JPS5946993B2 - adhesive for textiles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyesteramide fiber adhesive.

More specifically, it relates to a polyesteramide fiber hot melt adhesive with a specific copolymer composition that has excellent adhesive strength and texture at the bonded part, as well as water resistance and percleaning resistance (dry cleaning resistance). be.

Hot melt adhesives are becoming increasingly important in the clothing field, especially in applications such as adhesive interlining, adhesive sewing, non-woven fabric binders, and bonding of badges and labels, and several products have already been developed. It has been commercialized.

Hot melt adhesives have come to be widely used for fiber bonding because they take advantage of the major advantage of hot melt adhesives: they can instantly complete bonding by heating without using a melting point. This is because it greatly contributes to labor saving, rationalization, and speeding up of sewing systems.
Such hot melt adhesives are powder, film (tape)
, is used in the form of threads, but its required fiber adhesion performance is (1) first to soften under bonding temperature conditions;
Therefore, it has a softening point of about 100 to 140°C, (2) it has high adhesive strength, and (3) it has excellent dry cleaning resistance.

The basic conditions include (4) excellent washing resistance, and (5) no hardening of the texture of the bonded area. Of course, depending on how it is used, it may not be possible to satisfy all of these properties, and in reality, some adhesives are already used as coatings, but there are adhesives for textiles that have all of these properties. At present, the appearance of melt adhesives is eagerly awaited. For example, conventional hot melt adhesives for textiles include polyethylene, ethylene-vinyl acetate copolymer, copolyamide, copolyester, and polyvinyl chloride, but each has the following disadvantages. There is.

Polyethylene has low adhesive strength and can only be used as a temporary adhesive. Ethylene-vinyl acetate copolymer is flexible, so the texture of the bonded part is quite good, but it has poor dry cleaning resistance.
The adhesive properties are poor and the adhesive strength is not sufficient. Furthermore, the phenomenon of adhesive seeping out from the adhered fabric during bonding, expressed by terms such as strike-through and strike pack, tends to cause a decrease in adhesive strength, and in severe cases can even harden the texture of the bonded area. be. Conventionally known copolyesters have poor dry cleaning resistance and are said to have unsatisfactory texture at the bonded area. Polyvinyl chloride is generally used as an emulsion and is not a perfect hot melt, but it also has the disadvantage of low adhesive strength. Among these, copolyamide is the most used for high-grade adhesives, and is used as a permanent adhesive due to its relatively high adhesive strength and good dry cleaning resistance. has shortcomings,
Furthermore, it also has drawbacks such as a decrease in adhesive strength due to hot water washing and low adhesive strength to polyester synthetic fibers. The inventors
The present invention has been arrived at through intensive studies aimed at producing a fiber adhesive that overcomes the drawbacks of conventional fiber adhesives and has all of the above-mentioned basic adhesive properties.

That is, the present invention is composed of an ester component consisting of butylene terephthalate and/or butylene isophthalate units, and (B) an amide component consisting of dodecanamide and/or undecanamide units, and
The present invention provides a fiber adhesive characterized in that it is made of polyesteramide having a copolymer composition within the range of triangular coordinates ABCDEF shown in the figure.

Butylene terephthalate and/or butylene isophthalate forming the ester component, which is one component of the polyesteramide in the present invention, refers to terephthalic acid and/or isophthalic acid and 1,4-butanediol,
and ester-forming derivatives thereof by a condensation reaction, and is represented by the general formula (M and n are integers of 0 or 1 or more).

Here, when n=0, it becomes butylene terephthalate, when m=o, it becomes butylene isophthalate, and when m≠0 and n≠0, it becomes a butylene terephthalate/butylene isophthalate copolymer. The m:n ratio can be freely selected depending on the purpose and use, but in general, when the ester component is a single butylene terephthalate unit, it is highly crystalline and relatively hard, and has extremely excellent perchloride resistance. As the butylene isophthalate units are mixed and used, flexibility and adhesive properties increase, and high adhesive strength can be obtained under mild adhesive conditions (temperature, pressure). Dodecanamide, which constitutes the amide component, which is another component of the polyester amide in the present invention. and/or undecanamide unit means 12-aminododecanoic acid and/or 1
It is formed from 1-aminoundecanoic acid and their amide-forming derivatives and is represented by the general formula or.

