JPH0226646B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyesteramide polycondensate. More specifically, the present invention relates to a thermoplastic resin composition that has excellent solvent resistance, flexibility, water resistance, and transparency and is useful as an interlining adhesive.

In recent years, adhesive interlining has developed into an extremely useful material for sewing clothing due to the shortening of the sewing process, uniformity of finish, rationalization, etc.

Currently, nylon-based, polyester-based, high-density polyethylene, low-density polyethylene, ethylene/vinyl acetate copolymer, polyvinyl chloride, etc. are used as hot melt adhesives for interlining, but each has advantages and disadvantages, and The reality is that the performance as a hot melt adhesive for interlining is not satisfied.

For example, polyvinyl chloride requires high temperatures and pressures for adhesion, which can damage the fibers. Other polyolefins require seams due to their weak adhesive strength and are used only for temporary bonding.

On the other hand, nylon resins have strong adhesive strength and good dry cleaning resistance, but have a disadvantage of poor hot water washing resistance. On the other hand, polyester resins are highly amorphous and flexible, and have excellent adhesion to polyester clothing. However, although this material has better hot water washing resistance than nylon-based materials, it has a major drawback in that its dry cleaning resistance is extremely poor. Polyesteramide resins containing both polyester segments and polyamide segments have also been proposed (Japanese Patent Publication No. 49-13638), but these have not always been sufficient in terms of dry cleaning resistance and hot water washing resistance.

Therefore, the inventors of the present invention have conducted intensive studies to overcome the drawbacks of the above-mentioned nylon and polyester interlining adhesives, and have found that block polyesteramide containing specific components has excellent dry cleaning resistance and hot water washing resistance. The present invention was completed based on the discovery that the present invention is also excellent.

That is, the present invention comprises (A) a dicarboxylic acid or its ester derivative; and (B) an alkylene glycol having 2 to 8 carbon atoms (B-
1), and aromatic diol (B-2) represented by the following general formula (1) [In formula (1), R is an alkylene group having 2 to 4 carbon atoms and may be the same or different. x and y are numbers greater than or equal to 1, and x+y is less than or equal to 20. ] and (C) an aliphatic polyamide having carboxyl groups at both ends, the content of the aromatic diol (B-2) is 1 to 30% by weight, obtained by polycondensation reaction. A certain block polyesteramide polycondensate is provided.

Examples of the dicarboxylic acid component used in the present invention include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and phthalic acid, or ester derivatives thereof, and fatty acids having 6 to 12 carbon atoms such as adipic acid, azelaic acid, and sebacic acid. Mention may be made of group dicarboxylic acids or their ester derivatives.

Alkylene glycol having 2 to 8 carbon atoms (B-1), which is one of the diol components used in the present invention
Examples include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, and the like.

Aromatic diol (B-
2) is particularly important in the present invention. By adding this aromatic diol as one of the diol components, excellent dry cleaning resistance and hot water washing resistance not found in conventional products were obtained.
The proportion of the aromatic diol (B-2) in the polyesteramide polycondensate is 1 to 30% by weight, preferably 2 to 15% by weight. If the amount is less than this range, the remarkable effects of the present invention cannot be obtained, and if it is too much, the texture will be poor.

In general formula (1), R is an alkylene group having 2 to 4 carbon atoms and may be the same or different;
It means that (RO)x and (RO)y are (poly)oxyethylene, (poly)oxypropylene, (poly)oxybutylene chains, or blocks or random mixed chains thereof. Among them, (poly)
Oxyethylene chains are preferred. x and y are numbers greater than or equal to 1, and x+y is less than or equal to 20. x+y
If it exceeds 20, water resistance decreases. Most preferably x and y are 1.

Specific examples of aromatic diols represented by general formula (1) include polyoxypropylene (2)-2,2-bis(4-hydroxyphenyl)-propane, polyoxyethylene (2)-2,2- Bis(4-hydroxyphenyl)-propane, polyoxypropylene
(6)-2,2-bis(4-hydroxyphenyl)-
Examples include propane, polyoxyethylene(8)-2,2-bis(4-hydroxyphenyl)-propane, polyoxypropylene(16)-2,2-bis(4-hydroxyphenyl)-propane, etc. can.

The above (A) and (B) components form ester segments in the polyesteramide polycondensate of the present invention, but their proportion in the polycondensate is 10 to 10.
90% by weight, preferably 30-80% by weight. Among them, the proportion of dicarboxylic acid component (A) in the polycondensate is 2 to 60% by weight, and the proportion of diol component (B) is 8 to 50%.
It is preferable that the weight% or the proportion of the aliphatic diol component (B-1) is 7 to 49% by weight (the proportion of the aromatic diol component (B-2) is 1 to 30% by weight as described above). be.

