JPS6329903B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hot melt adhesive, particularly a hot melt adhesive suitable for use on textiles. In recent years, as clothing made of polyethylene terephthalate fibers has come into widespread use, polyester-based hot melt adhesives with good adhesive properties have come to be used as interlining for clothing. Currently commercially available polyester hot melt adhesives for interlining have lower elasticity and softness than polyamide adhesives, do not yellow, do not shine, and are suitable for thin polyester clothing. However, due to poor dry cleaning resistance, its use is limited to light clothing that does not need to be dry cleaned. The present inventors have conducted various studies on a hot melt adhesive for textiles that can improve these drawbacks, have excellent dry cleaning resistance, and have a soft texture that can be used in a wide range of textile bonding applications.
The inventors have now completed the present invention by discovering that a block polymer consisting of specific polyester segments and polyamide segments is suitable for the purpose of the present invention. That is, the present invention provides (a) aromatic dicarboxylic acid residues of 20 to 50
mol%, (b) 0 to 30 mol% of aliphatic dicarboxylic acid residues having 4 to 12 carbon atoms, (c) 30 to 49 mol% of aliphatic diol residues having 2 to 10 carbon atoms, (d) number average molecular weight 500~2500
Poly(oxyalkylene) glycol residues of 0 to
10 mol% and (e) general formula () (In the formula, R is an alkylene group having 2 to 4 carbon atoms, and x+y is 2 to 18.) 1 to 20 mol% of aromatic diol residues represented by
A polyamide chain (B) consisting of (f) an aliphatic diisocyanate having 6 to 12 carbon atoms and (g) an aliphatic dicarboxylic acid having 4 to 12 carbon atoms is attached to both ends of a polyester (A) consisting of 5 to 50 carbon atoms. The present invention provides a hot melt adhesive comprising a block polyester polyamide bonded in a proportion by weight. In this specification, a dicarboxylic acid residue refers to a chemical structure in which a hydroxyl group is removed from the carboxyl group of a dicarboxylic acid, and a diol residue refers to a chemical structure in which a hydrogen atom is removed from a hydroxyl group in a diol. The aromatic dicarboxylic acid residue (a) of the present invention includes:
For example, terephthalic acid, isophthalic acid, phthalic acid,
Diphenyl-p,p'-dicarboxylic acid, diphenyl-m,m'-dicarboxylic acid, diphenylmethane-
p, p'-dicarboxylic acid, diphenylmethane-m,
m'-dicarboxylic acid, 2,2'-bis(4-carboxyphenyl)propane, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene- 2,7-dicarboxylic acid, diphenyl ether-p,p'-dicarboxylic acid, diphenyl ether-m,m'-dicarboxylic acid, diphenylsulfone-p,p'-dicarboxylic acid, diphenylsulfone-
Examples include residues of m,m'-dicarboxylic acids and lower alkyl ester derivatives thereof. Examples of the carbon 4-12 aliphatic dicarboxylic acid residue (b) of the present invention include succinic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, Examples include residues of decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and lower alkyl ester derivatives thereof. Examples of the aliphatic diol residue (c) having 2 to 10 carbon atoms in the present invention include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neobentyl glycol, pentamethylene glycol, hexamethylene Examples include residues such as glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, diethylene glycol, and toluethylene glycol. Examples of the poly(oxyalkylene) glycol residue (d) of the present invention include residues such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol having a number average molecular weight of 500 to 2,500. The residue (e) of the aromatic diol represented by the general formula () of the present invention is polyoxyethylene (4).