In the polyesteramide of the present invention, the dodecanamide unit and the undecaneamide unit can be used individually or in the form of a copolymer without much difference in terms of polymerizability and physical properties, but they may be selected as appropriate for the purpose of controlling melting point, crystallinity, etc. may be used. It is important to use a selective combination of butylene terephthalate and/or butylene isophthalate as the ester structural unit and dodecanamide and/or undecaneamide as the amide structural unit in the polyester amide of the present invention.

For the first time in this copolymer-based polyester amide, polymerization progresses uniformly without phase separation over the entire copolymer composition range, and not only is a colorless polymer with a high degree of polymerization obtained, but also a novel polyester amide obtained. provides a flexible polymer with high adhesion to a variety of target substrates, as well as excellent resistance to hot water washing and per-cleaning. The copolymerization composition ratio of the polyester amide of the present invention is such that the butylene terephthalate units PB constituting the ester component^ are
T, butylene isophthalate unit PBI and dodecanamide unit N-12 and/or constituting amide component B)
Alternatively, it is necessary that the undecane amide unit N-11 is in the range surrounded by ABCDEF shown in the triangular coordinates of FIG. 1, and more preferably in the shaded range, and other copolymer compositions have the desired properties. It is not possible to obtain a hot melt adhesive for textiles.

Note that each point on the triangular coordinates in FIG. 1 specifically indicates the following composition. (Unit: weight %) Sodium chloride Polyesteramides having this copolymerization composition include polyesters such as polybutylene terephthalate and polybutylene terephthalate/polybutylene isophthalate copolymers, polyamides such as polydodecanamide and polyundecaneamide, and conventional Since then, polydodecanamide-based copolyamides, which have been used as adhesives for fibers, have shown remarkable new performance that could not be expected.

The polyesteramide of the present invention comprises (a) a dicarboxylic acid consisting of terephthalic acid and/or isophthalic acid, (
This is achieved by melt polymerizing b) 1,4-butanediol and (c) 12-aminododecanoic acid and/or 11-aminoundecanoic acid.

An example of a suitable polymerization method is terephthalic acid and/or
Or an aromatic dicarboxylic acid consisting of isophthalic acid,
1.05 to 2.0 times the mole of aromatic dicarboxylic acid
, 4-butanediol and 12-aminododecanoic acid and/or 11-aminoundecanoic acid, first in the presence of a customary esterification catalyst, from about 150 to 26
The reaction is carried out by heating at a temperature of 0°C under normal pressure. Within this time series is N
2 sealed gives favorable results. Then, by heating and polycondensing at 200 to 270°C under reduced pressure of 10 mmHg or less, preferably 1 mmHg or less,
It can be made into a polyesteramide with a high degree of polymerization that is transparent when melted. In addition, a polyester prepolymer having an average degree of polymerization of 3 to 8 is first prepared from both aromatic dicarboxylic acid and 1,4-butanediol under normal pressure and esterification conditions of 150 to 260°C. A uniform polyester amide with a high degree of polymerization can be similarly obtained by supplying aminododecanoic acid and/or 11-aminoundecanoic acid to a polymerization reactor and carrying out heating polycondensation at 200 to 2700C under reduced pressure. When polymerizing this polyester prepolymer and an aminocarboxylic acid, lower alkyl esters of terephthalic acid and/or isophthalic acid may be used in advance to prepare the polyester prepolymer. In addition, 12-aminododecanoic acid, which is a raw material for the polyamide structural unit of the present invention, is preferably used alone, but it can also be used in the form of laurolactam, which is partially or completely dehydrated and ring-closed. Polyesteramides are likewise obtained by delaying the reaction time of . Titanium-based catalysts give good results in the production of polyesteramides.