The aliphatic polyamide (C) used in the present invention has carboxyl groups at both ends, and has a number average molecular weight of 600 to 600.
6000 is preferred. The method for producing this polyamide is arbitrary and is not particularly limited, and the polyamide can be produced by a known method. For example, 11-aminoundecanoic acid,
A method of thermal polycondensation of aminocarboxylic acids such as 12-aminododecanoic acid in the coexistence of an appropriate amount of dicarboxylic acid, and ring-opening of lactams such as ε-calactam and ω-laurolactam in the coexistence of an appropriate amount of water and dicarboxylic acid. It is produced by heating polycondensation of a dicarboxylic acid such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, etc. and a diamine such as hexamethylene diamine in the presence of an excess amount of dicarboxylic acid.

The proportion of aliphatic polyamide in the polycondensate is
10 to 90% by weight, preferably 20 to 70% by weight.

The method for producing the block polyesteramide polycondensate consisting of the above components (A) to (C) is arbitrary, and the starting materials,
A known polycondensation method can be selected depending on the blending ratio and the like. An example is as follows.

First, an aliphatic polyamide having carboxyl groups at both ends is synthesized by a known method. Next, this aliphatic polyamide (C), dicarboxylic acid or its ester derivative (A), aliphatic diol (B-1),
The aromatic diol (B-2) represented by the general formula (1) is mixed, a transesterification catalyst is added thereto for transesterification, and then condensation polymerization is carried out under high vacuum.

In carrying out the present invention, other polycondensation components may be added to the extent that the effects of the present invention are not impaired. Among them, the above alkylene glycol (B-
A composition having an excellent hand when poly(alkylene oxide) glycol having a number average molecular weight of 500 to 10,000 is blended as another diol component into a diol mixture mainly consisting of 1) and aromatic diol (B-2). is obtained.

Examples of the poly(alkylene oxide) glycol include those having a number average molecular weight of 500 to 10,000, such as polyethylene glycol, polypropylene glycol, and polytetraethylene glycol. The proportion of this component in the polycondensate may be 20% by weight or less, but preferably 1 to 10% by weight.

The thus obtained block polyesteramide was heated at 100 to 170°C by the ring and ball method (JIS-K-5902).
It has a softening point of Further, the melt viscosity measured at 180° C. with a B-type viscometer at a rotor rotation speed of 0.6 to 60 rpm is 3000 to 60000 cps.

The block polyesteramide of the present invention is freeze-pulverized, made into a fine powder, applied to interlining, or molded into a film and used by thermally adhering it to clothing using a heat press or a household iron. The bonding temperature is preferably 110-180℃, and the appropriate bonding pressure is
It is 200-700g/ ^cm2 .

The block polyesteramide of the present invention has excellent dry cleaning resistance and hot water washing resistance, has a soft texture, and is suitable for cotton, wool, rayon, etc.
It also exhibits excellent adhesion to clothing made of acrylic, acetate, etc., making it ideal for use as an adhesive for the interlining of these clothing.

Further, in another embodiment of the present invention, by taking advantage of its excellent solvent resistance and flexibility, it can be used for applications such as films, fibers, molded products, coating agents, primers, and binders. Furthermore, the thermal and mechanical properties of polyester resin and polyamide resin,
It can also be used as a modifier for processing properties, etc.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

In addition, "parts" in the examples are "parts by weight" unless otherwise specified.
represents.

Example 1 300 parts of sebacic acid, 155 parts of hexamethylene diamine
The mixture was placed in a separable flask, and the temperature was raised to 250°C under a nitrogen stream while stirring to remove water.
The reaction was carried out at 250°C for 0.5 hours, and the temperature was further raised to 270°C, and the reaction was continued for 1.5 hours. Then 270℃, 3mm
A 6.10-nylon prepolyamide was obtained by reacting with Hg for 3 hours. The acid value of this thing is
The total amine value was 31.1KOHmg/g and 0.5KOHmg/g.

Next, this 6.10 - 100 parts of nylon, 57.4 parts of dimethyl terephthalate, 35 parts of dimethyl isophthalate
parts, 1,4-butanediol 59 parts, neopentyl glycol 28.6 parts, polyoxyethylene(2)-2,
10 parts of 2-bis(hydroxyphenyl)propane,
0.1 part of tetrabutyl titanate was charged into a separable flask, and the temperature was raised to 220°C under a nitrogen stream to perform transesterification, and methanol was distilled off.
The temperature was further raised to 250°C and the reaction was continued for 1.5 hours. Thereafter, the system was gradually evacuated and reacted at 2 mmHg for 1.5 hours to obtain a block polyesteramide.
The softening point of the obtained block polyesteramide is
The temperature was 164.5°C, and the melt viscosity was 16000 cps at 180°C.

