JPS5861164A - Polyester adhesive - Google Patents

Abstract

PURPOSE:The titled adhesive having a suitable melting point and crystallinity at a hot-melt adhesive, comprising a copolyester containing a specific dicarboxylic acid unit, a glycol unit, and a high-molecular weight diol unit as an active ingredient. CONSTITUTION:(A) A dicarboxylic acid component consisting of 50-99mol% preferably 70-90mol% terephthalic acid and 50-1mol%, preferably 30-10mol% isophthalic acid, (B) a glycol component consisting of 99-50mol% 1,6-hexanediol and 1-50mol% 2-methyl-1,3-propanediol, and (C) one or more high-molecular weight diols of a polyalkylene ether glycol and a polycaprolactone glycol are subjected to polycondensation, to give the desired copolyester. USE:For clothing, packaging, laminating, bookbinding, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive comprising a novel polyester copolymer as an active ingredient.

More specifically, compared to conventional polyester copolymers,
The present invention relates to an adhesive composition containing as an active ingredient a polyester copolymer having a lower melting point and an appropriate degree of crystallinity.

Conventionally, linear polyester copolymers have been used in a wide range of applications such as films, molded products, and fibers, but generally, polyester copolymers of this type with a moderate degree of crystallinity have a high molecular weight and a high The effective acid content of adhesives with a melting point, especially hot melt adhesives that do not use solvents, is not necessarily appropriate due to the balance between melting point and crystallinity. A polyester copolymer with a

A polyester copolymer is composed of a glycol component and a dicarboxylic acid component, and by various combinations of these two components, the crystallinity, melting point, etc. of the copolymer can be varied over a wide range. It is said that I as a true melt adhesive is determined by the adhesive resin's crystallinity, 61 degree of polymerization, and molecular structure';77. It is believed that the crystallinity and copolymer composition are the main factors for properties such as dry cleaning resistance, texture, etc.
, a crystalline melting point of 70°C to 140°C, an intrinsic viscosity of 04 or more, and a crystallinity with a heat of fusion of 1 to IO calories per gram, but conventionally proposed polyester adhesives have not been able to satisfy these requirements. It was difficult.

As a result of intensive research, the present inventors have satisfied the above conditions,
The inventors have discovered an adhesive containing a polyester copolymer as an active ingredient, which exhibits a moderate degree of crystallinity at the cutting point and has extremely excellent adhesive properties, and has thus arrived at the present invention.

That is, the present invention provides (A) 50 to 99 mole of terephthalic acid residue and 50 to 99 mole of terephthalic acid residue;
A dicarboxylic acid unit consisting of ~1 mol of isophthalic acid group and (13) a glycol unit consisting of 50 to 99 mol of 16-hexanediol residue and 50 to 1 mol of 2-methyl-13-propanediol residue. (Q) One or more high molecular weight diol components selected from polyalkylene ether glycol residues and polycaprolactone glycol residues (provided that the proportion of the high molecular weight diol component in the copolymer is 0 to 60% by weight) This relates to a polyester adhesive containing as an active ingredient a polyester copolymer composed of
゜The dicarboxylic acid component for making the polyester copolymer used in the adhesive of the present invention is a mixture of terephthalic acid and isophthalic acid.
0 to 99 molty is terephthalic acid and 50 to 1 molty is isophthalic acid component.

The reason why the ratio of terephthalic acid to isophthalic acid is limited to this range is to satisfy the softening temperature and elastic properties of the resulting polymer. That is, terephthalic acid is 50-9
9 molar, preferably 70 to 0 molar, and if it is less than 50 molar, the obtained Φ° polymer softening temperature will be too low and will not adhere well.

-Isophthalic acid is 50 to 1 mol, preferably 1r-
i: 3 (1 to 10 mol.) If it is 50 mol.
) 11 The glycol components used to make the polyester copolymer used in Hon 5 and Akira's adhesives include 16-hexanediol of 99 to 50 mol and 2 of 1 = -50 mol.
A mixture of -methyl-1,3-furono;diols is used. 2-Methyl-13gI"panediol has one methyl group in the side chain and is an asymmetric diol in its chemical structure. It irregularizes the structure of a polyester copolymer containing this as a copolymerization component, It is a very effective compound in lowering melting point and crystallinity. In addition, since both of the two hydroxyl groups are primary, they are highly reactive and easily react with compounds having a ruboquinyl group, such as terephthal 1★, to form an ester bond.