Particularly preferred are tetraalkyl titanates such as tetrabutyl titanate and tetramethyl titanate, and metal salts of titanium oxalate such as potassium titanium oxalate. Also with other catalysts. Examples include tin compounds such as dibutyltin oxide and dibutyltin laurate, and lead compounds such as lead acetate. In the above-mentioned method for producing polyesteramide of the present invention, the average segment length of the polyester units and polyamide units is generally determined by the copolymerization composition ratio, but it can also be controlled by the reaction conditions. 12 at the polymer stage
- Polymers polymerized by adding aminododecanoic acid and/or 11-aminoundecanoic acid have a longer segment length on average for each unit than polymers obtained by reacting all monomers at once; Melting point is several degrees Celsius
The polymer becomes about 20°C higher.

Therefore, the optimum method for producing the polymer should be selected depending on the intended use. The polyesteramide of the present invention may also be used by copolymerizing a small amount of monomer components other than terephthalic acid, isophthalic acid, 1,4-butanediol, 12-aminododecanoic acid and 11-aminoundecanoic acid.

For example, dicarboxylic acids such as adipic acid, sebacic acid, dodecanniic acid, naphthalenedicarboxylic acid, and cyclohexanedicarboxylic acid, diols such as ethylene glycol, pentanediol, neopentyl glycol, 1,6-hexanediol, and cyclohexanedimethanol, trimesic acid, Polyfunctional compounds such as glycerin, pentaerythritol, etc. may be used, as well as hexamethylene diamine-sebacate, hexamethylene diamine-isophthalate, hexamethylene diamine dodecanoate, ε-monocaprolactam, ε-aminocaproic acid. Amide-forming compounds such as amide-forming compounds can also be used within the range of small amounts of copolymerization. It is necessary that the melting point or softening point of the polyesteramide of the present invention is 80 to 180°C.

If the softening point is too low, it will not be heat resistant. It is unfavorable in terms of workability and moldability, and at high temperatures it is unfavorable because it impairs the performance and texture of the adhered fabric. Also, the melting point or softening point is 1
Products in the relatively high temperature range of 20 to 180°C can of course be used as hot melts for adhesion, but they also contain plasticizers, adhesives, adhesion aids, and thermoplastic resins with low melting points and good fluidity. It can also be used with improved low-temperature adhesion. The melt viscosity and polymerization degree of the polyesteramide are arbitrary as long as the relative degree is in the range of about 1.25 to 3.0 under the measurement conditions of 0.5% concentration at 25°C in orthochlorophenol. Can be set to Stabilizers such as antioxidants, thermal decomposition stabilizers, light stabilizers, and hydrolysis resistance improvers may be optionally added to the polyesteramide of the present invention during polymerization or molding.

Polyesteramide is used for bonding fibers in the form of powder, film, or thread, but when powdered,
After cooling with a refrigerant such as liquid nitrogen, it is crushed in a crusher, and sometimes lubricants such as magnesium stearate, calcium stearate, silicic acid anhydride, and talc are added to make adhesive powder. ,
It is coated using a Sukiyatsuta machine and used as adhesive interlining.

In addition, as a film forming method, a melt film forming method is preferable.
The chips or powder are fed into a conventional extruder and extruded into a film at a forming temperature that is about 20 to 100°C higher than the melting temperature to form a film that is not actively stretched.
The film-like hot-melt adhesive thus obtained is made into a tape form, sandwiched between the same or different types of woven fabrics, and bonded by heating and softening using a hot roller, hot press, ironing, or the like. Woven fabrics include synthetic fibers such as polyester, polyamide, and acrylic, natural fibers such as wool and cotton, and blends thereof, and can also be used to join watz pens and name marks. The present invention will be explained below with reference to Examples. In the examples, all "parts" or "%" are expressed as weight ratios. In addition, the relative viscosity shown in the text is a value measured in orthochlorophenol at 25°C and a concentration of 0.5%, and the melting point is also measured by DSC (Pel) unless otherwise specified.
- Melting peak temperature measured with KinElmerDSC-IB). The adhesive strength is determined by sandwiching the adhesive between the fabrics.
After adhering the breath, it was determined by a T-beer peel test using Tensilon manufactured by Toyo Sokki. Example 1 99.6 parts of terephthalic acid, 66.4 parts of isophthalic acid, 1
, 135 parts of 4-butanediol and 0.22 parts of titanium tetrabutoxide were placed in a flask, and after purging with N2, it was heated to 220°C with stirring, and the produced water and THF were distilled out of the reaction system for 3 hours. The esterification reaction was completed in minutes.

