JPS5950192B2 - Fiber fixing agent - Google Patents

Description

[Detailed description of the invention] The present invention relates to a fixing agent for fibers.

BACKGROUND ART Polyamide resin-based or polyester-based adhesives are conventionally known as heat-melting adhesives for fibers. However, in the case of polyamide resin adhesives, the adhesive strength retention rate after washing with hot water is insufficient. In the case of polyester resin adhesives, the adhesive strength retention rate after dry cleaning is insufficient, and a solution to this problem has been desired. Polyester resin adhesives with good dry cleaning resistance have been proposed, such as those described in Japanese Patent Publication No. 47-18357, but depending on the application, they may have poor hot water washing resistance or dry cleaning resistance. In addition to performance, more advanced performance is now required.
For example, in applications such as preventing fraying of cut parts of textile fabrics and adhering films and textile fabrics, it is necessary to improve performance such as hot water washing resistance and dry cleaning resistance, as well as transparency of the adhesive layer and adhesion after adhesion. High performance such as body shape retention and texture is required. Especially after the adhesive treatment, the adhesive solidifies and shrinks 1-,
Therefore, the problem of deformation of the adherend, in the case of a tape-shaped adherend, causes the phenomenon that the tape twists or curls. Therefore, a search has been made for a bonding agent that does not deform the adherend after the bonding process. The present inventors have continued various studies to solve these problems, and have discovered that excellent effects can be obtained when a copolymerized polyester resin with a specific composition is used as a fixing agent for fibers, and the present invention has been developed. reached. That is, the present invention consists of 36 to 84 mol% of terephthalic acid, 14 to 1 mol% of isophthalic acid, and 50 to 15 mol% of aliphatic dicarboxylic acid as the dibasic acid component, and 80 to 2 mol% of ethylene glycol as the glycol component.
0 mol% and 20 to 80 mol% of 1,4-butanediol, the intrinsic viscosity of which is at least 0.5;
The fixing agent for fibers is made of a copolyester resin having a melting point of 100 to 160°C. The fiber fixing agent of the present invention has extremely excellent adhesive performance, does not cause the above-mentioned twisting or curling when fixing the ends of fiber fabrics, or laminating fiber fabrics and films, and is transparent and resistant to hot water washing. It also has excellent dry cleaning resistance. The dibasic acid component of the copolyester resin used in the present invention consists of terephthalic acid, isophthalic acid, and an aliphatic dicarboxylic acid component, and the glycol component consists of two components: ethylene glycol and 1,4-butanediol.

Examples of aliphatic dicarboxylic acids include dicarboxylic acids having 4 to 12 carbon atoms, such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid. The aliphatic dicarboxylic acids may be one type or two or more types. Particularly preferred aliphatic dicarboxylic acids include adipic acid, azelaic acid, and sebacic acid. The proportions of the dibasic acid components are 36 to 84 mol% of terephthalic acid, 14 to 1 mol% of isophthalic acid, and 5 mol% of aliphatic dicarboxylic acid.
It is 0 to 15 mol%.

If the proportion of the dibasic acid component is outside the range of the present invention, it will lack the desired properties as a fixing agent for fibers in the present invention. For example, if the amount of isophthalic acid is less than 1 mol%, the adherend will be significantly deformed after the adhesive treatment, and in particular, tape-shaped adherends will not only be twisted but also have insufficient transparency. . Furthermore, if the content of isophthalic acid exceeds 14 mol %, the adhesiveness to fiber fabrics will decrease and the dry cleaning resistance will also be insufficient. On the other hand, if the aliphatic dicarboxylic acid content is less than 15 mol %, the adhesive layer becomes hard and brittle. On the other hand, if the aliphatic dicarboxylic acid content exceeds 50 mol %, the adhesion to fiber fabrics decreases. The proportions of the glycol components are 20-80 mol% ethylene glycol and 80-20 mol% 1,4-butanediol.

If the ethylene glycol content is less than 20 mol%, the transparency will deteriorate, and if it exceeds 80 mol%, the ethylene glycol content will be poor after adhesion. The adhesive layer is not sufficiently solidified and has stickiness. The copolymerized polyester resin of the present invention contains a small amount of trivalent or higher polybasic acid as an acid component in addition to the above-mentioned dibasic acid. The alcohol component may contain a small amount of polyhydric alcohol having a Ξ value or higher, or oxycarboxylic acids other than the above-mentioned glycols.

The intrinsic viscosity of the copolyester resin of the present invention is at least 0.5, preferably from 0.6 to 1.5.

When the intrinsic viscosity is less than 0.5, the melt viscosity of the copolymerized polyester resin becomes too low, causing oozing to the surface of the fabric to be adhered. Furthermore, the adhesive strength is also low and undesirable. The polyester resin of the present invention has a melting point of 100-160
It is necessary to select the molar ratio of the acid component and the alcohol component so that the temperature is 0.degree.

If the melting point exceeds 160°C, it is necessary to increase the temperature for adhesion, making it impractical. If the melting point is lower than 100°C, the copolyester resin may become sticky or the adherend may become sticky. This is undesirable as it causes leaching to the back (front) of the fabric. The method for producing the copolymerized polyester resin of the present invention includes transesterifying dimethyl terephthalate or dimethyl isophthalate with ethylene glycol or 1,4-butanediol, and then adding an aliphatic dicarboxylic acid to perform an esterification reaction. ．． A method of performing a polycondensation reaction, or a method of performing a polycondensation reaction after an esterification reaction between terephthalic acid, isophthalic acid, or an aliphatic dicarboxylic acid and ethylene glycol or 1,4-butanediol; 1,4
- Polyester resin obtained from butanediol and polyester resin obtained from terephthalic acid, isophthalic acid, aliphatic dicarboxylic acid, and ethylene glycol at 220°C to 27°C.
Any method such as melt-mixing at 0° C. can be used.

