JPS59172572A - Hot-melt adhesive - Google Patents

Abstract

PURPOSE:To provide the titled adhesive having excellent dry-cleaning resistance and soft hand, by bonding a polyamide chain to both terminals of a polyester contg. the residue of an arom. dicarboxylic acid, the residue of an aliph. diol and the residue of an arom. diol. CONSTITUTION:A hot-melt adhesive consists of a block polyester polyamide obtd. by bonding 5-50wt% polyamide chain composed of a 6-12C aliph. diisocyanate and a 4-12C aliph. dicarboxylic acid to both terminals of a polyester composed of 20-50mol% of the residue of an arom. dicarboxylic acid (a), 0- 30mol% of the residue of a 4-12C aliph. dicarboxylic acid (b), 30- 49mol% of the residue of a 2-10C aliph. diol (c), 0-10mol% of the residue of a poly(oxyalkylene) glycol (d) having a number-average MW of 500-2,500 and 1-20mol% of the residue of an arom. diol (e) of the formula (wherein R is a 2-4C alkylene; x+y=2-18).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a true-melt adhesive, particularly a true-melt adhesive that is not suitable for textiles.

In recent years, as clothing made of polyethylene terephthalate fibers has come into widespread use, polyester-based real-melt adhesives with good adhesion properties have also come to be used for the clothing. Polyester-based hot melt adhesives for interlining currently on the market have characteristics such as lower elasticity and softness than polyamide-based ones, and do not yellow or shine, making them suitable for use on 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 inventors of the present invention have investigated a true melt adhesive for textiles that has improved dry cleaning resistance, has a soft texture, and can be used in a wide range of textile bonding applications. The present invention was completed after discovering that a Pronk polymer consisting of polyester segments and polyamide segments is suitable for the purpose of the present invention.

That is, the present invention provides (a) aromatic dicarbonyl [fl group 20-5
0 mol%, (b) 0 to 50 mol% of aliphatic dicarboxylic acid residues having 4 to 12 carbon atoms, (C) 50 to 49 mol% of aliphatic di-ol groups having 2 to 10 carbon atoms, (,i ) 0 to 10 mol% of poly(oxyalkylene) glycol residues having a number average molecular weight of 500 to 2,500 and (e) general formula (INH3 (wherein, R is an alkylene group having 2 to 4 carbon atoms, x
+y is 2-18. ] At both ends of the polyester (A) composed of 1 to 20 mol% of aromatic diol residues represented by The present invention provides a true melt adhesive made of block polyester polyamide in which polyamide chains (B) made of aliphatic dicarboxylic acid are bonded in a proportion of 5 to 50% by weight.

In this specification, a dicarboxylic acid residue means a chemical structure in which a hydroxyl group is removed from a 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.

Examples of the aromatic dicarboxylic acid residues of the present invention include terephthalic acid, isophthalic acid, and phthalate.

diphenyl-p, magecarbon relatives, diphenyl□-m
, m'-dicarbonate W, dienylme p, 7-p, 〆-
dicarbone rR1') phenylmethane-m, a/-dicarbone d, 2,2'-bis(4-carboxyphenyl)
Furopane, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, dinzhenyl ether p, dicarboxylic W, Examples include residues of diphenyl ether-m, rrl-cyclonic acid, diphenylsulfone-p, medicarboxylic acid, dienylsulfone-m, d-dicarboxylic acid, and lower alkyl esters thereof.

C 4 -C 12 aliphatic dicarboxylic acid residues of the present invention (
b) Succinic acid, glutaric acid, adipic acid, β-
Examples include residues of methyladipic acid, pimelic acid, corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and lower alkyl esters thereof.

The aliphatic diol residue having 2 to 10 carbon atoms (O
j is ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol,
neopentyl glycol, pentamethylene glycol,
Residues such as hexamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, diethylene glycol, triethylene glycol, etc. are removed.

, the poly(oxyalkylene) glycol residue of the present invention (
d) has a number average molecular weight of 500 to 25.0 []
Examples include residues of polyethylene glycol, polyglobylene glycol, polytetramethylene glycol, and the like.