Next, the entire amount of the polyester prepolymer was transferred to a polymerization vessel equipped with a stainless steel helical ribbon stirring blade, and 120 parts of 12-aminododecanoic acid and 0.0 parts of titanium tetrabutoxide were added.
10 parts and 1" of stabilizer Irganox 1" (Ciba
1010 (tetrakis[methylene-3(3,5-
0.33 part (0.1% based on the polymer) of di-t-butyl-4-hydroxyphenyl)propionate (methane) was added, and the temperature was brought to 245° C. and 0.1 mmHg for about 1 hour. If stirring was continued under these conditions, the reaction system became a transparent viscous liquid in 2 hours and 40 minutes. The obtained polymer was discharged into water from a polymerization container in cut form and pelletized through a cutter. The obtained polymer is a polyesteramide having a composition ratio of polybutylene terephthalate: polybutylene isophthalate nipolydodecane amide 40:27:33 (weight ratio), relative viscosity (ηr) 1.39, and polymer melting point 123°C. showed that.

This polyesteramide pellet was heated to about 100℃ at 160℃.
Breath molding into a μ-thick film, IC! A tape of RL width was slit.

2 pieces of polyester/cotton (65/35) Proud (T/
C Prode) When the tape was sandwiched between the base fabrics and bonded using a hot press machine heated to 150℃ at a pressure of 300f1/(-77f) for 10 seconds, the peel strength of the bonded part was 3.4Ky. /Cm, showing high adhesive strength.

The percrene resistance and hot water washing resistance of this polymer were tested using the following method.The film was slit into 1 cnL width tape and immersed in percrene and water heated to 40℃ and 60℃ respectively, and the immersed film after 30 minutes. When the material was subjected to a tensile test using a strain gauge, it showed a strength of 150~/Cd or more and an elongation of 600% or more in all tests. For comparison, commercially available copolyamide (6/66/
610/12 copolymer; melting point 117/C) and copolymerized polyester (terephthalic acid/adipic acid/ethylene glycol/diethylene glycol copolymer: melting point 127°C)
) were subjected to similar tests, the former completely lost its strength and elongation in water at 60°C, and the latter in perchloren at 40°C.

Example 2 Twelve types of polyester amides shown in Table 1 were prepared in the same manner as in Example 1 by changing the copolymerization composition ratio.

their melting point, relative viscosity and tensile modulus of the film,
The tensile strength and elongation during immersion in perculane and water were measured. All of the polyesteramides within the scope of the present invention had low melting points and flexibility, and maintained high strength and elongation even in perchloromethane and water. Example 3 2.00 parts of terephthalic acid, iso? Talic acid 1
．． 33 parts, 1,4-butanediol 3.25 parts and 1
2.41 parts of 2-aminododecanoic acid was placed in a reaction vessel together with 0.0018 parts of titanium tetrabutoxide, and N2/-0
After the reaction mixture was stirred, the reaction mixture was heated at 230° C. for 3 hours and 45 minutes, and 1.25 parts of a mixture of water, THF, and 1,4-butanediol was distilled out of the system.

Next, the reaction mixture was transferred to a polymerization reaction vessel, and 0.0037 parts of titanium tetrabutoxide, 11 Irganox 111
After adding 0.010,0.0066 parts, 24
5℃, 0.1m7! Bringing the reaction conditions below LHg,
When the polymerization reaction was continued for an additional 1 hour and 55 minutes, a transparent viscous polymer was obtained. This polyesteramide is PBT
:PBI:N-12 ratio was 41:27:33, relative viscosity was 1.41, and melting point was 102°C.

The obtained polymer was discharged from a spinneret having a large number of spinning holes, and the filaments were captured by an air stream, and then an adhesive interlining was produced by collecting the filaments in a web shape on a polyester base fabric. The amount of adhesive applied is adjusted to 109/M2. Polyester/wool (
50/50) blended fabric was placed on top, and heated at 140°C, 30°C.
Hot-breathing was carried out under adhesive conditions of 0.09/cmD and 10 seconds.