The fixing agent of the present invention uses the copolymerized polyester resin as a living body, and contains antioxidants within limits that do not impair its performance. Additives such as ultraviolet absorbers, pigments, dyes, and nucleating agents can be added.

The fixing agent of the present invention is used for textile fabrics. It shows excellent performance especially for polyester fiber fabrics, but it also shows excellent performance for other fiber fabrics, such as polyamide fibers and cellulose fiber fabrics. It can also be applied to fiber fabrics such as wool. Also. Paper, metal. Especially metal foil. It can also be applied to adhesives such as leather, which are prone to deformation due to shrinkage of the adhesive layer. To fix fiber fabrics using the fixing agent of the present invention, there are two methods: immersing the fiber fabric in a molten copolyester resin, extruding and applying the molten copolyester resin onto the fiber fabric, or using a conventional method. Any method can be adopted, such as a method of applying a copolymerized polyester resin dissolved in a solvent onto the fiber fabric.

Further, when fixing a fiber fabric using the fixing agent of the present invention, a coating agent may be applied to the fiber fabric in advance, if necessary. The fixing agent of the present invention is applicable not only to woven fabrics but also to knitted fabrics, nonwoven fabrics, etc., and is effectively used in textile products for various uses such as clothing, industrial use, and decorative use.

The present invention will be explained in more detail with reference to Examples below.

In the examples, parts indicate parts by weight. The intrinsic viscosity of the saturated copolymerized polyester resin is phenol/tetrachloroethane = 6
/4 (weight ratio) mixed solvent at 30°C.
This is a value measured with ETTLER's MODELF 1). The copolymerized polyester resin was dissolved in chloroform at a concentration of 20% by weight, poured onto a Teflon-coated pad, and
By air drying day and night, a copolymerized polyester resin film of 100 to 150 μm was obtained. This copolymerized polyester resin film was pasted onto the end of a prop made of polyethylene terephthalate fibers, and the pressure was 21 < g/
After pressing under Cni at 160° C. for 10 seconds, transparency, curling, and twisting were visually determined. In addition, a copolymerized polyester resin film obtained by the above method was sandwiched between the above probe and a polyethylene terephthalate film (thickness 100μ), and the test piece was cut out after thermocompression bonding under the same conditions, and a T-peel test was conducted. The normal adhesive strength was measured. Further, a similar test piece was immersed in percrene at room temperature for 120 minutes with stirring, and a T-peel test was performed immediately after immersion to determine the adhesive strength retention rate from the ratio with the normal state. Further, a similar test piece was cut into a width 2 and a length 50 CTL, the upper end was fixed, and deformation such as twisting and curling after 7 days at room temperature and transparency were visually determined. Example 1 680 parts of dimethyl terephthalate was placed in a stainless steel autoclave equipped with a stirrer, thermometer, and cooling tube.
78 parts of dimethyl isophthalate, 3 parts of ethylene glycol
80 style 236 parts of 1,4-butanediol, 0.71 part of potassium oxalate titanate, and 0.58 part of ammonium trioxide were charged, and a transesterification reaction was carried out at 170°C to 220°C for 3 hours, followed by triphenyl phosphorite. Add 0.93 parts and 161 parts of adipic acid, and heat at 220°C to 250°C.
．． The esterification reaction was carried out for 5 hours.

Next, the pressure was gradually reduced at 265°C to remove excess glycol, and the temperature was 0.1 to 0.31 at 265°C. Under reduced pressure of Ht, 2
．． The polycondensation reaction was carried out for 5 hours. The resulting copolymerized polyester resin A had an intrinsic viscosity of 0.90 and a melting point of 135°C. As a result of compositional analysis by NMR, the composition of copolymerized polyester resin A was 70 mol% of terephthalic acid, 8 mol% of isophthalic acid, 22 mol% of adipic acid, and 60 mol% of ethylene glycol. 1,4-butanediol was 40 mol%. When a 100 to 150 μm film prepared by dissolving this polyester resin in chloroform was used to fix the ends of the prods made of polyethylene terephthalate fiber yarn, there was no curling due to shrinkage, and the film had excellent transparency. Separately, when the same film was used to adhere the above probe to a polyethylene terephthalate film (100μ thick), the T-type peel adhesive force was 1200 t/the peel adhesive force after immersion in Hepercrene was 960 t/, and the retention rate was 80%.
It was hot. In addition, in the retention test, there was no twisting or curling, and the transparency was excellent. Example 2 A copolymerized polyester resin (
B~) were manufactured.

Claims (1)

[Claims] 1 36-84 mol% terephthalic acid as dibasic acid component
, consisting of 14 to 1 mol% of isophthalic acid and 50 to 15 mol% of aliphatic dicarboxylic acid, and consisting of 80 to 20 mol% of ethylene glycol and 20 to 80 mol% of 1,4-butanediol as glycol components, whose intrinsic viscosity is at least 0.5 and a melting point of 100-160°C
A fixing agent for fibers comprising a copolymerized polyester resin.