JPS595133B2 - Manufacturing method of copolymerized polyamide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a polymerizable fatty acid (A), (B) an aliphatic dicarboxylic acid having 6 to 20 carbon atoms or an ester thereof, and (O) xylylene diamine through a polycondensation reaction. In producing the polymerized polyamide, (1) at least two or more types of (B) are used, and (2) (A) to B) are used in a molar ratio of 80:20 to 5:95. The present invention relates to a method for producing a copolymerized polyamide.

BACKGROUND ART Conventionally, it has been known to produce a copolyamide by subjecting a mixture of a polymerizable fatty acid, one type of aliphatic dicarboxylic acid, and xylylene diamine to a polycondensation reaction.

However, the properties of the polyamide obtained from the above composition give favorable results only in a range in which the molar proportion of the aliphatic dicarboxylic acid in the total acid component to be added is relatively small.

That is, generally 5 aliphatic dicarboxylic acids in the total acid component
When the molar proportion of polyamide increases, not only does the melting temperature of the resulting polyamide rise rapidly, but also the flexibility, transparency, processability, etc. of the polymer decrease, making it difficult to use it as a film, adhesive, etc. . On the other hand, if the molar ratio of the aliphatic dicarboxylic acid is too low (10), the melting temperature of the resulting polyamide will be too low and the resulting polyamide will be too sticky, causing problems such as blocking during film forming, which is not preferable. For example, in a polyamide obtained by copolymerizing adipic acid 15 as an aliphatic dicarboxylic acid in the coexistence of a polymerizable fatty acid and xylylene diamine, the molar ratio of adipic acid to the total acid components to be added is 0.2. If the temperature is exceeded, the melting temperature of the polymer will exceed 150°C and the flexibility will drop sharply.

On the other hand, if the molar ratio of adipic acid is less than 0.1, the polymer becomes extremely sticky, which causes problems during molding and quality.

Generally, a melting temperature range of 150° C. or less is a temperature range commonly used in many areas from the viewpoint of workability, economic efficiency, and furthermore, the heat resistance of the resulting products.

For example, in the fields of packaging films, hot melt adhesives, etc., the practical temperature is 150°C at the melting temperature of the polymer.
℃ or below (processing and working temperature below 30,170℃).

Therefore, in the conventional method of using one kind of aliphatic dicarboxylic acid and a polymerizable fatty acid as the acid component and obtaining a copolyamide from this and xylylene diamine, the proportion of the aliphatic dicarboxylic acid in the total acid component is extremely low. Good results are obtained only when the ratio of the aliphatic dicarboxylic acid is small, but even a small change in the ratio of the aliphatic dicarboxylic acid causes a considerable change in the properties such as the melting temperature of the copolyamide. Therefore, strict operation is required.

However, the performance of the polymers obtained in this way is still insufficient, and the field of use is limited in terms of practicality. In addition, the molar molecular weight of the polymerizable fatty acid is approximately 2.5 to 4.0 times that of the aliphatic dicarboxylic acid, and the melting temperature is 150
If we try to obtain a copolymerized polyamide with a temperature below Needless to say, using expensive polymerizable fatty acids as the main ingredient is extremely disadvantageous from an economic point of view. As a result of various studies in order to solve the above-mentioned drawbacks, the present inventors have discovered that a copolymerized polyamide can be produced by polycondensing a mixture consisting of (A) a polymerizable fatty acid, (B) an aliphatic dicarboxylic acid, and (0 xylylene diamine). In manufacturing, at least two or more types of (B) are used, and a combination of (
The present inventors have discovered that all of the above-mentioned drawbacks can be solved by using (g) at a specific mixing molar ratio, and have arrived at the present invention. The copolyamide obtained by the method of the present invention has the ability to be formed into soft and pliable films and filaments without the addition of plasticizers, and also has the following excellent properties: There is.

(a) The melting temperature is relatively low, generally within the range of 150°C or lower.

(b) Good melt adhesion and high adhesive strength.