Using a dry cleaner, the adhered fabric was immersed in a bark cleaner for 8 minutes with agitation, centrifuged for 5 minutes, and heated to dry and deodorized (60°C).
) A dry cleaning resistance test was conducted for 5 cycles with 7 minutes as one cycle. Separately, washing with warm water at 60° C. (containing 2% soap powder) was repeated 5 times, including stirring for 5 minutes, dehydration for 1 minute, and leaving to dry. These changes in adhesive strength are shown in Table 2, and no partial peeling was observed, indicating excellent dry cleaning resistance and hot water washing resistance. Example 4 The polyesteramide pellets of A1 obtained in Example 2 were sufficiently cooled with liquid nitrogen, crushed with dry ice in a crusher, classified with a sieve, and then powdered with a size of 80 to 250 mesh was placed on a cloth. Apply to a coating amount of /m',
100% wool woven fabric (Wool Polar) was layered and bonded under pressure at 150° C. for 10 seconds by applying a pressure of 3009/Cd.

The adhesive strength was 1,2509/5c1n, and even after fully automatic cleaning similar to Example 3, the adhesive strength remained 1,150f1.
/5CWL, which showed a high retention rate. Also, after washing with water at 60℃, it is 1,2009/5C! It had an adhesive strength of RL. Example 5 1.50 parts of terephthalic acid, 1.50 parts of isophthalic acid.
50 parts of 1,4-butanediol, 2.93 parts of 11-aminoundecanoic acid and 0.0020 parts of titanium tetrabutoxide were added to a reaction vessel at a temperature of 215-220°C under stirring after purging with tender N2. The reaction was carried out by heating for 3 hours and 20 minutes.

The reaction mixture was then transferred to a polymerization reaction vessel, and 0.0040 parts of titanium tetrabutoxide and 11.0 parts of titanium tetrabutoxide were added. Irganox 1″
1098 (N,N'-hexamethylene bis(3,5-
After adding 0.0070 parts of di-t-butyl-4-hydroxyhydrocinnamide), 245 C, 0.1 m
When polymerized by heating and stirring under reduced pressure conditions of mHg, a transparent viscous polymer was obtained in about 3 hours and 15 minutes. The obtained polyester amide had a weight ratio of constituent units of polybutylene terephthalate, polybutylene isophthalate, and polyundecane amide of 30:30 to 40, a melting point of 130°C,
It showed a relative viscosity of 1.43. It was press-molded at 180°C to form a 70μ film, and slit to form a tape with an ICWL width.

Apply this tape to two pieces of polyester/cotton blend (65/35
:T/C-Prode), 3009/Cl? Heat bonding was carried out at a pressure of L and a temperature of 150° C. for 10 seconds. The adhesive strength showed a high value of 2.7K9/CTn. Next, the adhered base fabric was subjected to the same dry cleaning and hot water washing treatments as shown in Example 3, but in both cases the results were 2.4~/c! N,
It maintained a high adhesive strength of 2.3~/(V7l).In Comparative Example Example 5, ε-aminocaproic acid was used instead of 11-aminoundecanoic acid (ε-aminocaproic acid was used in this polymerization process).
The adhesive strength of the obtained polyesteramide (1.2 - Cln/Cln, the adhesive strength after washing with hot water is 0.7 Ky/Cln, and it hardly peels off after dry cleaning) I woke up.

[Brief explanation of the drawing]

This is a diagram of a polyesteramide copolymer in which the vertices of a triangle are polybutylene terephthalate, polybutylene isophthalate, and polydodecanamide (and/or polyundecaneamide), and in the diagram ABCDE
The range surrounded by F indicates the composition region of the present invention.

Claims (1)

[Claims] 1 (A) an ester component consisting of butylene terephthalate and/or butylene isophthalate units and (B
) An adhesive for fibers comprising a polyesteramide comprising an amide component consisting of dodecanamide and/or undecaneamide units and having a copolymer composition within the range of the triangular coordinate ABCDEF shown in FIG. agent.