On the other hand, 1,6-hexanediol is a diol in which six methylene groups are bonded in a linear chain and has a primary hydroxyl group at both ends, and it easily reacts with a compound having a carboxyl group to form an ester bond. The polyester obtained by forming and reacting with a dicarboxylic acid exhibits high crystallinity. According to the present invention, the melting point and crystallinity of a polyester copolymer obtained by combining the two types of low molecular weight glycol components that exhibit contradictory tendencies as described above in terms of melting point and crystallinity can be controlled within a desired range. A polyester copolymer which can be easily controlled and has extremely excellent adhesive strength can be obtained, and by using this as an active ingredient, it is possible to provide an excellent adhesive particularly as a true melt adhesive.

The mechanism of why such excellent adhesive strength is obtained is not clearly understood, but as a pseudopod, it is due to the electron donating property of the methyl group at the 2-position of 2-methyl-13-propanediol. The electron density of the carbonyl oxygen of terephthalic acid is increased, creating a coordination bond with the atoms on the surface of the substrate to be bonded.
It is thought that the adhesion properties are improved due to the tendency to form intermolecular bonds and hydrogen bonds. The proportion in the glycol component is 1 to 50 moles,
The molar ratio is preferably 15 to 10, but if it is less than 1 molar, the above-mentioned characteristics of 2-methyl-13-propanediol cannot be exhibited, and the melting point and crystallinity of the resulting copolymer are lowered. If it exceeds 50 molar ratio, the melting point, r, and crystallinity of the resulting polyester co-merged material will be extremely low, which are both unfavorable.

-1. In the present invention, one or two (.11 or more) high molecular weight diols selected from polyalkylene ether glycol and polycaprolactone glycol are used as the polymerization reaction component.

These polymeric diols impart properties such as abrasion resistance, impact resistance, flexibility, or elastic recovery to the resulting copolymer.

Polyalkylene ether glycol is diethylene glycol, triethylene glycol and 1d.
, polyethylene glycol, poly(12- and 13-propylene oxide) glycol with a higher degree of polymerization5. poly(tetramethyl/ion oxide) glycol,
Examples include poly(hexamethylene oxide) glycol and copolymers thereof, and a mixture of these may also be used. The number average molecular weight of these polyalkylene ether glycols is 100 to 3,000, preferably 100 to 2,000. The above polycaprolactone glycol is obtained by ring-opening polymerization of lactone using an appropriate catalyst in the presence of a low molecular weight glycol such as ethylene glycol, and its number average molecular weight is 500 to 4000.
, preferably 800 to 30oo.

As such lactone, ε-caprolactone is most preferable, and 9 others include enantolactone, β-propiolactone, dimethylbutyrolactone, butyrolactone, γ-valerolactone, r-caprolactone, γ-caprylolactone, crotolactone, δ - Valerolactone, δ-caprolactone, etc. are also used. Two or more of these lactones can be used simultaneously. In the reaction of the present invention, the proportion of the polymer-diol component used is such that the proportion in the obtained polymer is 0 to 60% by weight, preferably 0 to 40% by weight, and 60% or more. If this happens, the resulting copolymer will become too soft, which is undesirable.

Conventionally known methods for producing polyester can be applied as they are to producing the above-mentioned polyester copolymer used in the present invention. That is, it can be produced either by direct polycondensation of a dicarboxylic acid compound and a diol compound, or by the force θ of reacting an ester-forming derivative such as a lower alkyl ester of a dicarboxylic acid or a diol compound with a diol compound. .

An example of a polycondensation method using a so-called transesterification method using a lower alkyl ester of nonorboxylic acid 11-・Small J
- and the excess molar number with respect to the mixture of dimethyl terephthalate and dimethyl inoclate, that is, the maximal number 1 is 11 to 20 times the mole of 16-hexanediol and 2-
Using a common esterification catalyst, a mixed diol of methyl-13-pronochlorodiol and a high-molecular-weight diol is subjected to an esterification exchange reaction at a temperature of 150 to 240°C at atmospheric pressure in a nitrogen stream, and methanol is distilled off. , after adding a catalyst, a coloring inhibitor, etc. as necessary,
Polycondensation is carried out at about 200-280° C. under reduced pressure as follows.

A wide range of catalysts can be used as the catalyst, including titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetra-propoquine titanium, tetra-1so-propoxytitanium, and tetrabutoquine titanium, di-n-butyl-
tin-dilaurate, di-n-butyl-tin-oxide,
Examples include combinations of tin compounds such as dibutyl-tin-diacetate, acetate salts of magnesium, calcium, zinc, etc., and antimony oxide or the above-mentioned titanium compounds. These catalysts produce 0.0% of the total copolymer produced.
It is preferable to use it in a range of 0.002 to 0.8% by weight.

In addition, phosphorus-containing compounds such as phosphorous acid, triphenyl phosphate, tridecyl phosphite, and triphenyl phosphite are effective as coloring inhibitors, and 0.001-03 It is preferable to use within a range. In addition to the coloring inhibitor, additives such as a crystallization accelerator, a polymerization accelerator, a whitening agent, and a light stabilizer can be added as necessary.