(c) Excellent transparency and gloss. (d) Water resistance;
Excellent chemical and oil resistance.

(It has good flow and excellent processability.) No copolyamide has been known that has the above-mentioned well-balanced properties.

The copolyamide produced by the method of the present invention can be used for general purposes because of the above-mentioned various properties. For example, it can be formed into a film and used as a packaging material for various articles or as a covering material for steam sterilization, or it can be laminated with a film of aluminum foil, ionomer resin, ethylene monovinyl acetate copolymer, poval cellophane, polystyrene, etc. using hot melt adhesive. It is possible to provide a strongly adhesive material with excellent water, oil, and chemical resistance for use in packaging foodstuffs and other items. Further, the filament formed into a filament can be used for producing highly elastic yarns, woven and knitted fabrics, web-like heat-sealable nonwoven fabrics, and the like. In addition, it can be used for various purposes by taking advantage of the above characteristics. The method of the present invention and its preferred embodiments will be further explained below.

The components to be subjected to the polycondensation reaction in the present invention include (A polymerizable fatty acid, (B) at least two types of aliphatic dicarboxylic acids having 6 to 20 carbon atoms or esters thereof, and It is a mixture obtained by mixing at a molar ratio.

Polymerizable fatty acid is a general term for polymers obtained by coupling unsaturated long-chain monocarboxylic fatty acids having 16 to 22 carbon atoms, such as oleic acid, linoleic acid, linolenic acid, etc. 80% or more preferably 85
% or more, and contains small amounts of other monomers and trimers, and those that are commercially available as industrial products can be used.

Commercially available products include Dimer Acid [trade name: Empol 1010 (analytical value after purification: monomer (Cl8)) manufactured by Emery & Co.
0.1%, dimer (C36) 99% Q trimer (C54)
0.5%, others 0.4%), Empol 1014 (analytical values after purification: monomer (Cl8) 1.1%, dimer (C
36) 97%, trimer (C54) 0.9%, other 1%
), Enpol 1016 (analytical value after purification: monomer (C
l8) 0.5%, dimer (C36) 94%, trimer (C
, 4) 3.5%, other 2%), Empol 1018 (
Analytical values after purification: Monomer (Cl8) 0.3%, dimer (
C36) 91%, trimer (C,4) 5.7%, other 3
%), Empol 1022 (analytical value after purification: monomer (
Cl8) 2.3%, dimer (C36) 84%, trimer (
C54) 12.2%, others 1.5%), General Mills Co., Ltd. and Daiichi General Co., Ltd. dimer acid [trade name,
Versadime 108S (analytical value after purification: monomer (Cl
8) 1.2%, dimer (C36) 83.6%, trimer (
C,4) 14.1%, others 1.1%) and Versadime 240 (analytical values after purification: monomer (Cl8) 1%, dimer (C36) 85.2%, trimer (C54) )11.5
%, others 2.3%], etc. Examples of aliphatic dicarboxylic acids having 6 to 20 carbon atoms used in combination with polymerizable fatty acids include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid, and eicosadionic acid. , hexadenedionic acid, eicosadienedionic acid, 2.2
- Saturated or unsaturated aliphatic dicarboxylic acids such as 4- and 2,4,4-trimethyladipic acid, and
Examples of these esters include alkyl esters such as hexadecenenionic acid methyl ester and eicosadienic acid methyl ester.

At least two or more of these aliphatic dicarboxylic acids or esters thereof are used in combination. In this case, when there are two kinds of aliphatic dicarboxylic acids or esters thereof to be mixed, it is preferable that the proportion of the aliphatic dicarboxylic acids or esters thereof is at least 20 mol % or more for the smallest component among both components. Further, when three or more types of aliphatic dicarboxylic acids or esters thereof are mixed, the largest component is 20 to 80 mol%, and the total amount of the other two or more components is 80 to 20 mol%. It is preferable. If the mixing ratio is outside the above range, the effect of using two or more types of aliphatic dicarboxylic acids or their esters will be small, and the effect of using two or more types of aliphatic dicarboxylic acids or their esters will be substantially the same as when using one type of aliphatic dicarboxylic acids or their esters, and the present invention The effect is not expressed. As xylylene diamine, meta or a mixture of meta and para-xylylene diamine may be used.