-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2)-2,2-bis(4
-hydroxyphenyl)propane, polyoxypropylene(2)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(12)-2,2
-bis(4-hydroxyphenyl)propane and the like. Carbon number 6 used in the present invention
to 12 aliphatic diisocyanates (f) include hexamethylene diisocyanate, decamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, and the like. Further, as the aliphatic dicarboxylic acid (g) having 4 to 12 carbon atoms, the aliphatic dicarboxylic acids exemplified as constituent components of the polyester can be mentioned. The block polyester polyamide of the present invention is obtained by polycondensing a dicarboxylic acid component and a diol component by a known method such as a direct esterification method or a transesterification method as a first step reaction, and then polycondensing a diisocyanate component as a second step reaction. By adding dicarboxylic acid and carrying out a polycondensation reaction, polyamide chains are bonded to both ends of the polyester in a block manner. Methods for bonding polyamide chains to polyester include (i) a method of simultaneously reacting diisocyanate and dicarboxylic acid; (ii) a method of simultaneously reacting diisocyanate and dicarboxylic acid;
A method of reacting diisocyanate and then reacting dicarboxylic acid; (iii) A method of reacting dicarboxylic acid and then reacting diisocyanate; (iv) A method of reacting a part of the diisocyanate, preferably 60 to 70% by weight, and then reacting dicarboxylic acid. Examples include a method in which the entire amount of diisocyanate is reacted and then the remainder of the diisocyanate is reacted, and method (iv) is particularly preferred. This second stage reaction is carried out at a temperature of 100 to 250° C. in the melt or in the presence of a high-boiling solvent that is inert to the isocyanate. For the latter method, see USP4129715
(1978) can be used. If necessary, amine catalysts such as triethylamine and diethylenetriamine, tin catalysts such as dibutyltin dilaurate and stannous octylate, cobalt compounds such as potassium acetate, cobalt naphthenate and cobalt-2-ethylhexoate, The reaction can also be carried out by adding iron compounds such as ferric chloride and ferric-2-ethylhexoate. If the proportion of the aromatic dicarboxylic acid residue (a) in the polyester segment of the block polyester polyamide of the present invention is less than 20 mol%, the dry cleaning resistance will deteriorate, which is not preferable.
Also, aliphatic dicarboxylic acid residues having 4 to 12 carbon atoms
If the proportion of (b) exceeds 30 mol%, the dry cleaning resistance will be adversely affected, so it is preferably 30 mol% or less. If the proportion of aliphatic diol residues (c) having 2 to 10 carbon atoms is small, the resin will become hard.
It is preferably used in a range of 30 mol% to 49 mol%. Poly(oxyalkylene) glycol residue (d) has a great effect on softening the resin, but if it is used too much, it will deteriorate the dry cleaning resistance, and the softening point of the resin will drop too much, making it more likely to cause blocking during storage. Therefore, 10 mol%
The following is preferable. The aromatic diol residue (e) represented by the general formula () has an excellent adhesive effect, but if its proportion in the polyester segment exceeds 20 mol%, the resin becomes hard and the softening point increases. The proportion is preferably from 20% to 20% by mole. More preferably, it is 1 to 10 mol%. The polyester segment thus constituted greatly contributes to the adhesion, hot water washing resistance, softness, etc. of polyethylene terephthalate clothing.
However, this alone does not provide sufficient dry cleaning resistance, so an aliphatic polyamide chain consisting of a polycondensate of an aliphatic diisocyanate (f) having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid (g) having 4 to 12 carbon atoms is used. It is necessary to combine in a proportion of 5 to 50% by weight. If the proportion of the aliphatic polyamide segment is less than 5% by weight, there is no effect of improving dry cleaning resistance, and if it exceeds 50% by weight, hot water washing resistance deteriorates. The block polyester polyamide of the present invention preferably has a softening point of 60 to 160°C as measured by the ring and ball method according to JIS K2817. Powder when the softening point is lower than 60℃,
This is undesirable because it tends to cause blocking when stored in the form of pellets, threads, etc., and is also prone to large plastic deformation during heat-press bonding by ironing, etc., resulting in changes in the texture and silhouette of clothing. If the softening point exceeds 160°C, thermal deformation of the fibers tends to occur during adhesion, which is undesirable. Antioxidants, fillers, colorants, lubricants, etc. can be added to the hot melt adhesive of the present invention as required. It is assumed that the block polyester polyamide synthesized by the method of the present invention has a teleblock structure of the polyamide-polyester-polyamide type, although there is a possibility that partial randomization has occurred due to the esteramide exchange reaction. Ru. In the hot melt adhesive of the present invention, the copolymerized polyester segment forming the intermediate block has hot water washing resistance, and the polyamide segments forming both end blocks exhibit dry cleaning resistance, resulting in hot water washing resistance and dry cleaning resistance. It has both excellent properties and is suitable for use as a fiber adhesive. The hot melt adhesive of the present invention can be processed into various forms such as powder, pellet, sheet, thread, web, net, and nonwoven fabric. The present invention will be further explained below with reference to Examples. Parts are parts by weight. Example 1 Dimethyl terephthalate 48.5 parts (25 mol%) Dimethyl isophthalate 29.1 (15) Adipic acid 17.4 (10) 1,4-butanediol 61.3 (68) Polytetramethylene glycol (molecular weight 1000)
20.0〃(2〃) Polyoxyethylene(2)-2,2-bis(4-hydroxyphenyl)propane 15.8〃(5〃) Tetra-n-butoxytitanium
The raw materials were charged into a reactor at a ratio of 0.080〃 and the temperature was raised to 220℃ to carry out the transesterification reaction, then the temperature was raised to 250℃ and the pressure was gradually reduced under a nitrogen atmosphere, and the mixture was kept in a vacuum of 1 mmHg or less for 2 hours. A polyester resin was obtained by performing a polycondensation reaction. Furthermore, excess 1,4-butanediol was removed from the system during the reaction. The acid value of the polyester resin was 1.2KOHmg/g, and the hydroxyl value was 16.5KOHmg/g. Then the temperature
After lowering the temperature to 180°C and adding 5.58 parts of hexamethylene diisocyanate to 100 parts of the polyester resin under normal pressure and reacting for 1 hour, 37.3 parts of sebacic acid was added.