The aromatic diol residue (e) represented by general formula (I) of the present invention is polyoxyethylene (4)-2,
2-bis(4-hydroxyphenyl)furopane, polyoxyethylene(2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2J-2,
M includes residues such as 2-bis(4-hydroxyphenyl)propane and polyoxyethylene-based 4-2.2-bis(4-hydroxyphenyl)glopane. Aliphatic diisocyanate having 6 to 12 carbon atoms (f
), examples thereof include hexamethylene diisocyanate, decamethylene diisocyanate, lysine diisocyanate, methyl hexamethylene diisocyanate, bis(isocyanatomethyl)cyclo-\xane, dicyclohexyl meta/diisocyanate, and the like. Also, carbon number 4
-12 aliphatic dicarboxylic acids (MAg) include the aliphatic dicarboxylic acids exemplified as constituent components of the polyester.

The block polynitride bolyamide of the present invention is obtained by polycondensation of 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 to obtain a polyester, and then a second step reaction. The polyester is obtained by adding a diisocyanate and a dicarboxylic acid to carry out a polycondensation reaction, thereby bonding polyamide chains to both ends of the polyester in a block manner. Methods for bonding polyamide chains to polyester include (1) a method in which diisocyanate and dicarboxylic acid are simultaneously reacted; (lv) A method of reacting a part of the diisocyanate, preferably 60 to 70% by weight, reacting the entire amount of dicarboxylic acid, and then reacting the remainder of the diisocyanate. The method is preferred. This second stage reaction is carried out at 100 to 250°C.
The reaction is carried out in the molten state or in the presence of an inert solvent inert to the incyanate. For the latter method, US
P4.129,715 (1978) can be used. In addition, if necessary, amine catalysts such as triethylamine and diethylenetriamine, tin catalysts such as diptyltin dilaurate and stannous octylate, and cobalt catalysts such as potassium sulfate, cobalt nanthenate, and cobalt-2-ethylhexoate are used. The reaction can also be carried out by adding an iron compound such as ferric chloride or ferric-2-ethylhexoate.

Aromatic dicarboxylic acid residue (a) occupied in the polyester segment of the block polyester polyamide of the present invention
If the proportion is less than 20 mol%, dry cleaning resistance deteriorates, which is not preferable. Also, the number of carbon atoms is 4 to 1
The proportion of aliphatic dicarboxylic acid residue (b) in No. 2 is 50 mol%
If it exceeds 50% by mole, the dry cleaning resistance will be adversely affected, so it is preferably 50% by mole or less. If the proportion of residual aliphatic diol having 27 to 10 carbon atoms and (C) is small, the resin will be hard (50 mol% to 49 mol% J
It is preferable to use it within the $i12 range.

Poly(oxyalkylene) glycol residue (d) has a great effect on softening the resin, but if too much is used, dry cleaning resistance deteriorates, and the softening point of the resin drops too much, causing blocking during storage. It is preferable to set it to 10 mol % or less because it becomes easier.

Aromatic diol residue (,) represented by general formula (1)
Although it provides an excellent adhesive effect, it is preferable that the proportion in the polyester segment exceeds 20 mol%, and is preferably 1 to 20 mol%. More preferably, it is 1 to 10 mol%.

The polyester segment composed of polyethylene terephthalate contributes greatly to the adhesion, hot water washing resistance, softness of the texture, etc. to polyethylene terephthalate clothing. 5 to 5 aliphatic polyamide chains consisting of a condensate of 6 to 12 aliphatic diisocyanates (f)
It is necessary to combine them at a ratio of 0 weight i%. If the proportion of the aliphatic polyamide segment is less than 5% by weight, there is no improvement in dry cleaning resistance, and if it exceeds 50% by weight, the hot water washing resistance will be poor. The temperature is preferably 60 to 160°C. If the softening point is lower than 60°C, blocking will occur easily when stored in the form of powder, pellets, thread, etc. Also, when ironing, etc., thermocompression bonding may cause thickening (plastic deformation and changes in the texture and silhouette of clothing). If the softening point exceeds 160° C., thermal deformation of the fibers tends to occur during welding, which is not preferable.

Antioxidants, fillers, colorants, lubricants, etc. can be added to the hot melt adhesive of the present invention depending on the requirements.

Although the polyester polyester polyamide synthesized by the method of the present invention may undergo partial randomization due to the ester amide exchange reaction, most of it has a polyamide-polyester-boryamide type teleblock structure. It is assumed that there are.

