JPS6312110B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel hot melt adhesive compositions. Conventionally, polyamide resin, polyester resin, etc. have been known as adhesives for textile materials.
When polyamide resin adhesives are used for textile fabrics, there is a disadvantage that the adhesive strength after washing with water is significantly reduced, and when polyester adhesives are used, the adhesive strength after dry cleaning is significantly reduced. It is acknowledged that there are shortcomings. For this reason, there has been a long-awaited new, durable hot melt adhesive that can withstand both wet washing and dry cleaning. However, as a result of intensive research, the present inventors have improved the shortcomings of conventionally known hot melt adhesives for textile materials, and have successfully maintained their excellent initial adhesion to textile materials, even after washing with water and dry cleaning. We have discovered a new adhesive composition that is highly effective, and have completed the present invention. That is, the present invention provides ``A) a --SO ₃ M group (M in the group is hydrogen, sodium, or (represents potassium atom)
(B) oxides, hydroxides, or organic or inorganic salts of metals selected from Groups 2 and 3 of the Periodic Table for 100 parts by weight of polyester, polyamide, polyurethane, or polyamide polyurea resin having 0.5 to 20 parts by weight of a novel hot melt adhesive composition. The adhesive composition of the present invention maintains excellent initial adhesion to textile materials even after washing with water and dry cleaning. Substantially at least 1 in the molecule of the present invention
A polyester, polyamide, polyurethane or polyamide polyurea resin having an SO ₃ M group is a polyester, polyamide, polyurethane or polyamide polyurea resin that is bonded to an aromatic nucleus.
Various polycondensation resins obtained using monomers such as dicarboxylic acids, diols, or condensable derivatives thereof having SO ₃ M groups are shown. Examples of such monomers include sulfoisophthalic acid, sulfoterephthalic acid, sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, or compounds in which the carboxyl group of these compounds is esterified with a lower alcohol. , or their sodium salts, potassium salts, etc.