In the present invention, those having a meta-isomer content of 50% or more are preferably used. The mixing molar ratio of both (A) polymerizable aliphatic and (B) at least two or more types of aliphatic dicarboxylic acids having 6 to 20 carbon atoms or esters thereof is 80:20.
~5:95.

If it is outside this range, a copolyamide having the desired good properties cannot be obtained. The proportion of aliphatic dicarboxylic acid or its ester in the total acid component is 20 to 50 mol%
Within this range, the effect of reducing the melting temperature of the obtained copolyamide is large, and the effect of improving transparency and adhesiveness is large. On the other hand, when the proportion of the aliphatic dicarboxylic acid or its ester in the total acid component is in the range of 50 to 95 mol%, it not only has the effect of reducing the melting temperature of the copolyamide and improving the transparency, but also has the effect of reducing the flexibility. The effect of giving is large. Generally, if the content of component A exceeds 80 mol %, the melting temperature of the resulting copolyamide becomes too low and the polymer becomes sticky, which is undesirable since workability and processability are reduced.

On the other hand, if the content of component (B) exceeds 95 mol %, not only the flexibility and transparency of the resulting copolyamide J are lost, but also the melting temperature becomes too high, resulting in poor processability, which is not preferred.

However, these molar ratios can be appropriately selected within the above range depending on the desired use of the copolyamide. A particularly preferred range is a molar ratio of component (A) to component (B) of 75:25 to 15:85. Here, the effects of each component subjected to the polycondensation reaction will be explained.

The polymerizable fatty acid imparts flexibility to the copolyamide, and the xylylene diamine imparts transparency and gloss. Also,
at least two aliphatic dicarboxylic acids or esters thereof
The mixture of more than one species serves to control the melting temperature of the copolyamide. For example, when only one type of aliphatic dicarboxylic acid or its ester is used, the melting temperature of the copolyamide will rise significantly even with the addition of a small amount of the aliphatic dicarboxylic acid or its ester, and the amount added will increase significantly. Since the melting temperature increases monotonically with increasing temperature, the amount of aliphatic dicarboxylic acid or its ester added must be extremely small in order to produce a copolyamide with the expected and desired low melting temperature. On the other hand, when at least two or more aliphatic dicarboxylic acids or esters thereof are added, the above-mentioned wide variation in the melting temperature is suppressed, and it becomes very easy to set the desired melting temperature of the copolyamide in actual operation. The polycondensation reaction of the polymerizable fatty acid, at least two or more aliphatic dicarboxylic acids or esters thereof, and xylylene diamine can be carried out by a conventional method for producing polyamide.

That is, each of the above components was heated to 100 to 25% under an inert atmosphere.
The mixture is heated to 0.degree. C. and the water that is released due to the formation and condensation of nylon salts is removed until it is almost completely eliminated. Adding a small amount of water at the beginning, for example, 1 to 30% by weight of water based on the total amount of monomer components, increases the thermal conductivity in the system at the initial stage of the reaction and creates a homogeneous copolyamide product. It is effective to obtain In addition, during the polycondensation reaction, small amounts of viscosity stabilizers such as monocarboxylic acids and monoamines, antistatic agents, antioxidants, light stabilizers,
Pigments and the like may also be added. According to the method of the present invention, it has excellent transparency and flexibility, and has a melting temperature of 150°C or less, which is of high practical value, without being subject to restrictions on the molar ratio of the aliphatic dicarboxylic acid or its ester in the total acid component. Copolymerized polyamide can be easily obtained, and its practical significance is great.

Examples and comparative examples are listed below to illustrate the present invention and its effects.