The film properties of this block polyester amide at 23°C are tensile strength of 185 kg/cm ² and elongation of 350%.
(tensile speed 50 mm/min).

Swelling rate for hot water washing solution (0.5% flake Marcel soap aqueous solution 60℃, shaking for 60 minutes, bath ratio 1/50
[Weight ratio]) was 0.49%, and the swelling ratio with respect to percrene (60°C, shaking for 60 minutes in percrene, bath ratio 1/50 [weight ratio]) was 9.2%.

This block polyester amide has a thickness of 100μ.
m film, sandwiched between polyester/cotton (65/35) broad cloth, and heat-pressed to 170 mm.
C., 500 g/ ^cm.sup.2 for 20 seconds, and the adhesive strength was measured using a T-peel at 23.degree. C. and a tensile speed of 100 mm/min, and found to be 4.6 Kg/25 mm. The adhesive strength after the dry cleaning test was 4.0 kg/25 mm, and the adhesive strength after the hot water washing test was 4.6 kg/5 mm, both of which showed high adhesive retention.

(Dry cleaning test: 60 in 20℃ perclean
Hot water washing test: Soaked at 60℃ for 60 minutes in a 0.5% flake marusene soap aqueous solution, rinsed in a 40℃ hot water bath for 10 minutes, then dried at 60℃ for 90 minutes) A similar test was conducted on polyester tropical cloth, and the adhesive strength was 5.1, 4.1, and 4.9 Kg/25 mm at the initial stage, after the dry cleaning test, and after the hot water washing test, respectively.

Example 2 100 parts of 6.10-nylon synthesized in Example 1, 57.4 parts of dimethyl terephthalate, 35 parts of dimethyl isophthalate, 59 parts of 1,4-butanediol, 28.6 parts of neopentyl glycol, polyoxyethylene
(2)-2,2-bis(hydroxyphenyl)propane 20 parts, polyethylene glycol (number average molecular weight
1000) and 0.1 part of tetrabutyl titanate were placed in a separable flask, and a block polyesteramide was synthesized in the same manner as in Example 1. The softening point of the resin was 154°C, and the melt viscosity at 180°C was 6400 cps. Tensile strength at 23°C is 120Kg/cm ² , elongation is 375%, and swelling rates for percrene and hot water washing liquid are 12.7% and 0.63%, respectively.
It was hot.

Initial adhesion strength to polyester/cotton (65/35) broad cloth and polyester tropical cloth is 4.6 and 5.1Kg/25mm, respectively, after dry cleaning test 4.0 and 4.1Kg/25mm, respectively, and after hot water washing test 4.6 and 5.1Kg/25mm, respectively. It was 4.9Kg/25mm, and all showed high adhesive retention rates.

Comparative Example 100 parts of 6.10-nylon synthesized in Example 1, 57.4 parts of dimethyl terephthalate, 35 parts of dimethyl isophthalate, 59 parts of 1,4-butanediol, 28.6 parts of neopentyl glycol, and 0.1 part of tetrabutyl titanate were placed in a separable flask. A block polyesteramide was synthesized in the same manner as in Example 1. The softening point of the block polyester amide is 151.5℃, and the melt viscosity is 13600cps at 180℃.
It was hot.

It was adhered to polyester/cotton (65/35) broad cloth and polyester tropical cloth in the same manner as in Example 1, and the initial strength was measured to be 5.1 and 5.3, respectively.
Kg/25mm. However, when a dry cleaning test was performed, the adhesive strength was 2.1 and 2.5, respectively.
Kg/25mm, which decreased significantly. Furthermore, the adhesive strengths after hot water washing were 2.5 and 3.6 Kg/cm ² , respectively, and the adhesive retention rates were only low at 49% and 68%.

Claims (1)

[Scope of Claims] 1 (A) dicarboxylic acid or its ester derivative; (B) alkylene glycol having 2 to 8 carbon atoms (B-
1), and aromatic diol (B-2) represented by the following general formula (1) [In formula (1), R is an alkylene group having 2 to 4 carbon atoms and may be the same or different, x and y are a number of 1 or more, and x+y is 20 or less. ] A block polyester in which the ratio of the aromatic diol (B-2) is 1 to 30% by weight is obtained by polycondensing a diol mixture mainly composed of (C) and an aliphatic polyamide having carboxyl groups at both ends. A method for producing a polyester amide polycondensate, the method comprising obtaining an amide polycondensate. 2 The diol mixture of (B) is (B-1), (B-2)
The method for producing a polyesteramide polycondensate according to claim 1, which further contains poly(alkylene oxide) glycol (B-3) having a number average molecular weight of 500 to 10,000.