【formula】

Examples include [Formula]. Most preferably used in the present invention are 5-sulfonodium isophthalate and 5-sulfonodium dimethyl isophthalate. In the present invention, substantially at least one
The method for producing polyester, polyamide, polyurethane or polyamide polyurea resin having -SO ₃ M groups bonded to aromatic nuclei is not particularly limited. For example, as a polyester resin, a compound having at least two carboxylic acid groups in the molecule or a lower alkyl ester thereof in a carboxylic acid, diol, or a condensable derivative thereof having an -SO ₃ M group bonded to the aromatic nucleus is used. 4,000 to 30,000, which is obtained by adding a compound having at least two hydroxyl groups in the molecule and condensation polymerizing it by a known method by dehydration, dealcoholization, or deglycol reaction.
Polyester resins having a number average molecular weight of Examples of polyamide resins include dicarboxylic acids or lower alkyl ester compounds thereof having -SO ₃ M groups bonded to aromatic nuclei, and organic amino compounds having at least two primary and/or secondary amino groups in the molecule. Examples include polyamide resins made by adding and condensation polymerizing. Examples of polyurethane resins having -SO ₃ M groups bonded to aromatic nuclei suitable for the present invention include -SO ₃ M groups bonded to aromatic nuclei.
A compound having at least two carboxylic acid groups in the molecule or a lower alkyl ester thereof and a compound having at least two hydroxyls in the molecule to a dicarboxylic acid, a diol, or a condensable derivative thereof having -OH/ An organic diisocyanate compound is added to a polyester polyol with a molecular weight of 500 to 3,000, which has an SO ₃ M group in the molecule whose COOR (R is H or an alkyl group) ratio is condensed with an excess of hydroxyl groups, and whose terminal group is a hydroxyl group. Examples include polyurethane resins that have been made into polymers by adding Further examples of polyamide polyurea resins include dicarboxylic acids or lower alkyl esters thereof having -SO ₃ M groups bonded to aromatic nuclei, and organic amino acids having at least two primary and/or secondary amino groups in the molecule. Compounds - NHR / -
-SO ₃ M group is present in the molecule obtained by condensation polymerization with COOR (R is H or alkyl group) ratio in excess of amino groups,
Molecular weight 500-3000 with terminal group being hydroxyl group
Examples include polyamide polyurea resins made by adding organic diisocyanate compounds to polyamide polyamines to polymerize them. In the present invention, compounds having at least two carboxylic acid groups in the molecule or lower alkyl of these carboxylic acids that can be used in combination with dicarboxylic acids, diols, or condensable derivatives thereof having an -SO ₃ M group bonded to an aromatic nucleus. Examples of esters include oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 -cyclohexanedicarboxylic acid,
Phthalic acid, terephthalic acid, isophthalic acid,
These include carboxyl compounds such as 2,5-naphthalene dicarboxylic acid and ester compounds of lower alcohols thereof, and particularly preferably used are terephthalic acid, isophthalic acid, and their dimethyl esters. Furthermore, compounds having at least two hydroxyl groups that can be used in the present invention include:
For example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, butanediols, especially 1,4-butanediol, pentanediol, especially 1,5-pentanediol, hexanediol, especially 1,6 -Hexanediol, others 1,10-decanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, polyoxyethylene glycol with a molecular weight of 200 to 2000, bis-(4-hydroxybutyl) ether, 2-methylene-1,3
-Propanediol, 2,4-dimethyl-2-ethylhexane-diol-1,3,2-ethyl-
2-butyl-1,3-propanediol, 2,2
-dimethyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,3-dihydroxycyclohexane, 1,4 -dihydroxycyclohexane, 1,
4-bis(hydroxymethyl)cyclohexane,
1,3-bis(hydroxymethyl)cyclohexane, 1,2-bis(hydroxymethyl)cyclohexane, 1,4-bis(hydroxymethylbenzene), 1,3-bis(hydroxymethyl)benzene, 2,6-bis (Hydroxymethyl)naphthalene and also diphenyls converted to araliphatic pishydroxy compounds by bilateral reaction with e.g. ethylene oxide, e.g. etc. can be mentioned. In addition, in the present invention, examples of organic amino compounds having at least two primary and/or secondary amino groups in the molecule used in the synthesis of polyamide resins and polyamide polyurea resins include ethylenediamine, hexamethylenediamine,
Primary diamines such as 1,4-cyclohexyldiamine-propylene diamine, 1,3-diaminopropane, hydrazine, isophorone diamine, N
Examples include amines such as -methylhydrazine, N-hydroxyethylhydrazine, piperazine, and aminoethylpiperazine, and polyamines such as diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. Further, as the compound having at least two isocyanate groups used in the production of polyurethane resins and polyamide polyurea resins, aromatic, aliphatic, and alicyclic compounds can be used. For example, hexamethylene-1,6- Diisocyanate, butane-1,4-
Diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethyl-methane diisocyanate, Diisocyanate compounds such as di- and tetraalkylene diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and tolylene diisocyanate are mentioned. Furthermore, compounds having two or more functional groups capable of reacting with these isocyanate compounds and isocyanate groups, such as relatively low molecular weight compounds having both terminal groups having a hydroxyl group, a carboxyl group, or a primary or secondary amino group, may be used. Also included are prepolymers having active isocyanate groups at both end groups, which are obtained by reacting a polyether, polyester, polyesteramide, or polyamide compound with an isocyanate compound in excess of the stoichiometric amount. The number average molecular weight of the resin obtained in the present invention is
Must be in the range 4000-30000. If the number average molecular weight of the obtained resin is lower than 4000, the adhesive strength of the obtained resin will be low and it will be difficult to use it as a hot melt adhesive for fiber materials, which is not preferable. Furthermore, if the number average molecular weight of the obtained resin is higher than 30,000, the viscosity of the obtained resin increases to such an extent that it is difficult to handle, which is not preferable. The preferred number average molecular weight of the resin obtained in the present invention is in the range of 5,000 to 20,000. Further, the resin obtained in the present invention has -SO ₃ M substantially bound to at least one aromatic nucleus in the molecule.