In addition, the physical property values were measured by the following method. Reduced viscosity polymer 0.5f to special grade m-cresol 100ml 5
A transparent polymer melted below 0°C and measured in a constant temperature bath at 30°C was heated to T
- Thickness 50-8 by die extruder or hot press
It was molded into a 0 μ film and the haze value was measured (AST
M-D-1003).

Melting temperature of flexibility sensory test repolymer +20~30℃
A film with a thickness of 80μ is made using a press heated at a temperature of

Pencil hardness: Hold a pencil vertically on the cross section of the polymer chip,
The state of the scratches on the tip and the state of penetration of the pencil lead at that time were judged by the hardness of the pencil, and those softer than H were judged to be flexible.

Water resistance (washing test) In an electric washing machine, wash the composite adhesive fabric in 0.8% soapy water at 50°C for 30 minutes, then wash it in 50°C water for 10 minutes.
Washed with water for a minute.

After repeating water washing twice, dehydration was performed, and after drying at 80° C., the peel strength retention rate was measured. Melting temperature An extremely thin piece of polymer was sandwiched between cover glasses and observed and measured using a micro melting point meter (manufactured by Yanagimoto Seisakusho) using transmitted light.

Peel strength: Conforms to ASTM-D-1876. Unless otherwise specified, the polymerizable fatty acids and xylylene diamine used in the Examples and Comparative Examples are Dimer Acid (trade name, Empol 1010) manufactured by Emery Co., Ltd.
Analytical values after purification: Monomer (Cl8) 0.1%, dimer (
C36) 99%, trimer (C54) 0.5%, others 0
．． 4%] and a meta/para mixed xylylene diamine with a meta content of 70 mol%.

Example 1 Polymerizable fatty acid 392.0k9 (70 mol%) Sebacic acid 16.2k9 (8 mol%) Dodecanedioic acid 50.7 kg (32 mol%) Xylylenediamine 136.21<9 Water
After charging 6.12 kg into an autoclave and completely purging the system with nitrogen, the mixture was heated at 100° C. for 60 minutes to produce nylon salt.

Next, the temperature was raised to 180°C and the internal pressure was reduced to 8k9/Cd.
And so. After 90 minutes had elapsed, the water added from within the system and the water produced by condensation were distilled off, and the inside of the system was brought to atmospheric pressure in 60 minutes.

Thereafter, the temperature was raised to 240°C. After heating at that temperature for 90 minutes, the resulting polymer was extruded under nitrogen pressure and pelletized by a conventional method. The obtained polymer is tough and has excellent gloss, a reduced viscosity of 0.50 d1/V, and a melting temperature of 105°C.
The pencil hardness was 4B or less, and the transparency was 1.9%.

Next, this polymer was ground into 50 to 100 meshes in a sample mill in the presence of dry ice.

The obtained powder is placed between a rayon nonwoven fabric and a cotton fabric for about 50y/
ml, and heated and pressed at 160° C. for 15 seconds. The obtained composite fiber was strongly bonded and had a peel strength of 3.21<g/1511tm. Also,
The washing resistance of this composite fiber was as shown below, and it was excellent in water resistance. Examples 2 to 4, Comparative Examples 1 to 3 Polymerizable fatty acids, adipic acid, sebacic acid, and xylylene diamine were used as raw materials, and 10% by weight of water was added to them, and the preparation composition was as shown in Table 1. A polycondensation reaction was carried out in the same manner as in Example 1.

Table 1 shows the physical properties of the obtained polymer. Example 5
212. A mixture consisting of 28.90 kg (50 mol%) of polymerizable fatty acid, 20 mol% of hexadecenenionic acid methyl ester, and 80 mol% of eicosadienic acid methyl ester.
4 kg (50 mol%), xylylenediamine 136.2
K9 and 4.5 kg of water were charged into an autoclave, and a polycondensation reaction was carried out in the same manner as in Example 1.

The obtained polymer had a transparency of 2.9%, flexibility (sensory test...extremely pliable, pencil hardness,
......Excellent HB), reduced viscosity 0.35d
1/y, and the melting temperature was 102°C.