The polyester copolymer used in the present invention can be used not only as a hot melt adhesive but also as a solvent adhesive. The adhesive of the present invention can be used as an adhesive in a wide range of applications such as clothing, packaging, laminating, bookbinding, wood industry, can manufacturing, shoe manufacturing, electrical work, crowns, etc. Depending on the purpose, 111! Mixed with Class J thermoplastic resin adhesives, such as polyethylene and ethylene copolymers, polyamide resins, polyzolopyrene resins, polyurethane resins, etc. 91. It can also be used as

Examples of the production of the polyester copolymer used in the present invention, the physical properties of the resin, and the performance when these are used as a hot melt adhesive are shown below as examples, but the present invention is not limited to these. do not have. In addition, the part in the example means a heavy inguinal part, and the measured value was obtained by the following measurement method.

l) The copolymer composition was determined by analyzing the nuclear magnetic resonance spectrum of the obtained copolymer.

Each diol residue constituting the resin is expressed as a molar ratio relative to all diol residues, and for high molecular weight diols, the residue is expressed as a weight % relative to the copolymer.

2) The intrinsic viscosity is tetrachloroethane-phenol (
This is a value measured at 25°C in a mixed solvent of 3 parts: 2 parts).

3) The melting point and heat of fusion were measured using a differential scanning calorimeter, and SrL was used as a reference material for the heat of fusion.

4) Adhesive Strength (1) Tensile Shear Adhesive Strength Tensile shear adhesive strength test method (JIS K6850) of the Japanese Industrial Standards ``Adhesives''. #i The tensile shear adhesive strength of the crimped test piece was measured using a universal testing machine manufactured by Toyo Baldwin Co., Ltd. Tensilo/UTM-11-500. Spread polyester resin powder with particle size at a rate of zsg/m and apply a pressure of 2kg/cy/l.
A test piece with a width of 25 mm was cut from the crimped material at a temperature of 1.50°C and a time of 2' () seconds, and the T-Beer peel adhesion strength was measured using Ten/Ron UTM-I manufactured by Toyo Baldwin Co., Ltd.
It was measured using a n-500 type universal testing machine.

Example-1 629 parts of dimethyl terentalate, 70 parts of isophthalic acid, 70 parts of isophthalic acid, 97 parts of 2-methyl-13-propa/diol, and 511 parts of 16-hexanediol were mixed with 007 parts of tetrabutquine titanium catalyst in a double helical ribbon type stirrer. into a reaction vessel equipped with
The mixture was heated at 80° C. for 1 hour and then at 230° C. for 25 hours, resulting in distillation of 89% of the theoretical amount of methanol. Next, 0.08 parts of tridecyl phosphite was added to the reaction mixture, the temperature was raised to 250°C, and the pressure in the system was reduced to 0.0000000000 over 40 minutes.
Polymerization was carried out for 35 hours under reduced pressure of 21 ml (.9 m).The intrinsic viscosity of the obtained polyester was 0.
．． 820 d e/g, the melting point is 125°C, and the heat of fusion is 5.
The 3° copolymerized polyester, which had a yield of 75 cal/g, was found to contain diol residues of 79 moles of 2-methyl-13-propanediol by nuclear magnetic resonance spectroscopy. Furthermore, the tensile shear strength of this polyester is 65. It was 4/cg/ad. The T-beer peel strength was 8309/25.

Examples 2 and 3 and Comparative Examples 1 and 2 Polymerization was carried out under exactly the same polymerization conditions as in Example 1 using the charged amounts shown in Table 1. Table 1 shows the measured values for each of the obtained polymers.

Procedural amendment (voluntary) February tA, 1980 Haruki Shimada, Commissioner of the Patent Office 1. Case description 1981 Patent Application No. 161509 2. Title of the invention Polyester adhesive 3. Relationship with the amended person case Patent Applicant address 1-4 Teppocho, Sakai City, Osaka Prefecture Subject of amendment Column 5 of detailed explanation of the invention in the specification Contents of amendment

Claims (1)

[Claims] 1. (A) a dicarboxylic acid unit consisting of 50 to 99 mol of terephthalic acid residue and 50 to 1 mol of isophthalic acid group; and (B) 50 to 99 mol of 1.6-hexane. A glycol unit consisting of a diol residue and a 2-methyl-1,3-propanediol residue of 50 to 1 molar ratio and (C) ho! /fulkylene ether y y 1 selected from cole residues and polycaprolactone glycol residues
A polyester system containing as an active ingredient a polyester copolymer composed of a species or two or more types of high molecular weight diol units (however, the proportion of the high molecular weight diol component in the copolymer is 0 to 60% by weight) glue