Although it is characterized by containing groups, it is common for the number of --SO ₃ M groups to be substantially 1.5 to 4 in one molecule from the viewpoint of processing effects and economical efficiency of the resin. In the present invention, particularly preferred resins as hot melt adhesives for fibers have a softening temperature of 90°C to 140°C,
It is a resin having physical properties of a melt index of 1 to 50 g/10 minutes and a temperature of 150°C, among which polyester resin is the most common and preferred. The thus obtained polyester, polyamide, polyurethane or polyamide polyurea resin having SO ₃ M groups
0.5 to 20 parts by weight, preferably 1 to 15 parts by weight of metal oxides, hydroxides, or organic or inorganic salts of metals selected from Groups 2 and 3 of the periodic table per 100 parts by weight. Added. Representative metals of Groups 2 and 3 of the periodic table in the present invention include magnesium, calcium, zinc, aluminum, etc., and examples of preferred metal compounds in the present invention include magnesium oxide, calcium oxide, zinc oxide, Oxides such as aluminum oxide, hydroxides such as magnesium hydroxide and calcium hydroxide, carbonates such as magnesium carbonate, calcium carbonate, and zinc carbonate, and other hydrochlorides, nitrates, sulfates, and phosphorus of these metals. Various inorganic salts such as acid salts, magnesium acetate, magnesium octylate, magnesium stearate,
Contains various organic salts such as magnesium oxalate. Metal compounds particularly preferably used in the present invention are carbonates such as magnesium carbonate and calcium carbonate, and phosphates such as magnesium phosphate and calcium phosphate. Substantially at least 1 in the molecule of the present invention
The method of adding the metal compound to the polyester, polyamide, polyurethane, or polyamide polyurea resin having -SO ₃ M groups bonded to aromatic nuclei is not particularly limited, and the metal compound may be added during the synthesis of these resins or immediately after the synthesis is completed. Alternatively, it may be mixed with the above-mentioned resins immediately before or during the hot-melt bonding process using these resins. Preferably, the above-mentioned polyester, polyamide, polyurethane or polyamide polyurea resin having an -SO ₃ M group bonded to the aromatic nucleus is converted into a form such as powder, pellets, dispersion, or emulsion, and then the above-mentioned metal compound powder is obtained. A uniform mixture of water, aqueous solution, or aqueous dispersion is used for adhesion. In the present invention, there are no particular limitations on the adhesion method; generally, a powder or dispersion adhesive is applied to a woven fabric, the same or different types of woven fabric are layered, and then ironing, hot pressing, hot pressing, etc. Adhesion is performed by heating and softening using a roller or other means. In this case, when the powder is in the form of powder, coating is performed using a dotting machine, scattering machine, etc., and the dispersion is applied by spraying, knife coating, etc. Woven fabrics include synthetic fibers such as polyester, polyamide, and acrylic, natural fibers such as wool and cotton, inorganic fibers such as glass fiber and asbestos, and blends thereof.It is also used for adhesion of badges, marks, etc. be able to. According to the adhesive of the present invention, it is possible to obtain an extremely excellent adhesive fabric that can withstand both water washing and dry cleaning. In addition to the above adhesives for fiber materials, the adhesive obtained in the present invention can also be used as a hot melt adhesive for plastics, metals, glass, leather, rubber, wood, paper, etc. It is also possible to add appropriate amounts of an antioxidant, an anti-slip agent, an anti-blocking agent and a tackifying agent to the adhesive of the present invention, if necessary. Next, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. Note that "parts" and "%" shown below are based on weight unless otherwise specified. Synthesis Example (Synthesis of E-1 to 4, C-1 to 2) 664 parts of isophthalic acid, 83 parts of terephthalic acid, 372 parts of ethylene glycol, 148 parts of 5-sulfonodium dimethyl isophthalate, and 0.135 parts of sodium acetate were added to a reaction pot. heated from 140°C to 200°C in a nitrogen stream for about 4 hours, then heated to 240°C.
℃ and a polycondensation reaction was carried out under reduced pressure of 10 mmHg for about 6 hours to synthesize a polyester resin (E-1) having -SO ₃ Na group bonded to an aromatic nucleus in the molecule. The acid value of the obtained polyester resin (E-1) was 4.4, and the molecular weight was 6,600. In addition, the softening temperature of the obtained polyester resin (E-1) is
It had a melt index of 12 g/10 minutes at 105°C and 150°C. Similarly, copolyester resins (E-2 to E-4) whose polymer compositions are shown in Table 1 were synthesized. Further, as comparative examples, copolymerized polyester resins shown by C-1 and C-2 were synthesized. Examples 1 to 6, Comparative Examples 1 to 3 Polyester resin E-1 obtained in Synthesis Example
4. C-1 to 2 are crushed by frozen crushing method,
Micronization was performed to have a particle size of 200 mesh or less. After adding oxides, hydroxides, or organic or inorganic salts of metals selected from Groups 2 and 3 of the periodic table to this powdered polyester resin as shown in Table 2, a Henschel mixer is used. The mixture was dispersed uniformly using a . The obtained powder composition is coated onto a polyester spun core by a powder coating method in an amount of 5 to 15 g/
Resin was deposited in an amount of ^m2 . The obtained adhesive interlining was press-bonded to a polyester/cotton = 65/35 blended broadcloth under the conditions of a press temperature of 150°C, a press pressure of 0.30 kg/cm ² , and a press steaming/second press of 9 seconds. Initial adhesive strength for the bonded base fabric,
The adhesive strength after the dry cleaning test according to JIS-L-1089 and the adhesive strength after washing with water were measured using an autograph at a peeling speed of 30 cm/min. The test results are shown in Table 2. It was found that processed fabrics bonded with ordinary polyester resin adhesives (C-1, C-2) had relatively good water resistance to washing, but could not withstand dry cleaning at all.