Example 6 Polymerizable fatty acid 280.0 kg (50.1 mol%)
Adipic acid 12.13k9 (8.3 mol%)
Azelaic acid 62.68 kg (33.3 mol%
] Dodecanedioic acid 19.121<9 (8.3 mol %) Xylylene diamide 136.2 kg and water 9.0 k9 were subjected to a polycondensation reaction in the same manner as in Example 1.

The obtained polymer was characterized by transparency, flexibility (sensory test...
・・・・・・Extremely flexible, pencil hardness 2B or less), reduced viscosity 0.52 d1/y, melting temperature 115°C
It was hot. The polymer pellets were then formed into a film using a T-die extruder at 165 DEG C., resulting in an extremely flexible film with an average thickness of 80 microns, free of blocking, and excellent in transparency and gloss.

Comparative example Tetrapolymerized fatty acid 289.58 kg (50.
1 mol%) azelaic acid 93.93 kg (49.
(9 mol %) xylylenedia 136.21<9mine water 9.0k9 was subjected to a polycondensation reaction in the same manner as in Example 1.

The obtained polymer had a reduced viscosity of 0.48 d1/7, a melting temperature of 170° C., a pencil hardness of H to 2H, and lacked flexibility. Comparative Example 5 Adipic acid 24.3k9 (16.6 mol%)
Azelaic acid 125.5 kg (66.7 mol%)
Dodecanedioic acid 38.2 kg (16.6 mol%)
136.0 kg of xylylene diamide and 18.0 kg of water were subjected to a polycondensation reaction in the same manner as in Example 1.

The obtained polymer showed flexibility (sensory test...
... Very hard, extremely poor pencil hardness (more than 3H), reduced viscosity 0.51d1/7, melting temperature 127℃
It was hot. Next, this polymer was molded into a film using the same extruder as in Example 6, and the processing temperature was changed to 2.
Not only is it difficult to melt and mold unless the temperature is 30℃,
The resulting film was hard and inflexible, and cracks were observed when bent.

Example 7 Polymerizable fatty acid 56.0k9 (10 mol%) Adipic acid 43.8 kg (30 mol%) Sebacic acid 60.7 kg (30 mol%) Dodecanedioic acid 69.11<9 (30 mol%) Xylylene diamine 136.0k9 water
9.0 kg was subjected to a polycondensation reaction in the same manner as in Example 1.

The obtained polymer is transparent, has excellent gloss, has good flexibility (sensory test: extremely flexible, pencil hardness HB), has a reduced viscosity of 0.48 d1/7, and a melting temperature of 104°C. It was hot. This polymer was then deposited to a thickness of 10 μm.
The sample was sandwiched between two sheets of aluminum foil, preheated at 130°C for 1 minute, and then hot pressed at 130°C and 2K9/Crii for 3 minutes.

The peel strength of the obtained laminated laminate was 4.2 kg/15 m.
m, and the adhesion was good. Comparative Example 6 A polycondensation reaction was carried out using 56.0 kg (10 mol%) of polymerizable fatty acid, 207.3 kg (90 mol%) of dodecanedioic acid, 136.2 k9 of metaxylylene diene, 20 k9 of amine water in the same manner as in Example 1. .

The obtained polymer had a reduced viscosity of 0.57 d1/y, a melting temperature of 190° C., a pencil hardness of 2H, and was extremely poor in flexibility. Next, this polymer was molded into a film using the same extruder as in Example 6, and it was found that unless the processing temperature was raised to 240°C or higher, not only did it have poor fluidity and was difficult to melt mold, but it was also difficult to obtain a film due to the high temperature molding. Coloring was observed on the film.

Claims (1)

[Claims] 1. In producing a copolyamide by polycondensing a mixture consisting of (A) a polymerizable fatty acid, (B) an aliphatic dicarboxylic acid having 6 to 20 carbon atoms or its ester, and (C) xylylene diamine, ( 1) A method for producing a copolyamide, characterized by using at least two or more types of (B), and (2) using (A) to (B) in a molar ratio of 80:20 to 5:95. .