1 part and 0.1 part of potassium acetate and stirred for 20 minutes.
Further, 20.2 parts of hexamethylene diisocyanate was added and reacted. After the generation of carbon dioxide gas decreased, the temperature was raised to 210°C and the reaction was carried out for 1 hour to obtain a block polyesteramide. The softening point of the resin is
It was 125℃. The resin was formed into a 60 μ thick film, sandwiched between polyester/cotton = 65%/35% broadcloth, and pressed with an iron at 130°C and a pressure of about 200 g/cm ² for 10 seconds to obtain a soft-textured adhesive sample. I got it. Using this adhesive sample, a hot water washing resistance test and a dry cleaning resistance test were conducted, and as shown in Table 1, a high retention rate was shown. In addition, in the hot water washing test, washing was repeated five times for 10 minutes at a detergent concentration of 0.3%, a bath ratio of 1:50, and a temperature of 60°C. The dry cleaning resistance test was conducted using percrene in a bath ratio of 1:50 and shaking at a temperature of 30°C for 10 minutes, which was repeated 5 times. In both cases, drying was done naturally (air drying). Peel strength is 23℃,
It was determined by T-peeling at a tensile speed of 200 mm/min and taking the average of five measurements.

[Table] Example 2 Dimethyl terephthalate 38.8 parts (20 mol%) Dimethyl isophthalate 58.3 parts (30 mol%) 1,4-butanediol 58.6〃(65〃) Neopentyl glycol 6.6〃(5〃) Polyoxyethylene (12)-2,2-bis(4-hydroxyphenyl)propane 37.8〃(5〃) Tetra-n-butoxytitanium
A transesterification reaction and a polycondensation reaction were carried out in the same manner as in Example 1 at a ratio of 0.080 to obtain a polyester resin having an acid value of 0.8 KOH mg/g and a hydroxyl value of 11.1 KOH mg/g. Subsequently, in the same manner as in Example 1, 3.75 parts of hexamethylene diisocyanate was added to 100 parts of the polyester resin and reacted for 1 hour, and then 11.5 parts of adipic acid, 11.6 parts of sebacic acid, and 0.1 part of potassium acetate were added and reacted for 20 minutes. After stirring, 15.5 parts of hexamethylene diisocyanate was further added and reacted in the same manner as in Example 1 to obtain a block polyester polyamide. The softening point of the resin was 120°C. The resin was formed into a film having a thickness of 60 μm, and the film was bonded to a polyester jersey cloth at 125° C. using an iron in the same manner as in Example 1. Table 2 shows the results of the same test as in Example 1.

【table】

Claims (1)

[Claims] 1 (a) 20 to 50 mol% of aromatic dicarboxylic acid residues, (b)
0 to 30 mol% of aliphatic dicarboxylic acid residues having 4 to 12 carbon atoms; (c) 30 to 30 mol% aliphatic diol residues having 2 to 10 carbon atoms;
49 mol%, (d) 0 to 10 mol% of poly(oxyalkylene) glycol residues with a number average molecular weight of 500 to 2500, and (e) General formula () (In the formula, R is an alkylene group having 2 to 4 carbon atoms, and x+y is 2 to 18.) 1 to 20 mol% of aromatic diol residues represented by
A polyamide chain (B) consisting of (f) an aliphatic diisocyanate having 6 to 12 carbon atoms and (g) an aliphatic dicarboxylic acid having 4 to 12 carbon atoms is attached to both ends of a polyester (A) consisting of 5 to 50 carbon atoms. Hot melt adhesive consisting of block polyester polyamide bonded in proportions of % by weight.