In the true melt adhesive of the present invention, the copolyester segment forming the intermediate block has hot water washability,
As a result of the polyamide segments forming both end blocks exhibiting dry cleaning resistance, it is suitable for use as a textile adhesive with excellent both hot water washing resistance and dry cleaning resistance.

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. The number of copies is xi copies.

Example 1 Dimethyl terephthalate 48.5g (25 mol%) Dimethyl isophthalate powder 29.1# (
15#) Adipic acid 17.4#(1
0#) 1,4-Butanediol 61.
5# (68#) Tetra-〇-butoxytitanium
Charge the raw materials into the reactor at a rate of 0.080 #220
After raising the temperature to ℃ and carrying out the transesterification reaction, the temperature was raised to 250℃.
The temperature was raised to 1,000 Hg, and the pressure was gradually reduced under a nitrogen atmosphere.
A polyester resin was obtained by carrying out a polycondensation reaction for 2 hours in the following Makabe. Still excessive.

1,4-Butanediol was removed from the system during the reaction. The polyester resin had an acid value of 1.2 KoHmg/i and a hydroxyl value of 16.5 KOH/l.

Subsequently, the temperature was lowered to 180°C and 100 parts of the polyester resin was treated with hexamethylene diisocyanate under normal pressure.
After adding 5.58 parts of Matsuka and reacting for 1 hour, 57.5 parts of sebacic acid and 0.1 part of potassium acetate were added and stirred for 20 minutes, followed by 20.2 parts of hexamethylene diisocyanate.
After the generation of carbon dioxide gas started to decrease, the temperature was raised to 210°C and the reaction was carried out for 1 hour to obtain a block polyester amide. The softening point of the resin was 125°C.

The resin was molded into a 60μ thick film and polyester/
M=lS5%755% blow)" On the cloth, use a scissors iron at 130℃ and a pressure of about 200y/crn2.
A piece of adhesive paper with a soft texture was obtained by pressing for 0 seconds. When the hot water washing test and dry cleaning test were carried out using the adhesive test piece, it showed a low retention rate as shown in Table IK. In addition, the hot water cleaning test was conducted at a detergent concentration of 0.5%.
Washing was repeated five times for 10 minutes at a bath ratio of 1:50 and a temperature of 60°C. The dry cleaning resistance test was carried out using Parkren in a bath ratio of 1:50 and a temperature of 50° C. for 10 minutes and repeated five times. In both cases, the dry veins were naturally dried (air-dried). The peel strength was determined by T-peeling at 23° C. and a tensile speed of 200 stm/min and taking the average of five measurements.

Table 1 Example 2 Dimethyl terephthalate 58.84 (20 mol%) Dimethyl isophthalate 58.3 parts (
50 mol%) 1,4-butanediol 58
．． 6 # (d5 1) Neopentyl glycol
6.61 (51) Tetra-n-butoxytitanium 0.080 # was subjected to the ester parent exchange reaction and subcondensation reaction in the same manner as in Example 1, and the acid value was 0.8 K.
OH■/11゜Human xyl value 11.1 KOH~/1
A polyester resin of No. 1 was obtained. 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, followed by 11.5 parts of adipine i, 11.6 parts of sebacic acid,
0.1 part of potassium acetate was added and stirred for 20 minutes, and 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, sandwiched between polyester jersey cloth, and adhered with an iron at 125° C. in the same manner as in Example 1. Table 2 shows the results of the same test as in Example 1.

Table 2

Claims (1)

[Claims] 1. (a) 20 to 50 mol% of aromatic dicarboxylic acid residues, (b) 0 aliphatic dicarboxylic acid residues having 4 to 12 carbon atoms
~30 mol%, (0) C2-C10 aliphatic diol residue 30-49 mol%, (d) Number average molecular weight 500-2
500 poly(oxyalkylene) glycol residues 0~
10 mol% and (θ) general formula (1) (wherein, R is an alkylene group having 2 to 4 carbon atoms, x +
y is 2-18. ) Both terminal K of polyester (A) composed of 1 to 20 mol% of aromatic diol residues represented by Polyamide chain consisting of dicarbonate branches (
A true melt adhesive made of a block polyester polyamide obtained by bonding B) with a sidetone of 5 to 50%.