid nitrogen, and sieved to obtain a powder with a diameter of 63 microns. Next, powder dot coating was performed on cotton broadcloth (#80) using this hot melt resin powder. That is, preheat the cotton broadcloth (#80) through a roll heated to 250℃, and pass it through a 50℃ engraving roll (17 points/25mm x 17 points/25
Transfer the above powder from mm; 0.80mmφ×0.3mmH),
The transferred dot-like powder was then baked onto the base fabric through infrared heating. The transfer speed at this time was 5 m/min, and the amount transferred to the base fabric was 18.3 g/min.
It was ^m2 . This adhesive cotton broadcloth was used as a test sample for press bonding with cotton broadcloth (#80). The press pressure was kept constant at 300g/cm ² and the press time was kept constant at 10 seconds, and the press temperature was changed from 110℃ to 150℃ for press bonding. After conditioning the humidity at 23℃ and 50% RH for 24 hours, the adhesive strength was determined by T-peeling. was measured. The tensile speed is 200
mm/min. The obtained results are shown as curve A in Figure 1.
It was shown in For comparison, a polyamide copolymer obtained from 40% by weight of lauryl lactam, 30% by weight of caprolactam, and 30% by weight of a salt of hexamethylene diamine and dodecanedicarboxylic acid (relative at 25°C in a metacresol solution with a concentration of 0.5 g/100 ml) Viscosity 1.45; DSC
Using 63 micron pass powder with a melting peak temperature of 110℃), transfer to cotton broadcloth (#80) under the same conditions as above (transfer amount 19.1 g/m ² ), then press adhesion test with cotton broadcloth (#80) The adhesive strength of the sample was measured. This result is shown by curve C in FIG. Furthermore, for comparison, lauryllactam 30% by weight,
Polyamide quaternary copolymer (relative viscosity 1.35; DSC
Transferred to the same base fabric under the same conditions (transfer amount 20.6
Curve B in FIG. 1 shows the results of the adhesive strength measured in the same manner for a press adhesion test sample with cotton broadcloth (#80) (g/m ² ). As is clear from these results, the polyamide copolymer (curve A) containing a bispiperidylalkane salt as a component has a low melting point and exhibits good adhesive strength even at a relatively low adhesive press temperature. Examples 2 to 5 According to the composition shown in Table 1, the charged amount was 1200 g and placed in a 3-volume stainless steel autoclave, and as in Example 1, pure water and a small amount of ω-amino acid were added as needed. Polymerization was carried out by adding dodecanoic acid. Relative viscosity and DSC of the obtained polymer
The melting peak temperatures are shown in Table 1. For comparison, a ternary copolyamide consisting of lauryl lactam, caprolactam and hexamethylenediamine adipate, which does not contain DP salt as a component, was similarly polymerized and used as a comparative example, which is shown in Table 1. Each polymer was made into a powder by freeze-pulverization using liquid nitrogen, and a powder with a diameter of 63 microns was obtained by sieving. Using these powders, powder dot coating was performed on cotton broadcloth (#80) under the same conditions as in Example 1. The amount of transcription is 18.0 to 19.0 in both cases.
g/ ^m2 . Using this adhesive cotton broadcloth, press adhesion was performed with cotton broadcloth (#80), and the adhesion was measured. The results are shown in Table 1 along with comparative examples. Compared to the comparative example, it shows good adhesion, especially in the region of low press temperatures.

[Table] Example 6 Using the same polymerization method as in Example 1, 25% by weight of lauryl lactam, 25% by weight of caprolactam, 25% by weight of the salt of hexamethylene diamine and dodecanedicarboxylic acid, and azelaic acid and 1,5-dicarboxylic acid were added. −
A polyamide copolymer containing 25% by weight of (4-piperidyl)-pentane salt was obtained. This copolymer
The relative viscosity at 25°C of a metacresol solution with a concentration of 0.5 g/100 ml was 1.50, and the DSC melting peak temperature was 92°C. The same cotton broadcloth (#80) as in Example 1 was prepared using a 63 micron pass powder of this polyamide copolymer.
A press adhesion test was conducted between the two. Powder transfer amount
Adhesive strength under pressing conditions of 18-19g/m ² , press pressure 300g/cm ² , and press time 10 seconds
Width) is 500 at press temperature 120℃, press temperature 130
It was 700 at ℃ and 720 at press temperature of 140℃. Example 7 Using the same polymerization method as in Example 1, 33% by weight of lauryl lactam, 33% by weight of caprolactam, octadecanedicarboxylic acid and 1,3-di(4
A polyamide copolymer consisting of 34% by weight of a salt of -piperidyl)-propane was obtained. 0.5 of this copolymer
The relative viscosity at 25°C of the metacresol solution with a concentration of g/100ml was 1.62, and the DSC melting peak temperature was 112°C. Using this polyamide copolymer powder with a 63 micron pass, a press adhesion test between cotton prosthetics (#80) was conducted in the same manner as in Example 1. Powder transfer amount 18-19g/m ² , press pressure 300g/cm ² ,
The adhesive strength (g/25 mm width) under pressing conditions with a pressing time of 10 seconds was 180 at a pressing temperature of 120°C, 350 at a pressing temperature of 130°C, and 500 at a pressing temperature of 140°C.

[Brief explanation of the drawing]

Figure 1 shows the adhesive strength between cotton broadcloth (#80) and cotton broadcloth (#80) when the pressing temperature was changed.

Claims (1)

[Claims] 1. A saturated aliphatic dicarboxylic acid that can be represented by HOOC-A-COOH; 5 _to 80% by weight of a nylon salt or an equimolar mixture thereof _consisting of _a secondary diamine _represented by A divalent hydrocarbon group in which a portion of hydrogen is substituted with an arbitrary alkyl group having 1 to 4 carbon atoms, l is a positive integer of 4 to 20, m is a positive integer of 1 to 10) 2 methylene chain Nylon consisting of kratam having 8 or more carbon atoms or its ω-aminocarboxylic acid and/or an aliphatic diamine and an aliphatic dicarboxylic acid, and having 8 or more carbon atoms in the methylene chain of at least one component of the diamine or dicarboxylic acid. Salt or equimolar mixture 95 to 20% by weight 3 Consisting of kratam or its ω-aminocarboxylic acid and/or aliphatic diamine and aliphatic dicarboxylic acid having 7 or less carbon atoms in the methylene chain, at least one of the diamine or dicarboxylic acid One component contains at least one nylon salt or an equimolar mixture of up to 7 methylene chain carbon atoms.
A novel polyamide copolymer having a relative viscosity of 1.4 to 2.5 in m-cresol solution with a concentration of 0.5 g/100 ml obtained by polymerization from 0 to 40% by weight of different types.