【table】

【table】

[Table] Example 7, Comparative Example 4 394 parts of isophthalic acid, 394.5 parts of terephthalic acid,
708 parts of 1,6-hexamethylene glycol, 5-
74 parts of sulfonodium dimethyl isophthalate,
and 0.135 parts of sodium acetate into the reaction vessel,
The temperature was raised from 140°C to 220°C in a nitrogen stream over 8 hours, and then maintained at 220°C to remove the OH in the resin.
Continuing the polycondensation reaction while measuring the value and acid value,
A polyester resin with an OH value of 55.9 and an acid value of 0.2 and having -SO ₃ Na groups in its molecules was created. 377.7 parts of the obtained polyester, 34.8 parts of ethylene glycol, and toluene diisocyanate (2,4-,2,6
- isomer ratio = 80/20) were mixed and heated to obtain a polyurethane mass with a molecular weight of 15,000.
This polyurethane lump was pulverized by a freeze pulverization method and pulverized to have a particle size of 200 mesh or less. This powdered polyurethane resin 100%
5 parts of magnesium carbonate powder were added to the mixture, and the mixture was uniformly dispersed using a Henschel mixer. The obtained powdered resin composition was spread on the surface of a nylon nonwoven fabric in an amount of 8 g/m ² and fixed by heat to prepare a fused interlining. This fused interlining was fused to a tropical fabric (55% wool, 45% polyester blend) by dry heat pressing at 140°C for 10 seconds. The initial adhesive strength of this adhesive fabric is 2.3Kg/inch, and the adhesive strength of the fusion interlining after dry cleaning test and water washing is 1.92Kg/inch and 1.98Kg/inch, respectively, which is an extremely excellent adhesive strength. was holding it. For comparison, a fused interlining was made under the same conditions as above without adding magnesium carbonate powder, and an adhesion test was conducted.The adhesion test was 1.45 kg/inch after washing with water, and 1.37 kg/inch after dry cleaning.
A considerable decrease of Kg/inch was observed. The results are shown in Table 3. Example 8, Comparative Example 5 740 parts of 1,3-diaminopropane was charged into a reaction vessel, and stirring was started. In a nitrogen stream, 332 parts of isophthalic acid, 365 parts of adipic acid, and 148 parts of 5-sulfonodium dimethyl isophthalate were slowly added at a temperature of 60° C. or lower while being careful not to generate heat.
After the addition was completed, the temperature was started to rise, and it took about 1 hour to slowly raise the temperature to 160°C. Next, a dehydration condensation reaction was carried out at 160° C. for about 3 hours to synthesize a polyamide derivative. The amine value of the obtained polyamide derivative is 400
It was hot. This polyamide derivative was cooled to 120°C, and 3000 parts of water previously heated to 80°C was slowly added to obtain a pale yellow and transparent aqueous solution, and the pH of the aqueous solution was 10.7. Next, 1,6-hexamethylene diisocyanate was added to the resulting aqueous solution of the polyamide derivative while stirring at high speed.
When 756 parts were slowly added, a uniform emulsion of polyamide polyurea resin which gradually became cloudy was obtained. The resulting polyamide polyurea resin emulsion had a nonvolatile content of 41.6%, a pH of 6.8, and a molecular weight of about 16,000 when measured. The resulting polyamide polyurea resin aqueous solution was spray applied to a polyester pen interlining to a resin solid content of 11.2 g/m ² , and then 50% of aluminum acetate was applied on top.
% aqueous solution in an amount of 10 g/m ² (wet) and dried at 60° C. for 3 hours to prepare an adhesive interlining. The obtained polyester adhesive interlining with the polyamide polyurea resin adhered to it was pressed using an Aparol press machine at a pressure of 1 Kg/cm ² and a temperature of 170°C using a polyester dioset fabric as the adhered fabric.
It was crimped for 10 seconds. The peel strength of the obtained adhesive fabric was 1.76 Kg/inch initially, and the peel strength after washing with water and dry cleaning was 1.67 Kg/inch and 1.58, respectively.
It had excellent durability of Kg/inch. The initial adhesive strength without spraying the aluminum acetate aqueous solution was good at 1.71 Kg/inch, but the peel strength after washing with water and dry cleaning was 1.05 Kg/inch and 0.63 Kg/inch, respectively. It was observed that the number of people in Japan was decreasing. The results are shown in Table 3.

【table】

Claims (1)

[Claims] 1 (A) -SO ₃ M group having a number average molecular weight of 4,000 to 30,000 and substantially bonded to at least one aromatic nucleus in the molecule (M in the group is hydrogen, sodium or potassium atom) per 100 parts by weight of polyester, polyamide, polyurethane, or polyamide polyurea resin, (B) 2nd and 3rd part of the periodic table
1. A novel hot melt adhesive composition comprising 0.5 to 20 parts by weight of an oxide, hydroxide, or an organic or inorganic salt thereof of a metal selected from the group consisting of: 2. The novel invention according to claim 1, wherein the polyester, polyamide, polyurethane, or polyamide polyurea resin is obtained by copolymerizing sulfonium isophthalic acid or a lower alkyl ester of its carboxylic acid. hot melt adhesive composition.